Dissertations / Theses on the topic 'Pump-probe'

The study of photovoltaic materials is important so as to develop new solar energy technologies: in particular, quantum-confined semiconductors could offer increased quantum efficiencies at a much lower manufacture cost. This thesis contains results from a number of pump-probe experiments designed to probe the carrier dynamics in bulk and quantum-confined photovoltaics. A THz time-domain spectrometer was designed, built and commissioned. The THz refractive indices and absorption coefficients of toluene and hexane were determined, and the spectrometer was benchmarked using a photoexcited GaAs wafer. Results are presented of time-resolved THz spectroscopy of photoexcited bulk InP as a function of laser excitation wavelength. These data were used to extract the quantum efficiency of bulk InP in order to compare with recent results for InP quantum dots. The quantum efficiency in quantum dots increases when the incident photon energy is at least twice the band gap energy, whereasthe efficiency of the bulk material is found to decrease. This is because of surface recombination, and these measurements therefore verify the potential superiority of quantum dot materials over bulk materials for use in solar energy applications. Initial measurements of quantum dots using THz spectroscopy highlighted the various experimental challenges involved and the upgrades required to study such samples in the future.The time-dependence of the photoinduced surface photovoltage (SPV) in Si was studied on nanosecond timescales by synchronizing an ultrafast laser system to a synchrotron radiation source (the SRS at Daresbury, UK), and measuring the resulting shift in the photoelectron spectrum. The equilibrium band bending was determined, and the decay of the SPV was attributed to the recombination of charge carriers across the band gap. Results are presented for the SPV in bulk ZnO and for PbS quantum dot chemically attached to ZnO. The fact that the PbS quantum dots were chemically attached to the surface without becoming oxidized was verified using X-ray photoelectron spectroscopy (XPS). The changes caused by photoexcitation occur on much longer timescales in ZnO than Si (sub-milliseconds rather than nanoseconds), and these timescales were conveniently accessed using the time-resolved XPS facility at the TEMPO beamline at Synchrotron SOLEIL (Paris, France). This is due to oxygen adsorption and desorption processes at the ZnO surface affectingthe transfer of charge carriers. The addition of PbS quantum dots to the ZnO surface was found to increase the speed of this charge transfer due to injection of carriers directly from the PbS quantum dot to the bulk ZnO conduction band.

The present thesis concerns theoretical studies of molecular interactions investigated by infrared and X-ray spectroscopic techniques, with emphasis on using these two techniques combined in pump-probe experiments. Four main types of studies are addressed: the use of near-edge X-ray absorption fine structure spectra (NEXAFS) to manifest through-bond and through-space interactions; the role of hydrogen bonding in the formation of X-ray photoelectron spectra as evidenced by simulations of the water dimer; the development of theory, with sample applications, for infrared X-ray pump-probe spectroscopy; and molecular dynamics simulations of light-induced fragmentation of water clusters.

Ab initio calculations indicate that NEXAFS spectra give direct information about the through-bond and through-space interactions between vacant non-conjugated π* orbitals. It is found out that the X-ray photoelectron spectrum of the water dimer differs dramatically from the monomer spectrum in that two bands are observed, separated by the chemically shifted ionization potentials of the donor and the acceptor. The hydrogen bond is responsible for the anomalously strong broadening of these two bands. The studies show that X-ray core electron ionization of the water dimer driven by an infrared field is a proper technique to prove the proton transfered state contrary to conventional X-ray photoelectron spectroscopy.

The physical aspects of the proposed new X-ray spectroscopic method - phase sensitive Infrared - X-Ray Pump-Probe Spectroscopy - are examined in detail using the wave packet technique in three applications; the NO molecule and the dynamics of proton transfer in core ionized water dimer and glyoxalmonoxime. It is found out that the phase of the infrared pump field strongly influences the trajectory of the nuclear wave packet on the ground state potential, which results in a phase dependence of the X-ray pump-probe spectra. A proper choice of the delay time of the X-ray pulse allows the direct observation of the X-ray transition in the proton transfered well of the core excited potential. It is found out that the glyoxalmonoxime molecule possesses an important feature; proton transfer accompanied by core hole hopping. Special attention is paid to the quantum control of the populations of vibrational level which is of crucial importance to shape the wave packet of desirable size.

The wave packet technique becomes computationally very expensive when the number of nuclear degrees of freedom is large. Molecular dynamics is used instead in studies of light-induced nuclear kinetics in the water hexamer cluster. We predict a novel mechanism of the mechanical action of light on atoms and molecules. This mechanism is based on the rectification of the Lorentz force, which gives a unique opportunity of direct site selective mechanical action of light on atoms and molecules inside large systems like clusters or biomolecules.

Ultrafast pump-probe spectroscopy is a powerful technique for measuring decay times for an optically excited system, e.g. a semiconductor, on the pico- to femtosecond time scale. We present both a classical approach and a quantum mechanical density matrix approach to simulate the pump-probe signal and compare the two. The main features of a typical pump-probe experiment are explained and the "coherent artifact" is accounted for. With a three-level density matrix approach we explain some experimental features from pump-probe studies of gallium arsenide (GaAs). A simple model for simulating pump-probe of semiconductors is introduced, and the relation to the density matrix approach is derived. We also show how the semiconductor model reproduces the main features of experimental data from pump-probe studies of GaAs.

