Thesis (M. S.)--Ohio State University, 2008. / Title from first page of PDF file. Includes bibliographical references (p. 45-46).

Measurement of the intrinsic properties of processing plasmas is critically important in understanding discharges so that the optimum conditions can be achieved. Several different diagnostic methods have been developed and tested. A planar probe has been used to measure the ion flux and electron temperature in both inductively coupled and capacitively coupled plasma systems, at various pressures and applied powers, using the assumption that the electron energy distribution is a Maxwellian.</p> Frequency modulation spectroscopy (FMS) has been used to detect species in a plasma. It has been shown to be very effective, giving a significantly increased S/N ratio compared to both single pass absorption and low frequency mechanical modulation techniques. It has been used to measure excited argon atom concentrations, in both capacitively and inductively produced plasmas. The argon atom 4s[3/2]₁ level concentration was found to be between 2 x 10⁸ and 1 x 10¹¹ atom/cm³ and to generally increase with increasing applied power and to decrease with increasing total pressure. The temperature of the atoms was also measured and was found to be approximately 323 ± 17 K. A simple compact laser source at 308 nm has been produced from a frequency doubled cooled commercial diode laser. This has been used to detect the OH radical, by absorption, within the afterglow of a microwave discharge, produced either directly or chemically. Simple kinetic models have provided explanations of the variations in OH concentration with discharge conditions. A novel method, cavity laser induced fluorescence (CLIP), that combines the advantages of both laser induced fluorescence (LIF) and cavity ring down spectroscopy CRDS, has been shown to increase the sensitivity of a diagnostic system compared to absorption. This method could be used to follow concentration variations of a reaction in a single laser shot. Although such variation can be observed using LIF, it requires a calibration and a many laser shot experiment with a signal recorded at each time point. Whilst CRDS allows temporal information about the absolute concentrations of the species observed to be obtained, it is not as sensitive as LIF. By combining the two in CLIP, it may be possible to retain the sensitivity of LIF with the advantage of CRDS so that absolute and time varying concentrations can be obtained in a single pulsed laser shot. LIF and CRDS signals have been observed using the A ²?_u ? X ²S_g⁺ transition of the N₂⁺ ion. The lifetime of the A ²?_u state in the discharge was found to be sufficiently long for a time of flight experiment to be contemplated (an ion with a velocity of 10 kms^-1 on average would travel 5 mm before radiating). Although the preliminary tests for the time of flight experiment have shown that this method is not feasible with a pulsed laser, the basic cavity locking procedures required for an analogous continuous wave experiment have been successfully demonstrated. A frequency doubled diode laser source has been constructed and tested, with the eventual aim of detecting N₂⁺ via the B ²S_u ? X ²S_g⁺ electronic transition. This has been found to be insufficiently intense to be used for a proposed two dimensional velocity mapping experiment, but several strategies to improve its performance are suggested.

The wurtzite GaN has either Ga or N polarity. The direction of polarization, hence it¡¦s associated polarization-induced electric fields (Fp), is determined by the polarity of the sample. In the present work, we prepared both N-face polarity and n-type doping of GaN with thicknesses are 1.1£gm and 70nm. Photoreflectacne (PR) and contactless electroreflectance (CER) were used in combination to study the nature of the surface band bending which was found to be determined by the type of doping for the thick sample and by the polarity for the polarity for the thin sample. This is in agreement with a theoretical calculation by Poisson-Schr&#x00F6;dinger solver. Hence, CER can determine the polarity of GaN film as long as the sample is thin enough of the Fp to become dominant in the surface region.

The electronic bandstructure of solids near room temperature has been successfully explored with previous versions of modulation spectroscopy. Modulation of parameters which enter into the bandstructure produce a dielectric function variation. This changes the optical observables, such as reflectance or absorptance. Modulation resonances are observed near singularities in the joint density-of-states function. These resonances must also be detectable in the emittance, an observable which also depends on the dielectric function. Thus, this work investigates the possibility of detection of optical resonances riding on the temperature derivative of the blackbody emission from a solid at high temperature. The modulated emittance was separated from the thermal background by a detection scheme utilizing a CCD and computer. The resonances were not observed because of excessive CCD noise. The existance and magnitude of the resonances was based upon results from other modulation spectroscopies.

