Blue and green-blue-variable light-emitting diodes based on the blend of polymer and organic molecules

Organic light-emitting diodes based on the blend of poly (p-phenylene vinylene) (PPV) derivative and naphthyl-imine–gallium complex have been fabricated by spin-coating method. Blue emission and blue-green variation depending on the ratio of the PPV derivative to the complex and the applied voltage have been observed. The investigation on PL (photoluminescence) and EL (electroluminescence) properties demonstrates that the improvement of the luminescent efficiency is related to the injection balance between holes and electrons, and the color variation is attributed to the variation of the recombination zone. Received: 7 July 1999 / Accepted: 11 October 1999 / Published online: 8 March 2000     

Ultrafast spin dynamics in magnetic semiconductor quantum wells studied by magnetization modulation spectroscopy

1-x Mn_xTe quantum well structures at room temperature using time-resolved magnetization modulation spectroscopy. Access to the different electron and hole spin dynamics is obtained by carefully measuring the spectroscopic changes of the magneto-optical response during the first hundreds of femtoseconds after excitation. Experimental results are discussed in the framework of a simple model for a two-dimensional band structure. The spectroscopy is shown to be intimately related to the spectral band width of the applied ultrashort laser pulses. The general potential of the method for fundamental studies on other materials and systems is addressed. Received: 20 September 1998     

Rapid formaldehyde monitoring in ambient air by means of mid-infrared cavity leak-out spectroscopy

We report the spectroscopic detection of formaldehyde in ambient air using cavity leak-out spectroscopy, a cw variant of cavity ring-down spectroscopy. This technique proved to be suitable for a real-time quantitative analysis of polluted air without any preprocessing of the air sample. Using a tunable CO-overtone sideband laser for the λ=3 μm spectral region and a ring-down cell with R=99.95% mirrors, we achieved a detection limit of 2 parts per billion formaldehyde in ambient air, corresponding to a minimum detectable absorption coefficient of 7×10^-9/cm (sampling time: 2 s). Calibration problems arising from the polarity of the molecule and due to HITRAN database uncertainties are discussed. Received: 28 March 2002 / Revised version: 7 June 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +49-211/811-3121, E-mail: muertz@uni-duesseldorf.de     

Real-time monitoring of ethane in human breath using mid-infrared cavity leak-out spectroscopy

We report on spectroscopic real-time analysis of ethane traces in exhaled human breath. Ethane is considered the most important volatile marker of free-radical induced lipid peroxidation and cell damage in the human body. Our measurements were carried out by means of mid-infrared cavity leak-out spectroscopy in the 3 μm region, a cw variant of cavity ring-down spectroscopy. The spectrometer is based on a CO overtone laser with tunable microwave sidebands. The resulting system proved to be an unique tool with high sensitivity and selectivity for rapid and precise breath testing. With a 5 s integration time, we achieved a detection limit on the order of 100 parts per trillion ethane in human breath. Thus, sample preconcentration is unnecessary. Time-resolved monitoring of the decaying ethane fraction in breath after smoking a cigarette is demonstrated. Received: 13 March 2001 / Published online: 9 May 2001     

Isotopic ratio measurement of methane in ambient air using mid-infrared cavity leak-out spectroscopy

We report on infrared laser spectroscopic measurements of the isotopic composition of methane (¹²CH₄, ¹³CH₄) in natural air samples with a cavity ring-down technique. A CO overtone sideband laser is utilized to excite a high-finesse cavity which provides an effective optical absorption path length of 3.6 km. We achieved a detection limit of 105 ppt methane in ambient air using an integration time of 20 s. This corresponds to a minimum detectable absorption of 1.9×10^-9 /cm. Rapid determination of the ¹³C/¹²Cisotopic ratio of methane in ambient air without sample preconcentration or gas processing is realized. The present system requires only few minutes for an isotopic ratio measurement with a precision of 11%o . Received: 14 July 2000 / Revised version: 25 October 2000 / Published online: 6 December 2000     

Pulsed cavity ring-down spectroscopy of NO and NO2 in the exhaust of a diesel engine

