Theoretical and experimental study of intracavity laser absorption spectroscopy

In this thesis, a dual mode tunable gas sensor based on intracavity laser absorption spectroscopy (ICLAS) principle is investigated, both, numerically and experimentally. In order to minimize the cost and size of the gas sensor, relative intensity noise (RIN) is implemented as a detection parameter. Investigation is performed to determine the effect of injection current, operating temperature, mode spacing, and cavity length on RIN. It has been found that it is best to operate the gas sensor at smaller mode spacing and near the threshold current or at larger mode spacing and far above the threshold current for the use of RIN as the readout parameter.

Atomistic-continuum modeling of ultrafast laser-induced melting of silicon targets

In this work, we present an atomistic-continuum model for simulations of ultrafast laser-induced melting processes in semiconductors on the example of silicon. The kinetics of transient non-equilibrium phase transition mechanisms is addressed with MD method on the atomic level, whereas the laser light absorption, strong generated electron-phonon nonequilibrium, fast heat conduction, and photo-excited free carrier diffusion are accounted for with a continuum TTM-like model (called nTTM). First, we independently consider the applications of nTTM and MD for the description of silicon, and then construct the combined MD-nTTM model. Its development and thorough testing is followed by a comprehensive computational study of fast nonequilibrium processes induced in silicon by an ultrashort laser irradiation. The new model allowed to investigate the effect of laser-induced pressure and temperature of the lattice on the melting kinetics. Two competing melting mechanisms, heterogeneous and homogeneous, were identified in our big-scale simulations. Apart from the classical heterogeneous melting mechanism, the nucleation of the liquid phase homogeneously inside the material significantly contributes to the melting process. The simulations showed, that due to the open diamond structure of the crystal, the laser-generated internal compressive stresses reduce the crystal stability against the homogeneous melting. Consequently, the latter can take a massive character within several picoseconds upon the laser heating. Due to the large negative volume of melting of silicon, the material contracts upon the phase transition, relaxes the compressive stresses, and the subsequent melting proceeds heterogeneously until the excess of thermal energy is consumed. A series of simulations for a range of absorbed fluences allowed us to find the threshold fluence value at which homogeneous liquid nucleation starts contributing to the classical heterogeneous propagation of the solid-liquid interface. A series of simulations for a range of the material thicknesses showed that the sample width we chosen in our simulations (800 nm) corresponds to a thick sample. Additionally, in order to support the main conclusions, the results were verified for a different interatomic potential. Possible improvements of the model to account for nonthermal effects are discussed and certain restrictions on the suitable interatomic potentials are found. As a first step towards the inclusion of these effects into MD-nTTM, we performed nanometer-scale MD simulations with a new interatomic potential, designed to reproduce ab initio calculations at the laser-induced electronic temperature of 18946 K. The simulations demonstrated that, similarly to thermal melting, nonthermal phase transition occurs through nucleation. A series of simulations showed that higher (lower) initial pressure reinforces (hinders) the creation and the growth of nonthermal liquid nuclei. For the example of Si, the laser melting kinetics of semiconductors was found to be noticeably different from that of metals with a face-centered cubic crystal structure. The results of this study, therefore, have important implications for interpretation of experimental data on the kinetics of melting process of semiconductors.

Kinetics and dynamics measured using IntraCavity Laser Absorption Spectroscopy

IntraCavity Laser Absorption Spectroscopy (ICLAS) is a high-resolution, high sensitivity spectroscopic method capable of measuring line positions, linewidths, lineshapes, and absolute line intensities with a sensitivity that far exceeds that of a traditional multiple pass absorption cell or Fourier Transform spectrometer. From the fundamental knowledge obtained through these measurements, information about the underlying spectroscopy, dynamics, and kinetics of the species interrogated can be derived. The construction of an ICLA Spectrometer will be detailed, and the measurements utilizing ICLAS will be discussed, as well as the theory of operation and modifications of the experimental apparatus. Results include: i) Line intensities and collision-broadening coefficients of the A band of oxygen and previously unobserved, high J, rotational transitions of the A band, hot-band transitions, and transitions of isotopically substituted species. ii) High-resolution (0.013 cm-1) spectra of the second overtone of the OH stretch of trans-nitrous acid recorded between 10,230 and 10,350 cm-1. The spectra were analyzed to yield a complete set of rotational parameters and an absolute band intensity, and two groups of anharmonic perturbations were observed and analyzed. These findings are discussed in the context of the contribution of overtone-mediated processes to OH radical production in the lower atmosphere.