Electron spin echo envelope modulation (ESEEM) spectroscopy is widely used to study the radical pairs created during the primary steps of photosynthesis. In this thesis the analysis of ESEEM spectra is improved, and some new applications and variations of this experiment suggested. Experimental spectra from species such as P⁺Q^-_A, the secondary radical pair formed in the reaction centre of the bacterium Rhodobacter sphaeroides, give information about the exchange and dipolar couplings between the radicals. The model used to analyse the data affects the results; this thesis suggests two improvements. First, the effect of anisotropic hyperfine couplings in the radicals is considered by the addition of a single spin-1/2 nucleus to the model. This approach suggests that previous models neglecting the effect of nuclei may have been slightly in error. Secondly, several model fittings are performed in the time domain. This approach avoids the Fourier transformation to the frequency domain so that experimental dead-time does not corrupt the data. An excellent fit to experimental data is found with a model containing one spin-1/2 nucleus on each radical. The hyperfine coupling parameters resulting from the fit are consistent with independent experimental results. Use is made of the method of Cramér-Rao lower bounds to assess the precision to which experimental parameters are determined from a time domain curve fitting. It is shown that the lower bounds may also be used to determine the optimum sampling strategy for the experiment. An example is given of the novel use of ESEEM to determine the distance between the radicals in the strongly coupled, uncorrelated radical pair Q^-_AQ^-_B ESEEM has not yet been used for this purpose, and the simulated spectra produced here indicate that the experiment could be used to evaluate the dipolar coupling and hence the inter-radical distance. This thesis considers the possibility of performing ESEEM at higher frequencies than are usually considered. Calculations show that the increased resolution of the g-tensors allow an experiment performed at the W-band frequency of 95 GHz to make a correlation between the relative orientations of the radicals and the dipolar axis, information which has previously been unavailable from a single experiment.

Contactless electroreflectance (CER), a modulation spectroscopy (MS) technique, has been used to study the A and C exciton transitions in A1xGa1-xN layers for a composition range of 0 ≤ x ≤ 0.48 at room temperature. Taking the entire composition range (0 ≤ x ≤ 1) into account by incorporating a previously reported band gap energy for AlN, the dependence of the A-exciton transition on composition showed a downward bowing from linearity. A bowing parameter of b = 1.7 eV was found. Analysis of the lower composition range 0 ≤ x ≤ 0.48 resulted in a linear fit, as did the trend for the detectable C exciton transitions. The slope of the linear trendlines for the A and C exciton were practically the same.

Existem algumas técnicas destinadas ao estudo das características fotofísicas de materiais orgânicos ou dispositivos eletrônicos e optoeletrônicos a base de semicondutores orgânicos. A exemplo disso, a técnica de espectroscopia de absorção fotoinduzida de onda contínua (Continuous Wave Photoinduced Absorption/cw-PIA) apresenta grande sensibilidade como método destinado ao estudo dos processos eletrônicos envolvendo espécies excitadas de vida longa. Esta técnica emprega dois feixes ópticos distintos, um para excitação da amostra e outro (feixe de prova) para investigar os estados excitados remanescentes em amostra após bombeio óptico. O presente trabalho tem como objetivo a construção, desenvolvimento e caracterização de um aparato experimental para espectroscopia cw-PIA. A montagem bem sucedida da técnica foi testada em filme do polímero semicondutor P3HT, em filme de blenda (1:1) de P3HT/PCBM (comumente utilizada como camada ativa em células solares orgânicas) e em filmes automontados camada-a-camada (LbL) do tipo doador-aceitador de carga (P3KHT/P6N), sendo que a molécula P6N foi sintetizada pelo Grupo de Polímeros Bernhard Gross do IFSC-USP. Os filmes LbL de P3KHT/P6N, em comparação aos filmes blenda de P3HT/PCBM, demonstraram uma eficiência maior quanto a geração de portadores de carga com tempo de vida longo. / There are some techniques for the study of photophysical characteristics of organic materials or electronic and optoelectronic devices based on organic semiconductors. For example, the technique of continuous wave photoinduced absorption spectroscopy (cw-PIA) is a highly sensitive method for the study of the electronic processes involving long-lived excited species. This technique uses two distinct optical beams, one for sample excitation and another for probing the excited states remaining in the sample after optical pumping. The present work aims at the construction, development and characterization of an experimental apparatus for cw-PIA spectroscopy. The successful implementation of the technique was tested in a film of the semiconducting polymer P3HT and of the blend (1:1) P3HT/ PCBM (usually employed as active layer in organic solar cells), and also in a Layer-by-Layer (LbL) film of donor-acceptor molecules P3KHT/P6N, where the P6N molecule has been synthesized by Polymer Group Bernhard Gross at IFSC- USP. The comparison between P3KHT / P6N LbL film and the blend P3HT/PCBM has demonstrated higher charge carrier generation efficiency (with long lifetime) for the LbL film.