L'étude de la dynamique hors équilibre des systèmes fortement corrélés, à l'aide de laser femtoseconde, a révélé une variété de phénomènes sans analogue en physique d'équilibre. Dans cette thèse, nous étudions théoriquement la dynamique hors équilibre des degrés de liberté du réseau et leur signature en spectroscopie pompe-sonde. Nous développons une description microscopique des phonons cohérents displacive excité par le laser. La théorie capture la rétroaction de l'excitation des phonons sur le fluide électronique, qui manque dans la formulation phénoménologique actuelle. Nous montrons que cette rétroaction conduit à une oscillation avec une fréquence qui dépend du temps aux temps courts, même si le mouvement des phonons est harmonique. Pour les temps longs, cette rétroaction apparaît comme une phase résiduelle dans le signal oscillatoire. Nous appliquons la théorie au BaFe2As2, nous expliquons l'origine de la phase du signal oscillatoire rapporté dans des expériences récentes, et nous prédisons que le système oscille avec une fréquence décalé vers le rouge pour les grandes fluences. Notre théorie ouvre également la possibilité d'extraire des informations d'équilibre à partir la dynamique des phonons cohérents. Un autre phénomène intéressant qui a été observé en spectroscopie pompe-sonde est l'oscillation des fluctuations du réseau au double de la fréquence d’un phonon du système étudié. Ces oscillations sont interprétées comme une signature d'états de phonons squeezé macroscopique. Dans ce travail, nous identifions d'autres mécanismes d'oscillations à une fréquence double autre que le squeezing. Nous montrons qu'un quench de la température du bain thermique induite par la pompe, à laquelle le phonon est couplé, ou l'excitation d'un phonon cohérent pour lequel l'anharmonicité cubique est permise par symétrie peut également produire de telles oscillations en spectroscopie sans que le phonon soit dans un état squeezé. Nous concluons que, contrairement à ce qui est communément admis, les oscillations à double fréquence phononique en spectroscopie de bruit ne sont pas nécessairement une signature des phonons squeezés. Nous soulignons ce qui peut être un critère fiable pour identifier un phonon squeezé en utilisant la spectroscopie pompe-sonde
The study of the out of equilibrium dynamics of strongly correlated systems, using ultrafast pulses, uncovered a plethora of phenomena with no analog in equilibrium physics. In this thesis, we theoretically investigate the out of equilibrium dynamics of the lattice degrees of freedom and their signature in pump-probe spectroscopy. We develop a Hamiltonian-based microscopic description of laser pump induced displacive coherent phonons. The theory captures the feedback of the phonon excitation upon the electronic fluid, which is missing in the state-of-the-art phenomenological formulation. We show that this feedback leads to chirping at short timescales, even if the phonon motion is harmonic. At long times, this feedback appears as a finite phase in the oscillatory signal. We apply the theory to BaFe2As2, explain the origin of the phase in the oscillatory signal reported in recent experiments, and we predict that the system will exhibit redshifted chirping at larger fluence. Our theory also opens the possibility to extract equilibrium information from coherent phonon dynamics. Another interesting phenomenon that have been reported in pump-probe spectroscopy is the oscillation of the lattice fluctuations at double phonon frequency. These oscillations are invariably interpreted as a signature of macroscopic squeezed phonon states. In this work, we identify other mechanisms of double phonon frequency oscillations that do not involve squeezing. We show that a pump induced temperature quench of the bath, to which the phonon is coupled to, or exciting a coherent phonon for which cubic anharmonicity is allowed by symmetry can also produce such oscillations in noise spectroscopy without squeezing the phonon state. We conclude that, in contrast with what is commonly believed, double phonon frequency oscillations in noise spectroscopy are not necessarily a signature of macroscopic phonon squeezing. We point out what can be a reliable criterion to identify a squeezed phonon using pump-probe spectroscopy

Recent advances have led to the demonstration of trains of attosecond pulses and isolated attosecond pulses in the vacuum ultraviolet (VUV) and extreme ultraviolet (XUV) regions of the electromagnetic spectrum in a number of laboratories. This has raised the possibility of direct time resolved measurements of correlation driven electron dynamics within molecules, with a long term aim of unprecedented control over the dynamics of matter at atomic and molecular length scales. Particular interest has arisen towards the possibility of a charge migration mechanism within molecules, in which purely electron driven processes result in the movement of charge around an excited molecule in the absence of any nuclear dynamics. However, even once these sources have been established, using them in time resolved experiments is challenging. This is due to extremely short time-scales involved, the complexity of the processes under study, and the limitations of currently available attosecond sources. In this thesis I describe the development of novel instrumentation and methods for attosecond pump – probe experiments on electron dynamics in molecules. Strategies for the experimental study of charge migration are reviewed in detail which motivates the design and implementation of a purpose built instrument combining an electron velocity map imaging (VMI) spectrometer and an ion time of flight (iTOF) spectrometer. This instrument is designed in tandem with the development and characterisation of an isolated pulse at the new photon energy of 20eV. This 20eV pulse is intrinsically synchronized with another attosecond pulse at 90eV. Together, the new instrument and light source represent a unique capability for the investigation of electron dynamics in molecules. Finally, the first experimental results are presented and perspectives for future studies using the new developments are discussed.

In order to make cost effective solar cells from mc-Si materials, the negative contributions from defects and impurities should be reduced. The analysis of the photogenerated carrier properties is therefore of great importance for characterising carrier processes and hence, for improving the material performance.In this work, pump-probe measurement of a range of silicon wafers have been performed, using anultrafast laser of 800 nm wavelength and 85 fs pulses. The optical response in the samples were analysed by measuring the reflected probe beam initial transient.The purpose of this theses was to explore the use of pump-probe experiment to study carrier dynamics in mc-Si. Measurements of single c-Si samples were used as a basis for developing good experimental skills as well as achieving knowledge about carrier dynamics in c-Si. The initial Delta R/R was studied for a range of input parameters, aiming to characterise important contributions to the measurements.The effects of passivation has been studied, indicating a significant contribution to R~R. Etchingoff the passivated layer of an oxide (SiO2) wafer, showed a radically increased in pump beam reflectivity, from 9% to 32%, and a reduced DeltaR~R from 47×10-6 to 37×10-6 was be observed. Analysis has showed that incident angle may be chose such that the pump reflection loss is at a minimum for the given passivation thickness.The final results showed a R~R is in the range of (14-41)e-6 for bare c-Si, and (47-171)e-6 for passivated c-Si wafers.Ultrafast initial recovery has been observed for mc-Si samples, and attributed to trapping of carriers. Decay times in the range of 1-6 ps are deduced and trapping densities are found as (1:3 - 4:3) × 10^18 cm-3, which is in the same order as the excitation densities.A methodology for using pump-probe measurements to analyse mc-Si samples is established, and the technique is used in characterising the observed defect states, which is of great interest for improving solar cell materials.