The application of pulsed cavity ring-down spectroscopy has been demonstrated for the in situ quantitative determination of NO and NO₂ in the exhaust of a diesel engine. NO absorption has been monitored at the transition from the Χ²Π ground state to the A²Σ⁺ state at 226 nm. For NO₂, absorption bands in the spectral region from 438 nm to 450 nm were used. At the selected engine conditions, concentrations of 212±22 ppm and 29±4 ppm have been measured for NO and NO₂, respectively, in good agreement with separate chemical exhaust gas analysis. The method is sensitive enough to meet the European Euro V standard directive on NO_x emissions. This communication discusses the relatively simple setup needed for this type of measurement, the problems encountered, as well as the prospects for single-stroke, simultaneous measurements of both NO and NO₂ at the sub-ppm level. Received: 30 November 2001 / Revised version: 18 February 2002 / Published online: 14 March 2002     

Quantification of stable minor species in confined flames by cavity ring-down spectroscopy: application to NO

Cavity ring-down spectroscopy (CRDS) is used to measure the NO mole fraction formed in the burnt gases of low-pressure premixed flames. It is shown that the line-of-sight absorption is greatly increased by the contribution of the NO molecules surrounding the burner. This contribution has been quantified by developing a mathematical procedure taking into account the spatial and spectral features of the CRDS measurement. Calculations have been undertaken in the general case of a stable species not consumed in the flame. The most sensitive parameter is the temperature both in the flame and outside the flame. Simulations allow the selection of the best spectroscopic transitions for a given flame (i.e. a given temperature profile), ensuring the weakest influence of the inaccuracy affecting the temperature determination. High quantum states belonging to the A–X (0–1) band of NO have been found to be the most valuable and have led to a NO mole fraction determination with an accuracy of ±13%. NO absorption in the flame was completely masked using the A–X (0–0) band. Finally, the prompt-NO mole fraction formed in a methane/air flame stabilized at 33 Torr is obtained by combining CRDS and laser induced fluorescence techniques. Received: 12 October / Revised version: 1 February 2002 / Published online: 14 March 2002     

Optimization of the mode matching in pulsed cavity ringdown spectroscopy by monitoring non-degenerate transverse mode beating

A simple and reliable method is presented for optimizing the mode matching of a laser beam to the high-finesse cavity used in pulsed cavity ringdown spectroscopy (CRDS). The method is based on minimizing the excitation of higher-order transverse cavity modes through monitoring the non-degenerate transverse mode beating which becomes visible with induced cavity asymmetry caused by slight misalignment. No additional instrument is required other than a pinhole aperture, thus this method can be applied for CRDS experiments in the whole wavelength range. Measurements of the CRDS absorption spectrum of acetylene (C₂H₂) near 571 nm demonstrate that the mode-matching optimization improves the sensitivity of pulsed CRDS. Received: 22 October 2001 / Revised version: 16 January 2002 / Published online: 14 March 2002     

Laser intracavity absorption spectroscopy

Emission spectra of multimode lasers are very sensitive to spectrally selective extinction in their cavity. This phenomenon allows the quantitative measurement of absorption. The sensitivity of measurements of intracavity absorption grows with the laser pulse duration. The ultimate sensitivity obtained with a cw laser is set by various perturbations of the light coherence, such as quantum noise, Rayleigh scattering, four-wave mixing by population pulsations, and stimulated Brillouin scattering. It depends on the particular laser type used, and on its operative parameters, for example pump power, cavity loss, cavity length, and length of the gain medium. Nonlinear mode-coupling dominates the dynamics of lasers that feature a thin gain medium, such as dye lasers, whereas Rayleigh scattering is more important in lasers with a long gain medium, such as doped fibre lasers, or the Ti:sapphire laser. The highest sensitivity so far has been obtained with a cw dye laser. It corresponds to 70000 km effective length of the absorption path. The ultimate spectral resolution is determined by the spectral width of mode emission, which is 0.7 Hz in this dye laser. High sensitivity and high temporal and spectral resolution allow various practical applications of laser intracavity spectroscopy, such as measurements and simulations of atmospheric absorption, molecular and atomic spectroscopy, process control, isotope separation, study of free radicals and chemical reactions, combustion diagnostics, spectroscopy of excited states and nonlinear processes, measurements of gain and of spectrally narrow light emission. Intracavity absorption in single-mode lasers shows enhanced sensitivity as well, although not as high as in multimode lasers. Received: 10 May 1999 / Published online: 29 July 1999     