Mechanisms of femtosecond laser-induced refractive index modification of poly(methyl methacrylate)

The mechanisms of refractive index change in poly(methyl methacrylate) by frequency doubled femtosecond laser pulses are investigated. It is demonstrated that positive refractive index modificaton can be caused by a combination of depolymerization and crosslinking.

New-on-line method for water isotope analysis of speleothem fluid inclusions using laser absorption spectroscopy (WS-CRDS)

A new online method to analyse water isotopes of speleothem fluid inclusions using a wavelength scanned cavity ring down spectroscopy (WS-CRDS) instrument is presented. This novel technique allows us simultaneously to measure hydrogen and oxygen isotopes for a released aliquot of water. To do so, we designed a new simple line that allows the online water extraction and isotope analysis of speleothem samples. The specificity of the method lies in the fact that fluid inclusions release is made on a standard water background, which mainly improves the δ D robustness. To saturate the line, a peristaltic pump continuously injects standard water into the line that is permanently heated to 140 °C and flushed with dry nitrogen gas. This permits instantaneous and complete vaporisation of the standard water, resulting in an artificial water background with well-known δ D and δ18O values. The speleothem sample is placed in a copper tube, attached to the line, and after system stabilisation it is crushed using a simple hydraulic device to liberate speleothem fluid inclusions water. The released water is carried by the nitrogen/standard water gas stream directly to a Picarro L1102-i for isotope determination. To test the accuracy and reproducibility of the line and to measure standard water during speleothem measurements, a syringe injection unit was added to the line. Peak evaluation is done similarly as in gas chromatography to obtain &delta D; and δ18O isotopic compositions of measured water aliquots. Precision is better than 1.5 ‰ for δ D and 0.4 ‰ for δ18O for water measurements for an extended range (−210 to 0 ‰ for δ D and −27 to 0 ‰ for δ18O) primarily dependent on the amount of water released from speleothem fluid inclusions and secondarily on the isotopic composition of the sample. The results show that WS-CRDS technology is suitable for speleothem fluid inclusion measurements and gives results that are comparable to the isotope ratio mass spectrometry (IRMS) technique.

Assignment and frequency measurement of rotational transitions of (CD3OH)-C-13 by intracavity laser Stark spectroscopy

We present the results of an intracavity Stark spectroscopy experiment on the fundamental state of (CD3OH)-C-13. We use an optically pumped hybrid waveguide FIR laser, CH2F2 as active molecule, and (CD3OH)-C-13 as absorbent molecule. No Brewster window is needed to separate the lasing gas from the absorbing deuterated methanol. An absorption line is assigned as E(l) symmetry (n, K, J): (1,4,18) --> (1,5,18) and its frequency is measured as 63.08631 cm(-1) with a precision of a few parts in 10(7); two more absorptions are reported and a tentative assignment for one of them.

Electron trapping of laser-induced carriers in Er-doped SnO2 thin films

In order to investigate optically excited electronic transport in Er-doped SnO2, thin films are excited with the fourth harmonic of an Nd:YAG laser (266nm) at low temperature, yielding conductivity decay when the illumination is removed. Inspection of these electrical characteristics aims knowledge for electroluminescent devices operation. Based on a proposed model where trapping defects present thermally activated cross section, the capture barrier is evaluated as 140, 108, 100 and 148 meV for doped SnO2, thin films with 0.0, 0.05, 0. 10 and 4.0 at% of Er, respectively. The undoped film has vacancy levels as dominating, whereas for doped films. there are two distinct trapping centers: Er3+ substitutional at Sn lattice sites and Er3+ located at grain boundary. (C) 2007 Elsevier Ltd. All rights reserved.