The generation of few-cycle pulses at near-infrared wavelengths is now a robust technology, as is their application to the efficient production of high-order harmonics in the extreme ultraviolet region with temporal confinement to hundreds of attoseconds. Recent years have seen considerable efforts directed to the study of electron dynamics in complex molecules in real time, with relevance to processes such as photosynthesis and radiation damage of proteins and DNA. This work describes the development of new and unique sources suited for the study of such dynamics, together with novel instrumentation and experimental methodology. This includes a pair of synchronised attosecond pulses at different photon energies in the VUV and XUV regions, which we have generated via high harmonic generation from a few-cycle NIR source and characterised with attosecond streaking. We have also explored the possibilities of sub-cycle control of these attosecond pulses by adding a second harmonic field to the high- harmonic generation process, and simultaneously characterised this second harmonic field with a novel characterisation technique known as ARIES, capable of waveform sampling at arbitrary optical wavelengths. In parallel, we have developed a few-cycle short-wavelength IR source for a UK user facility, to take advantage of the favourable wavelength scaling of the maximum photon energy achievable via high-harmonic generation. Using a commercial optical parametric amplifier and a hollow-core fibre compression system, we have generated sub-2-cycle pulses at 1750 nm, characterised via third-harmonic autocorrelation and a novel implementation of the dispersion scan technique. We have commissioned a beamline for attosecond pump-probe studies in the gas phase, including a purpose-built dual spectrometer with capabilities for simultaneous measurement of mass spectra of ions and velocity-map imaging of electrons. We have performed initial VUV-NIR pump-probe experiments on a small organic molecule, namely isopropanol, and identified a time- dependent signature as an IR-induced coupling. Finally, we have considered perspectives for future studies in attosecond pump-probe experiments with the demonstration of a two-VUV-photon process in helium performed with a moderate energy, high repetition rate attosecond source.

In this thesis I describe the development of novel light sources to be applied in attosecond pump-probe experiments, together with new methods dedicated to their characterisation and optimisation. Femtosecond pulses are a necessary tool to enter the attosecond domain. For this reason their development is a key element to unlock more capabilities in pump-probe attosecond experiments. The dynamics of generation and compression of few-cycle femtosecond pulses has been studied in a hollow core fibre system. The carrier envelope phase stability performance under increasing input power to the fibre system has been examined systematically, showing the effects of ionisation on the carrier envelope phase stability. Two characterisation techniques have been developed to measure ultrafast femtosecond pulses. A version of the d-scan technique has been demonstrated in the single shot regime for the first time, extending the utility of this diagnostic. An all optical technique (ARIES) for the characterisation of the full waveform of a femtosecond pulse has been developed, exploiting the high harmonics generation process and the sensitivity of the cut-off emission to the instantaneous amplitude of the generating electric field. The main results of the thesis are concerned with the generation of isolated attosecond pulses in new spectral regions. Vacuum ultraviolet few-femtosecond and attosecond pulses have been generated by filtering with metallic foils the high harmonics emission driven by sub-4 fs pulses, and were characterised with the attosecond streaking technique. When using indium as spectral filter a pulse duration of 1.7±0.1 fs was measured at a photon energy of 15 eV. When using tin as spectral filter a pulse duration of 585±31 as was measured at a photon energy of 20 eV. The experimental techniques developed in this thesis allow these pulses to be generated simultaneously with a XUV pulse with a measured duration of 270±25 as. This work will open new opportunities for pump-probe experiments, for example studies of ultrafast charge migration in large molecules.