High-resolution spectroscopy of velocity-selected atoms in a thin cell

We propose a novel technique of sub-Doppler spectroscopy using a thin vapor cell. Optical pumping in a thin cell transfers atoms with small velocity components to a specific quantum state. The resultant velocity distribution appears as a sub-Doppler structure in the absorption spectrum of a probe light. A single laser beam from a laser diode is split into two paths: one beam optically pumps Cs atoms on the D₂ line, and the other probes the absorption on the same line from a perpendicular direction. Observed hyperfine-resolved spectra and their parameter dependence are analyzed on the basis of rate equations. Received: 16 January 2002 / Revised version: 11 February 2002 / Published online: 24 April 2002     

Thermal grating and broadband degenerate four-wave mixing spectroscopy of OH in high-pressure flames

2 ∑–X²Π(0,0) band of OH has been studied in premixed methane/air flames using a cw Ar⁺ laser probe. Measurements of flame temperature and pressure were derived from fits of theoretical simulations to the observed time variation of signals over a pressure range of 10 to 40 bar and for different stoichiometry that were in agreement with independent measurements using N₂ CARS and predictions of a one-dimensional flame calculation. Broadband DFWM spectra in the same band of OH were observed up to a pressure of 9 bar, above which signals were obtained only from scattering from thermal gratings. Received: 10 November 1997/Revised version: 28 May 1998     

Cavity ring-down spectroscopy of photochemically produced NaH for the determination of relative dipole transition moments

-30 Cm of isolated lines in the A¹Σ⁺←X¹Σ⁺ NaH transition band were measured. Received: 18 November 1996/Revised version: 10 May 1997     

Europium ion as a probe for binding sites to carrageenans

Carrageenans, sulfated polysaccharides extracted from red algae, present a coil-helix transition and helix aggregation dependence on the type and concentration of counterions. In this study, we focus attention on a mixed valence counterion system: Eu³⁺/Na⁺ or K⁺ with different gel-forming carrageenans: kappa, iota, and kappa-2. Results of stationary and time-dependent luminescence showed to be a suitable tool to probe ion binding to both the negatively charged sulfate group and the hydroxyl groups present in the biopolymer. For lower europium ion concentrations, a single longer decay emission lifetime was detected, which was attributed to the binding of europium ion to the carrageenan sulfate groups. An additional decay ascribed to europium binding to hydroxyl groups was observed above a threshold concentration, and this decay was dependent on the carrageenan charge density. Symmetry of the europium ion microenvironment was estimated by the ratio between the intensities of its emission bands, which has been shown to depend on the concentration of europium ions and on the specificity of the monovalent counterion bound to the carrageenan.     

Laser frequency stabilization using selective reflection spectroscopy

1 line. We discuss the performance of this novel frequency stabilization scheme and analyze its dependence on various system parameters. The technique is compared to the commonly used saturation spectroscopic techniques. Received: 8 September 1997/Revised version: 16 October 1997     

Artifacts in femtosecond transient absorption spectroscopy

The paper discusses three different artifacts related to two-photon absorption (TPA), stimulated Raman amplification (SRA) and cross-phase modulation (XPM), all intrinsic to transient absorption measurements with femtosecond time resolution. Certain properties of these signals are analysed and shown to superimpose onto measured transient absorption spectra. Ways of reducing the influence of the artifacts discussed are suggested. A simple correcting procedure based on the linear intensity dependence of the artifacts discussed is proposed. Received: 29 May 2001 / Final version: 15 October 2001 / Published online: 29 November 2001     

Coherent phonon and electron spectroscopy on surfaces using time-resolved second-harmonic generation

pump (ω)E_probe ^*(ω)|E_probe(ω)|². This is much easier to detect than transient grating, photon echo, or four-wave mixing schemes that use higher-order nonlinearities. We have applied this technique to measure the energy gap and dephasing time of the dangling bond interband transition on the GaAs(110)-relaxed (1×1) surface. Surface-carrier/surface-phonon interaction plays an important and perhaps dominant role in surface carrier dephasing consistent with the larger electron-phonon coupling on the surface compared to the bulk. Received: 13 October 1998     

Two-color pump-probe ionization spectroscopy of gaseous water enhanced by preliminary impulsive Raman excitation