Enhancement of laser induced Au nanoparticle formation by femtosecond pulse shaping

We report the control of Au nanoparticle (NP) formation by using shaped 30 fs pulses, in a solution containing HAuCl4 and chitosan. By using a sinusoidal spectral phase, a periodic train of pulses is generated. When the period of the pulse train matches certain Raman resonances of chitosan, the reducing agent of the process, an enhancement of the Au NP formation is observed. Theoretical quantum chemical calculations indicate that the outer groups of the chitosan are mostly influenced by low Raman frequencies, which is in reasonably agreement with the experimental data and indicates an enhancement in the Au NP formation as the pulse train period increases (low frequency).

Grazing incidence pumped Zr x-ray laser for spectroscopy on Li-like ions

X-ray laser fluorescence spectroscopy of the 2s-2p transition in Li-like ions is promising to become a widely applicable tool to provide information on the nuclear charge radii of stable and radioactive isotopes. For performing such experiments at the Experimental Storage Ring ESR, and the future NESR within the FAIR Project, a grazing incidence pumped (GRIP) x-ray laser (XRL) was set up at GSI Darmstadt using PHELIX (Petawatt High Energy Laser for heavy Ions eXperiments). The experiments demonstrated that lasing using the GRIP geometry could be achieved with relatively low pump energy, a prerequisite for higher repetition rate. In the first chapter the need of a plasma XRL is motivated and a short history of the plasma XRL is presented. The distinctive characteristic of the GRIP method is the controlled deposition of the pump laser energy into the desired plasma density region. While up to now the analysis performed were mostly concerned with the plasma density at the turning point of the main pump pulse, in this thesis it is demonstrated that also the energy deposition is significantly modified for the GRIP method, being sensitive in different ways to a large number of parameters. In the second chapter, the theoretical description of the plasma evolution, active medium and XRL emission properties are reviewed. In addition an innovative analysis of the laser absorption in plasma which includes an inverse Bremsstrahlung (IB) correction factor is presented. The third chapter gives an overview of the experimental set-up and diagnostics, providing an analytical formula for the average and instantaneous traveling wave speed generated with a tilted, on-axis spherical mirror, the only focusing system used up to now in GRIP XRL. The fourth chapter describes the experimental optimization and results. The emphasis is on the effect of the incidence angle of the main pump pulse on the absorption in plasma and on output and gain in different lasing lines. This is compared to the theoretical results for two different incidence angles. Significant corrections for the temperature evolution during the main pump pulse due to the incidence angle are demonstrated in comparison to a simple analytical model which does not take into account the pumping geometry. A much better agreement is reached by the model developed in this thesis. An interesting result is also the appearance of a central dip in the spatially resolved keV emission which was observed in the XRL experiments for the first time and correlates well with previous near field imaging and plasma density profile measurements. In the conclusion also an outlook to the generation of shorter wavelength XRL’s is given.

Metastability exchange optical pumping in 3 He gas up to 30 mT: Efficiency measurements and evidence of laser-induced nuclear relaxation

Advances in metastability exchange optical pumping (MEOP) of 3He at high laser powers, with its various applications, but also at high gas pressures p3 and high magnetic field strengths B, have provided strong motivation for revisiting the understanding and for investigating the limitations of this powerful technique. For this purpose, we present systematic experimental and theoretical studies of efficiency and of relaxation mechanisms in B≤30 mT and p3=0.63−2.45 mbar. 3He nuclear polarisation is measured by light absorption in longitudinal configuration where weak light beams at 1083 nm parallel to magnetic field and cell axis with opposite circular polarisations are used to probe the distribution of populations in the metastable state. This method is systematically tested to evaluate potential systematic biases and is shown to be reliable for the study of OP dynamics despite the redistribution of populations by OP light. Nuclear polarisation loss associated to the emission of polarised light by the plasma discharge used for MEOP is found to decrease above 10 mT, as expected, due to hyperfine decoupling in highly excited states. However, this does not lead to improved MEOP efficiency at high laser power. We find clear evidence of additional laser-induced relaxation instead. The strong OP-enhanced polarisation losses, currently limiting MEOP performances, are quantitatively investigated using an angular momentum budget approach and a recently developed comprehensive model that describes the combined effects of OP, ME and relaxation, validated by comparison to experimental results.