Thesis (PhD)--Stellenbosch University, 2011.
ENGLISH ABSTRACT: The generation of ultrafast light pulses and the development of time resolved spectroscopic techniques, such as the femtosecond pump probe spectroscopy technique, have facilitated the study of ultrafast energy transfer in the photosynthetic systems of green plants and photodynamic therapy drugs. It has allowed the investigation of biological and chemical processes that take place on the ultrafast timescale and has allowed us to obtain spectral and kinetic information on energy transfer. In addition, it has allowed time resolved experiments in which the transient absorption of species under investigation was observed and has elucidated molecular dynamics. In the present work this was done with a temporal resolution of approximately 200 fs and covering a pump-to-probe delay range of 300 fs to 2 ns. The main aims of this study were to characterise the femtosecond pump probe spectroscopy system, to investigate the energy transfer in the natural light harvesting complex II (LHC II) in view of future expansion to the study of synthesized arti cial functional light harvesting complexes and nally to study ultrafast processes in zinc phthalocyanine (ZnPc) systems. In photosynthetic organisms, LHC II is the most abundant light harvesting complex and it plays an important role in light harvesting and photoprotection. The light energy is absorbed by light harvesting complexes and transferred to a reaction centre (RC) in an ultrafast timescale. Phthalocyanines are a new class of photosensitiser used for photodynamic therapy. These drugs are used to treat small and super cial tumours. The energy transfer from the singlet excited state to the triplet excited state occurs on an ultrafast timescale. However, recent work done on zinc phthalocyanine has proved that the determination of the ultrafast component remains a challenge. Several ultrafast studies carried out on ZnPc in solvents have been not only unsuccessful to give a clear picture of the ultrafast dynamics but have also produced divergent results. In this study, a characterisation of the femtosecond pump probe spectroscopy setup was done. The samples under investigation were probed by a white light continuum. The generation of the white light continuum introduced chirp, which in uenced the temporal evolution of the transient absorption results. The technique used to correct the chirp introduced by white light generation is discussed in detail. Our femtosecond pump probe spectroscopy setup was benchmarked by using a well known dye, namely malachite green. In addition, the investigation of the transient absorption change of LHC II, an active component in photosynthesis, as extracted from spinach leaves and the ultrafast dynamics of a promising photosensitiser ZnPc in dimethyl sulfoxide (DMSO) as well as in dimethyl formamide (DMF) was done. The spectral and dynamic results obtained using these three samples are described and exponential ts to the absorbance decay curves used to estimate the timescales of the energy transfer processes are presented. In this experiment, the dynamics and measured time constants related to the energy transfer between the different types of chlorophyll in LHC II was monitored, whereas with ZnPc, the dynamics and the measured time constants associated with solvation dynamics and vibrational relaxation was examined.
AFRIKAANSE OPSOMMING: Die vorming van ultravinnige lig pulse en die ontwikkeling van tyd opgelosde spektroskopiese tegnieke, soos die femtosekonde pomp proef spektroskopie tegniek, het die studie van ultravinnige energie oordrag in fotosintetiese stelsels van groen plante en chemiese prosesse gefasiliteer, wat kan plaasvind op die ultravinnige tyd skaal en laat dit toe om spektrale en kinetiese informasie oor die energie oordrag te kan bepaal. Dit het ook dit moontlik gemaak om tyd opgelosde eksperimente te kan doen waarin ons veranderlike absorbsie van die monster kon ondersoek en die molekulere dinamika kon ontrafel. In hierdie werk is dit gedoen met n tyd resolusie van omtrent 200 fs termyl 'n pomp-tot-proef tydvertraging van 300 fs tot 2 ns gebruik is. Die hoof doelwitte van hierdie werk was om 'n femtosekonde pomp proef spektroskopie stelsel te karakteriseer, die energie oordrag in die natuurlike ligoes kompleks II te ondersoek met die toekomstige uitbreiding van die studie na sintetiese lig-oes komplekse as oogmerk en laastens om ultravinnige prosesse in Sink Ftalosianiene stelsels te ondersoek. In fotosintetiese organismes, is lig oes kompleks II die mees volop lig oes kompleks en speel 'n belangrike rol in lig oes en foto skerming. Die lig energie word geabsorbeer deur lig oes komplekse en dan oorgedra na reaksie middelpunte in 'n ultravinnige tydskaal. Ftalosianiene is 'n nuwe klas fotosensiteerder wat gebruik word in fotodinamiese terapie. Hierdie dwelms word gebruik om klein en oppervlakkige gewasse te behandel. Die energie oordrag van die opgewekte singlet tot die triplet toestand vind plaas op die ultravinnige tydskaal. Onlangse navorsingswerke het getoon dat die bepaling van die ultravinnige komponent 'n uitdaging bly. Verskeie vorige ondersoeke is gedoen op Sink Ftalosianiene in verskeie oplosmiddels, en nie net het hierdie studies nie 'n helder prentjie verskaf van die ultravinnige dinamika nie, maar het ook divergerende resultate opgelewer. In hierdie werk word 'n karakterisering van die femtosekonde pomp proef spektroskopie stelsel gedoen. Die monsters is ondersoek met 'n wit lig kontinuum proef. Die vorming van die wit lig kontinuum het tjirp veroorsaak, wat die tyd evolusie van die veranderlike absorbsie resultate beinvloed het. Die tegniek wat gebruik was om die tjirp te korregeer word bespreek. Ons femtosekonde pomp proef spektroskopie stelsel is gestandardiseer deur die welbekende kleurstof malachiet groen. Ons het ook die veranderlike absorbsie van lig oes kompleks II ondersoek, 'n aktiewe komponent in fotosintese, soos dit onttrek is uit spinasie blare, asook die ultravinnige dinamika van die belowende photosensitizer Sink Ftalosianiene in DMSO asook DMF. Die spektrale en dinamiese resultate verkry vanaf hierdie drie monsters word beskryf en eksponensiele passings aan die absorbsie verval kurwes is gebruik om die tydskale van die energie oordrag prosesse te skat. In hierdie eksperiment is dinamika en gemete tydkonstantes waargeneem wat toegeskryf kan word aan die energie oordrag tussen verskillende soorte chloro l in lig oes kompleks II. In die Sink Ftalosianien eksperimente is dinamika en gemete tydkonstantes waargeneem wat toegeskryf kan word aan solverings dinamika asook vibrasionele ontspanning.

This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections.
Thesis: Ph. D., Massachusetts Institute of Technology, Department of Electrical Engineering and Computer Science, 2019
Cataloged from student-submitted PDF version of thesis.
Includes bibliographical references (pages 155-168).
This thesis focuses on the development of dual-echelon single-shot spectroscopy and its applications to study irreversible photoinduced dynamics. First, the ultrafast laser sources and the related control and characterization techniques are discussed. In particular, we have invented a two-stage dual-beam noncollinear optical parametric amplifier to provide tunable sources for pump-probe spectroscopy. Next, the experimental setup of dual-echelon single-shot spectroscopy is illustrated with great detail and possible noise sources and correction methods are explored. Using the single- shot technique, we studied photoinduced dynamics in three different materials. In bismuth, we found a transition into a transient symmetric phase at high fluences. We showed the coherent control of phonon parameters with pump-pump-probe experiments. We also simulated the carrier and phonon dynamics using a modified two-temperature model. In tellurium, we demonstrated that the amorphization of crystalline tellurium induced by femtosecond pulses is a thermal process. We also estimated the lattice temperature by the change in phonon frequency. In a strained manganite film, we observed a photoinduced persistent insulator-to-metal transition and showed the partial recovery of the generated metallic phase to the insulating phase.
by Yu-Hsiang Cheng.
Ph. D.
Ph.D. Massachusetts Institute of Technology, Department of Electrical Engineering and Computer Science

The terahertz (THz) region of the electromagnetic spectrum remains relatively underdeveloped and unexploited. This is due to the lack of compact and high-power sources which are able to output radiation between 100 GHz and 10 THz. In this thesis two separate methods of generating THz radiation are considered; the quantum cascade laser (QCL) and the photoconductive (PC) emitter. THz-QCLs generate radiation through the intersubband transition of electrons within quantum wells. Electrons are then transported into the adjacent quantum well, where they are recycled. Alternatively, PC emitters generate THz radiation through the excitation, acceleration and recombination of electron-hole pairs in semiconducting material, leading to the emission of short pulse THz radiation. In this work, the gain dynamics of two different designs of THz-QCL are investigated using well-established time domain spectroscopy (TDS) techniques. The gain recovery time of a bound-to-continuum (BTC) device, a property known to be responsible for the prevention of mode-locking in the laser, is recovered through use of THz-pump-THz-probe TDS. This was performed multiple times, both with and without anti-reflective coating applied to the QCL facets. This coating prevents the QCL from lasing. Furthermore, this approach was then used to investigate the carrier dynamics of a hybrid active region device, which yielded some interesting preliminary results. To facilitate these measurements, a new form of quartz-mounted PC device was designed and fabricated. This entails removing the LT-GaAs active layer from its SI-GaAs growth substrate and bonding it directly to a layer of z-cut quartz. In emission, this device has been shown to produce significantly higher THz output fields, when compared to the previously used PC devices. In addition to this, the use of an optically transparent substrate provides the ability to perform back-side illumination, which is shown to improve the output characteristics of the device. Furthermore, when used in detection, the newly fabricated devices have shown significantly increased sensitivity, when compared to other methods of detection.