We use sub-10-fs pulses at 400 nm and 15-fs pulses at 800 nm to ionize water molecules and their isotopomers HDO and D₂O in a pump–probe scheme. Pulses are generated via spectral broadening of 25-fs pulses of a 1-kHz Ti:sapphire amplifier system by self-phase modulation in a noble-gas-filled hollow waveguide and subsequent compression using chirped mirrors. At this time scale vibronic excitation of the first bending mode of water in the electronic ground state by impulsive Raman scattering is possible (e.g. the fundamental bending mode of H₂O: t_vib=20 fs). The effect of this pre-excitation on the ionization rate is shown. Received: 14 May 2001 / Revised version: 24 August 2001 / Published online: 19 September 2001     

Hydroxyl tagging velocimetry (HTV) in experimental air flows

 The new nonintrusive instantaneous molecular flow tagging method, hydroxyl tagging velocimetry (HTV), previously demonstrated only for high-temperature reacting flows, is now demonstrated in low-temperature (300 K) ambient air flowfields. Single-photon photodissociation of ground-state H₂O by a ∼193-nm ArF excimer laser ‘writes’ very long grid lines (>50 mm) of superequilibrium OH and H photoproducts in a room air flowfield due to the presence of ambient H₂O vapor. After displacement, the positions of the OH tag lines are revealed through fluorescence caused by A²Σ⁺ (ν^′=0)?X²Π_i (ν^′′=0) OH excitation using a pulsed frequency-doubled dye laser with an operating output wavelength of ∼308 nm. The dye ‘read’ laser accesses the strong Q₁(1) line, compensating for the relatively weak 193-nm absorption of room-temperature H₂O. The weak absorption of ground vibrational state H₂O has previously precluded the use of HTV at low temperatures, since previous HTV systems relied on a KrF excimer ‘read’ laser that could only access a weak (3?0) OH transition. The instantaneous velocity field is determined by time-of-flight analysis. HTV tag lifetime comparisons between experimental results and theoretical predictions are discussed. Multiple-line tag grids are shown displaced due to an experimental air flowfield, thus providing 2-D multipoint velocity information. Due to the instantaneous nature of the HTV tag formation, HTV is particularly suitable for, but not limited to, a variety of fast flowfield applications including nonreacting base flows for high-speed projectiles and low-temperature hypersonic external or internal flows. Received: 3 July 2001 / Revised version: 6 November 2001 / Published online: 17 January 2002     

Isotope effect in the linewidth distribution of single-molecule spectra in doped toluene at 2 K

The low-temperature dynamics of two different varieties of a low-molecular glass—protonated toluene (C₆H₅CH₃) and perdeuterated toluene (C₆D₅CD₃)—weakly doped with tetra-tert-butylterrylene (TBT) molecules was investigated with single-molecule spectroscopy. In both glassy matrices the distributions of the spectral widths were measured for a large number of single TBT molecules at T=2 K. The marked shift of the distribution upon deuteration of matrix was observed and attributed to an isotope effect which is qualitatively analyzed. It was found that at this temperature the tunneling dynamics of the matrix dominates the broadening behavior and hydrogen/deuterium atoms are involved in the tunneling motions.     

High-precision pulsed photoacoustic spectroscopy in NO2-N2

A method for high-precision pulsed photoacoustic spectroscopy applied to a simple system for detection of NO₂ traces in nitrogen is presented. The acoustic signal from a closed cell containing NO₂/N₂ samples irradiated by a pulsed visible laser is analyzed in the frequency domain. A signal-processing method to obtain a high-resolution Fourier spectrum of the signal was developed. An accurate fitting of the resonance peaks with Lorentzian profiles gives high-precision determination of the amplitude and width of the resonance peaks. The resonance maximum is proportional to the absorbed energy; therefore, the choice of the laser wavelength, linewidth and frequency stability are critical for a precise calibration due to the fine structure of the NO₂ optical spectrum. The method also allows high-accuracy measurement of the Q of the acoustic cavity. The dependence of Q on the buffer gas pressure is characteristic of an acoustic cavity where energy losses near the walls predominate. Consequently, an important enhancement of sensitivity takes place at high N₂ pressure. Received: 1 June 2001 / Revised version: 27 July 2001 / Published online: 7 November 2001