Faraday modulation spectroscopy (FAMOS) is a laser-based spectroscopic dispersion technique for detection of paramagnetic molecules in gas phase. This thesis presents both a new theoretical description of FAMOS and experimental results from the ultra-violet (UV) as well as the mid-infrared (MIR) regions. The theoretical description, which is given in terms of the integrated linestrength and Fourier coefficients of modulated dispersion and absorption lineshape functions, facilitates the description and the use of the technique considerably. It serves as an extension to the existing FAMOS model that thereby incorporates also the effects of lineshape asymmetries primarily originating from polarization imperfections. It is shown how the Fourier coefficients of modulated Lorentzian lineshape functions, applicable to the case with fully collisionally broadened transitions, can be expressed in terms of analytical functions. For the cases where also Doppler broadening needs to be included, resulting in lineshapes of Voigt type, the lineshape functions can be swiftly evaluated (orders of magnitude faster than previous procedures) by a newly developed method for rapid calculation of modulated Voigt lineshapes (the WWA-method). All this makes real-time curve fitting to FAMOS spectra feasible. Two experimental configurations for sensitive detection of nitric oxide (NO) by the FAMOS technique are considered and their optimum conditions are determined. The two configurations target transitions originating from the overlapping Q22(21=2) and QR12(21=2) transitions in the ultra-violet (UV) region (227nm) and the Q3=2(3=2)-transition in the fundamental rotational-vibrational band in the mid-infrared (MIR) region (5.33 µm). It is shown that the implementations of FAMOS in the UV- and MIR-region can provide detection limits in the low ppb range, which opens up the possibility for applications where high detection sensitivities of NO is required.

Abstracts Photoreflectance(PR) of surface-intrinsic n+ type doped GaAs has been measured for various power densities of pumping laser.The spectra exhibited many Franz-Keldysh oscillations,where by the electric field(F) can be determined from the technique of the fast fourier transform.It is known that F's determined from PR are subjected to photovoltaic effect ,but it is difficult to estimate the strength of modulating field in the PR measurements.Hence we have investigated the relation between F and modulating field by using electroreflectance to simulate PR.In this work,the relation will be confirmed by using solely PR.Here a method was devised to obtain the strength of modulating field in the PR measurements.The photo-voltage(Vs)of the pump beam can be measured directly with a lock-in amplifier by making electrical contacts on the front and rear sides of the sample.The strengh of modulation field is equal to Vs/d due to a uniform F in the undoped layer,where d is the thickness of the undoped layer.

Existem algumas técnicas destinadas ao estudo das características fotofísicas de materiais orgânicos ou dispositivos eletrônicos e optoeletrônicos a base de semicondutores orgânicos. A exemplo disso, a técnica de espectroscopia de absorção fotoinduzida de onda contínua (Continuous Wave Photoinduced Absorption/cw-PIA) apresenta grande sensibilidade como método destinado ao estudo dos processos eletrônicos envolvendo espécies excitadas de vida longa. Esta técnica emprega dois feixes ópticos distintos, um para excitação da amostra e outro (feixe de prova) para investigar os estados excitados remanescentes em amostra após bombeio óptico. O presente trabalho tem como objetivo a construção, desenvolvimento e caracterização de um aparato experimental para espectroscopia cw-PIA. A montagem bem sucedida da técnica foi testada em filme do polímero semicondutor P3HT, em filme de blenda (1:1) de P3HT/PCBM (comumente utilizada como camada ativa em células solares orgânicas) e em filmes automontados camada-a-camada (LbL) do tipo doador-aceitador de carga (P3KHT/P6N), sendo que a molécula P6N foi sintetizada pelo Grupo de Polímeros Bernhard Gross do IFSC-USP. Os filmes LbL de P3KHT/P6N, em comparação aos filmes blenda de P3HT/PCBM, demonstraram uma eficiência maior quanto a geração de portadores de carga com tempo de vida longo. / There are some techniques for the study of photophysical characteristics of organic materials or electronic and optoelectronic devices based on organic semiconductors. For example, the technique of continuous wave photoinduced absorption spectroscopy (cw-PIA) is a highly sensitive method for the study of the electronic processes involving long-lived excited species. This technique uses two distinct optical beams, one for sample excitation and another for probing the excited states remaining in the sample after optical pumping. The present work aims at the construction, development and characterization of an experimental apparatus for cw-PIA spectroscopy. The successful implementation of the technique was tested in a film of the semiconducting polymer P3HT and of the blend (1:1) P3HT/ PCBM (usually employed as active layer in organic solar cells), and also in a Layer-by-Layer (LbL) film of donor-acceptor molecules P3KHT/P6N, where the P6N molecule has been synthesized by Polymer Group Bernhard Gross at IFSC- USP. The comparison between P3KHT / P6N LbL film and the blend P3HT/PCBM has demonstrated higher charge carrier generation efficiency (with long lifetime) for the LbL film.