Ce travail est consacré à l’étude de la dynamique ultrarapide d’électrons chauds photo-excité dans des structures plasmonique. L’intérêt particulier de ce domaine réside dans le fait que les SPs, en raison de leurs caractéristiques spatio-temporelles spécifique, offrent un nouvel attrait technologique pour les processus de transport d’information ultra-rapide aux nano-échelles. Dans ce contexte, ce manuscrit offre une compréhension et une exploitation de l’une des principales limitations des technologies à base de SP : les pertes par effet Joule. Nous exploitons le fait que le mécanisme d’absorption des plasmons dans les métaux est suivi par la génération d’électrons chauds à l’échelle femtoseconde, ainsi les pertes peuvent être considrées comme une conversion d’énergie plasmon-électrons chauds. Cette conversion d’énergie est mesurée à l’aide d’une technique pompe-sonde laser femtoseconde. Nous lançons des impulsions SP que nous sondons sur des centaines de femtosecondes grace aux variations de permittivité diélectrique induites par le gaz d’électrons chaud accompagnant la propagation de SP. Le profil de température électronique est par conséquent une image de la distribution de densité de puissance de plasmon (absorption) non élargi spatialement et temporellement par diffusion de porteurs d’énergie. Nous avons pu démontrer la capacité de relier la mesure de température électronique à l’absorption du SP, révélant une absorption anormale autour d’une fente nanométrique. Les résultats expérimentaux sont en accord quantitatif avec les prédictions théoriques de la distribution de densité de puissance. Dans une seconde partie, nous avons étudié les pertes plasmoniques et leurs caractéristiques lors de sa propagation sur un film métallique semi-infini. Nous avons déterminé la vitesse de l’onde thermique électronique et son atténuation. Dans la dernière partie, nous utilisons une structure en pointe pour guider adiabatiquement et focaliser le plasmon à l’extrémité. Nous avons démontré ainsi la génération d’un point chaud nanométrique et avons mis en évidence un retard dans l’échauffement des électrons à l’extrémité de la pointe. Les perspectives et les questions ouvertes sont également discutées
In this work we explored the ultrafast dynamics of photo-excited hot electrons in plasmonic structures. The particular interest of this field resides on the fact surface plasmons (SP), because of their unrivaled temporal and spatial characteristics, provide a technological route for ultrafast information processes at the nanoscale. In this context, this manuscript provides a comprehension and the harnessing of one of the major limitation of the SP-based technologies : absorption losses by Joule heating. We exploit the fact that the mechanism of plasmon absorption in metals is followed by generation of hot electrons at femtosecond time scale, thus losses can be seen as a plasmon-to-hot-electron energy conversion. This energy conversion is measured with femtosecond pump-probe technique. Femtosecond SP pulses are launched and probed over hundred femtoseconds through the permittivity variations induced by the hot-electron gas and which accompany the SP propagation. The measured electron temperature profile is therefore an image of plasmon power density distribution (absorption) not broadened spatially and temporally by energy carrier diffusion. As an important result we demonstrated the capability to link the electronic temperature measurement to the plasmonic absorption, revealing an anomalous light absorption for a sub- slit surroundings, in quantitative agreement with predictions of the power density distribution. In a second part we studied plasmon losses and their characteristics when they propagate on semi-infinite metal film. We determined the electronic thermal wave velocity and damping. In the last part we used a focusing taper-structure to adiabatically guide and focus the plasmon at the apex. Was demonstrated the generation of a nanoscale hot spot and put in evidence a delayed electron heating at the taper apex. Perspectives and the remaining open questions are also discussed

Thesis: Ph. D., Massachusetts Institute of Technology, Department of Mechanical Engineering, 2019
Cataloged from PDF version of thesis.
Includes bibliographical references.
The optical resolution of microscopy is limited by the wave-like characteristic of the light. There are many recent advances in overcoming this diffraction limited resolution, but mostly focused on fluorescent imaging. Furthermore, there are few non-fluorescence wide-field super-resolution techniques that can fully utilize the applicable laser power to optimize imaging speed. Structured illumination microscopy is a super-resolution method that relies on patterned excitation. This thesis has presented novel applications of structured illumination microscopy to surface plasmon resonance fluorescence and pump-probe scattering imaging. First, structured illumination microscopy was introduced to surface plasmon resonance fluorescence imaging for high signal-to-noise and high resolution. Secondly, a theoretical framework for three-dimensional wide-field pump-probe structured illumination microscopy has been developed to increase the lateral resolution and enable depth sectioning. Further, structured illumination wide-field photothermal digital phase microscopy is proposed as a high throughput, high sensitivity super-resolution imaging tool to diagnose ovarian cancer. Finally, I have derived the exact analytical solution to the heat conduction problem in which a sphere absorbs temporally modulated laser beam for photothermal microscopy. The proposed method also has a great potential to be applied to other pump-probe modalities such as transient absorption and stimulated Raman scattering.
Funding sources and sponsors: National Institutes of Health (9P41EB015871-26A1, 5R01NS051320, 4R44EB012415, and 1R01HL121386-OlAl), National Science Foundation (CBET-09395 11), Hamamatsu Corporation, Singapore-Massachusetts Institute of Technology Alliance for Research and Technology (SMART) Center, BioSystems and Micromechanics (BioSyM), and Samsung Scholarship
by Yang-Hyo Kim.
Ph. D.
Ph.D. Massachusetts Institute of Technology, Department of Mechanical Engineering

Thesis (MSc (Physics))--University of Stellenbosch, 2009.
An ultrafast pump-probe spectroscopy experiment was developed in order to investigate the fast photoinduced isomerization reaction of the molecule resveratrol. Characteristics of the resveratrol molecule are discussed, including the photoisomerization reaction from trans- to cis-resveratrol. The experimental setup for the conventional spectroscopy measurement was developed and characterized in order to investigate and understand the conventional absorption and uorescence spectroscopy of resveratrol thoroughly. The absorption spectra for both trans- and cis-resveratrol, as well as the uorescence spectra were measured, discussed and explained. This therefore forms a foundation and serves as an initial step to develop a pump-probe spectroscopy experiment for resveratrol. A general overview of ultrafast pump-probe spectroscopy is presented, as well as an explanation of the nal developed experimental setup. The principles and characteristics of the chirped pulse ampli cation (CPA) femtosecond laser source and the tunable noncollinear optical parametric ampli er (NOPA) employed as the pump pulse are discussed. The process of white light continuum (WLC) generation was investigated to utilize as the ultrashort probe pulse. Two white light continuum generation experimental setups were developed and characterized for WLC generation in a transparent medium with the fundamental CPA laser light at 775 nm (in sapphire) and with the second harmonic (SH) of the CPA light at 387 nm (in quartz). A spectrometer was designed, built and characterized in conjuction with a line focus, for simultaneous measurement of the absorption in the pumped, unpumped and reference regions in the sample. In this way the photoisomerization of resveratrol could be measured with temporal resolution as a transient absorption signal. A 420 μg/ml resveratrol solution in ethanol was investigated in this pump-probe spectroscopy experiment and the results obtained are discussed accordingly.

Thesis (PhD (Physics))--University of Stellenbosch, 2010.
ENGLISH ABSTRACT: Silicon/silicon dioxide (Si/SiO2) interface is widely used in microelectronics as the gate between the drain and source of most metal oxide semiconductor field effect transistors (MOSFETs). The functionality, reliability and electrical properties of such transistors are strongly dependent on the quality of the Si/SiO2 structure forming the gate. Characterization of the Si/SiO2 interface is important in understanding device degradation therefore the Si/SiO2 interface is a subject of intensive investigation. Research studies of Si/SiO2 interfaces using optical methods have been reported by many groups around the world but to date many open questions still exist. The physics of photoinduced trap or defect generation processes and the subsequent trapping of charge carriers, the precise role of photoinduced interfacial electric field in altering optical properties of the Si/SiO2 interface and its role in affecting the second harmonic (SH) yield measurements are not well understood. In this work a commercial near infrared femtosecond (fs) laser source [1.55 eV, 75 ± 5 fs, 10 nJ, 80 MHz] is used to study native Si/SiO2 interfaces of free standing single crystalline Si membrane and bulk Si. Optical second harmonic (SH) generated at the Si/SiO2 interfaces of a Si membrane in reflection and for the first time in transmission is demonstrated as well as stationary, single colour, pump-probe reflectivity measurements from the Si/SiO2 interface of bulk n-type Si. The experimental setups for the second harmonic generation (SHG) and pump-probe techniques were designed and implemented, and measurements were recorded by a computer controlled data acquisition system. Free standing Si membrane samples were successfully produced at the Institut f¨ur Photonische Technologien (IPHT) in Jena, Germany from bulk Si using a chemical etching process and were characterised using the z-scan technique. The penetration depth of light with a photon energy of 1.55 eV in silicon allows transmission of the fundamental fs laser pulses through the Si membrane (∼ 10 μm in thickness) and this is exploited to generate a SH signal in transmission from the Si/SiO2 interfaces of the Si membrane. In the presence of sufficiently intense fs laser light defects are created at the interfaces and populated by multiphoton transfer of charges from Si to SiO2 where they are subsequently trapped. The transfer of charge establishes interfacial electric fields across the interfaces of the Si membrane and this enhances SHG. This phenomenon is called electric field induced second harmonic (EFISH) generation. To our knowledge, EFISH measurements from interfaces of Si membrane performed in transmission are demonstrated for the first time in the present study. The demonstration of EFISH in transmission revealed new results which allowed us to provide additional perspectives on the EFISH generation process at Si/SiO2 interfaces never reported before. The temporal response of SH signals from virgin spots were recorded at different incident laser powers for both reflection and transmission geometries. The SH responses measured in transmission were observed to be time dependent and show an increase during irradiation of the sample corresponding to EFISH process. A series of SH measurements were recorded at different laser powers to compare the magnitudes of SH yield in each detection geometry for a single Si/SiO2 interface. The magnitude of the SH yield measured in transmission was higher than expected and surpassed the SH yield measured in reflection. The expectation is based on the fact that the local intensity of the fundamental beam at the second interface where the SH in transmission is generated is low compared to the local intensity at the first interface where the SH in reflection originates. A physical model is developed to consistently interpret the experimental results obtained in this study. In this model we established the origin of EFISH signals in each detection geometry, explain the unexpected high SH signals measured in transmission and provide an analysis of the time constants extracted from SH response in transmission and reflection. In addition, we also report for the first time stationary pump-probe reflectivity measurements from bulk n-type Si(111) samples with native oxide. A strong pump beam was focused on the same spot as a weak probe beam from the same fs laser source. The change in reflectivity of the Si(111)/SiO2 system was recorded by monitoring the change in intensity of the weak reflected probe beam. The temporal evolutions of the reflectivity of the material were recorded at different pump powers. The reflectivity of the material increases over several minutes of irradiation and reaches steady-state after long time irradiation. The change in reflectivity of the material is attributed to a nonlinear process called Kerr effect, and the temporal response arises from the photoinduced interfacial electric field across the Si(111)/SiO2 interface caused by multiphoton charge transfer from bulk Si(111) to the SiO2 layer. The results reported in this study contribute to the understanding of the photoinduced interfacial electric field caused by charge carrier separation across buried solid-solid interfaces. They also reveal nonlinear optical processes such as the Kerr effect caused by charge dynamics across the interface in addition to the well known SHG process.
AFRIKAANSE OPSOMMING: Die silikon/silikon dioksied (Si/SiO2) skeidingsvlak word algemeen gebruik in mikro-elektronika as die hek tussen die put en die bron van die meeste metaaloksied halfgeleier veld-effek transistors (MOSFETs). Die werkverrigting, betroubaarheid en elektriese eienskappe van sulke transistors word grootliks bepaal deur die kwaliteit van die Si/SiO2 struktuur wat die hek vorm. Karakterisering van die Si/SiO2 skeidingsvlak is belangrik om die degradering van die transistor te verstaan en daarom is die Si/SiO2 skeidingsvlak die onderwerp van intensiewe ondersoek. Ondersoek van die Si/SiO2 skeidingsvlak deur van optiese metodes gebruik te maak is geraporteer deur verskeie internasionale groepe, maar daar bestaan tot vandag toe nog n groot aantal onbeantwoorde vrae. Die fisika van die fotogenduseerde generering van defekte en van posisies waarin ladings gevang kan word, asook die daaropvolgende vasvang van ladingsdraers, die presiese rol van die fotoge¨ınduseerde elektriese veld oor die skeidingsvlak in die verandering van die optiese eienskappe van die Si/SiO2 skeidingsvlak en die grootte van die tweede harmoniek (SH) sein word nog nie goed verstaan nie. In hierdie werk word n kommersile naby-infrarooi femtosekonde (fs) laserbron [1.55 eV, 75 ± 5 fs, 10 nJ, 80 MHz] gebruik om natuurlike Si/SiO2 skeidingsvlakke van vrystaande enkelkristallyne Si membrane en soliede Si te bestudeer. Optiese tweede harmoniek (SH) wat by die Si/SiO2 skeidingsvlakke van ’n Si membraan gegenereer word - in refleksie en vir die eerste keer in transmissie - is gedemonstreer, asook stasionˆere, een-golflengte pomp-toets refleksiemetings op die Si/SiO2 skeidingsvlak van soliede n-gedoteerde Si. Die eksperimentele opstellings vir die tweede harmoniek generering (SHG) en pomp-toets tegnieke is ontwerp en uitgevoer en metings is opgeneem deur ’n rekenaarbeheerde dataversamelingstelsel. Vrystaande Si membraan monsters is suksesvol by die Institut f¨ur Photonische Technologien (IPHT) in Jena, Duitsland vervaardig uit soliede Si deur ’n chemiese etsproses en is gekarakteriseer met behulp van die z-skanderingstegniek as deel van hierdie studie. Die diepte waartoe lig met ’n fotonenergie van 1.55 eV in silikon indring laat die transmissie van die fundamentele fs laserpulse deur die Si membraan (met ∼ 10 μm dikte) toe en dit word ontgin om ’n SH sein van die Si/SiO2 skeidingsvlakke van die Si membraan in transmissie te meet. In die teenwoordigheid van fs laserlig met voldoende intensiteit word defekte by die skeidingsvlakke geskep en bevolk deur meer-foton ladingsoordrag van die Si na die SiO2 waar die ladings daaropvolgens vasgevang word. Die oordrag van ladings skep elektriese velde oor die skeidingsvlakke van die Si membraan en dit versterk die SHG. Hierdie verskynsel word elektriese veld ge¨ınduseerde tweede harmoniek (EFISH) generering genoem. Sover ons kennis strek is die meting van EFISH seine van skeidingsvlakke van Si membrane in transmissie vir die eerste keer in hierdie studie gedemonstreer. Die demonstrasie van EFISH in transmissie het nuwe resultate opgelewer wat ons toegelaat het om bykomende perspektiewe op die EFISH genereringsproses by Si/SiO2 skeidingsvlakke te verskaf waaroor nog nooit vantevore verslag gedoen is nie. Die tydafhanklike gedrag van die SH seine van voorheen onbestraalde posisies is gemeet by verskillende drywings van die inkomende laserbundel vir beide die refleksie en transmissie geometrie¨e. Die gedrag van die SH sein in transmissie is waargeneem om tydafhanklik te wees en ’n toename te toon gedurende bestraling van die monster in ooreenstemming met EFISH prosesse. ’n Reeks van SH metings is opgeneem by verskillende laserdrywings om die groottes van die SH opbrengste in elke meetgeometrie vir ’n enkele Si/SiO2 skeidingsvlak te vergelyk. Die grootte van die SH opbrengs wat in transmissie gemeet is was ho¨er as verwag is en het die grootte van die SH opbrengs in refleksie oortref. Die verwagting is gebaseer op die feit dat die lokale intensiteit by die tweede skeidingsvlak waar SH in transmisie gegenereer word relatief laag is in vergelyking met die lokale intensiteit by die eerste skeidingsvlak waar SH in refleksie ontstaan. ’n Fisiese model is ontwikkel om die eksperimentele resultate wat in hierdie studie verkry is op ’n konsekwente wyse te interpreteer. In hierdie model het ons die oorsprong van EFISH seine in elke meetgeometrie vasgestel, die onverwagte ho¨e SH seine wat in transmissie gemeet is verklaar en ’n analise van die tydkonstantes wat uit die SH gedrag in transmissie en refleksie afgelei is gedoen. Verder rapporteer ons ook vir die eerste keer stasionˆere pomp-toets reflektiwiteitsmetings van soliede n-gedoteerde Si(111) monsters met ’n natuurlike oksied. ’n Sterk pompbundel is gefokus op dieselfde posisie as ’n swak toetsbundel van dieselfde laserbron. Die verandering in reflektiwiteit van die Si(111)/SiO2 stelsel is gemeet deur die verandering in die intensiteit van die swak weerkaatste toetsbundel te monitor. Die tydevolusie van die reflektiwiteit van die mate riaal is gemeet by verskillende pompdrywings. Die reflektiwiteit van die materiaal neem toe gedurende etlike minute van bestraling en bereik ’n stasionˆere toestand na ’n lang tyd van bestraling. Die verandering in reflektiwiteit van die materiaal word toegeskryf aan ’n nielini ˆere prosess, naamlik die Kerr effek, en die tydafhanklike gedrag ontstaan as gevolg van die fotoge¨ınduseerde elektriese veld oor die Si(111)/SiO2 skeidingsvlak wat veroorsaak word deur meer-foton ladingsoordrag van die soliede Si(111) na die SiO2 laag. Die resultate wat in hierdie studie gerapporteer word dra by tot die verstaan van die fotoge ¨ınduseerde elektriese veld oor die skeidingsvlak wat veroorsaak word deur die skeiding van ladingsdraers oor die bedekte kristal-kristal skeidingsvlak. Dit lˆe ook nie-liniˆere optiese prosesse soos die Kerr effek bloot wat veroorsaak word deur die dinamika van ladings oor die skeidingsvlak, bykomend tot die bekende SHG proses.

A sufficiently strong electric field is able to change the cell membrane permeability, forming aqueous pores across it, hence the name electroporation, permitting the passage, otherwise forbidden, of ions and molecules. Since its efficient application in biotechnology and medicine (e. G. Electrochemotherapy), ms/μs-pulse-induced electroporation draws growing interest. Recently, the application of nanosecond pulses has showed electroperturbation on intracellular membranes, opening the way to subcellular manipulations. To date, the mechanisms beyond the electroporation are not still well known. The lack of ultra-rapid and flexible pulsers for cell stimulation on the one hand, and the rapid and subcellular-scale involved dynamics on the other hand, make the investigations complex. In this context, we have designed and realized a compact system providing both the electric pump and the optical probe for electroporation studies. The electric pump consists of a photocommutation-based pulse generator triggered by a sub-nanosecond microchip laser that also provides the optical excitation of the multiplex-CARS microscope used for cell imaging. The main innovation of this system is represented by the sub-nanosecond regime of the common laser source. This choice is justified by the need for synchronizing the nanosecond electrical stimulation with the optical detection. A detailed analysis in the time and frequency domains has been performed in order to verify the whole system efficiency and applicability to nano-electroporation investigations
Un champ électrique suffisamment intense induit des effets sur la membrane cellulaire, notamment la formation des pores qui permettent le passage , autrement interdit, de ions et molécules, d’où le nom électroporation. Grâce à son application à la biotechnologie et à la médecine (électrochimiothérapie), l’électroporation représente un phénomène de grand intérêt. Récemment, des impulsions de l’ordre de la nanoseconde ont étés appliquées, montrant des effets sur les membranes intracellulaires. Les mécanismes qui sont à la base de l’électroporation ne sont pas encore complètement compris. D’une part, il n’y a pas en commerce de générateurs ultra-rapides et flexibles pour une stimulation électrique adaptée. D’autre part, la détection de phénomènes à l’échelle subcellulaire et de dynamiques temporelles rapides résulte très difficile. En ce contexte, nous avons conçu et réalisé un système électro-optique pompe-sonde. Il se compose d’un système optoélectronique dédié à la génération d’impulsions ultracourtes et de forte intensité, et d’une source pour l’imagerie optique non linéaire basée sur la microspectroscopie multiplex-CARS. Les deux sources sont déclenchées par le même laser fonctionnant en régime sub-nanoseconde. Ce régime temporel permet une synchronisation efficace des deux systèmes, mais il nécessite d’une étude approfondie des effets optiques non linéaires qui induisent l’élargissement spectral du faisceau, indispensable pour l’imagerie multiplex-CARS. Une caractérisation dans le temps et en fréquence a été menée afin de vérifier les performances du system entier et son emploi aux études de nano-électroporation

The thesis is dedicated to investigation of carrier dynamics in InN, InGaN, and GaAsBi heterostructures by using light-induced transient gratings and differential transmission techniques. The experimental studies in a wide range of excess carrier densities and temperatures revealed that trap-assisted Auger recombination is the dominant recombination mechanism in MBE-grown InN layers at room temperature. Investigation of carrier dynamics in In-rich InGaN alloys revealed that density of fast nonradiative recombination centers increases with Ga content. The correlation between excess carrier lifetime and diffusion coefficient in MOCVD-grown single InGaN layer with 13% In is governed by diffusive flow to the extended defects. Investigations of carrier lifetime and diffusivity dependence on excitation fluence indicated that both nonradiative and radiative recombination contribute to an increase of excess carrier recombination rate at high photo-excitation levels in MOCVD-grown InGaN multiple quantum wells. Transient grating measurements in MBE-grown GaAsBi layers with different Bi content revealed that Bi induced potential fluctuations determine the tenfold decrease in nonequilibrium hole mobility, if compare to GaAs.
Disertacija skirta nepusiausvirųjų krūvininkų dinamikos tyrimams InN, InGaN ir GaAsBi heterosandarose naudojant šviesa indukuotų dinaminių gardelių ir skirtuminio pralaidumo metodikas. Atlikti tyrimai plačiame nepusiausvirųjų krūvininkų tankių ir bandinio temperatūrų intervale parodė, kad krūvininkų rekombinacijos sparta MBE būdu užaugintuose InN sluoksniuose dominuojantis rekombinacijos mechanizmas kambario temperatūroje yra gaudyklių įtakota Ožė rekombinacija. Nustatyta koreliacija tarp krūvininkų gyvavimo trukmės ir difuzijos koeficiento MOCVD būdu užaugintame InGaN sluoksnyje su 13% In parodė, kad krūvininkų gyvavimo trukmę lemia difuzinė jų perneša link rekobinacijos centrų. Parodoma, kad MBE metodu užaugintuose InGaN sluoksniuose su dideliu In kiekiu (x>0,7) didėjant Ga kiekiui didėja nespindulinės rekombinacijos centrų tankis, o krūvininkų rekombinacijos sparta yra termiškai aktyvuojama. MOCVD metodu užaugintose InGaN kvantinėse sandarose dinaminių gardelių tyrimais parodoma, kad spartėjančią krūvininkų rekombinaciją didėjant sužadinimo intensyvumui lemia ne tik spindulinė rekombinacija, tačiau reikia atsižvelgti ir į nespindulinės rekombinacijos spartėjimą. Nustatyta, kad į GaAs įterpiant Bi atomus daugiau nei dešimt kartų sumažėja skylių judris dėl Bi atomų kuriamų valentinės juostos fliuktuacijų.

Doctor of Philosophy
Department of Physics
Itzhak Ben-Itzhak and Charles Lewis Cocke
A commercially available modern laser can emit over 10^15 photons within a time window of a few tens of femtoseconds (10^-15 second), which can be focused into a spot size of about 10 um, resulting in a peak intensity above 10^14 W/cm^2. This paves the way for table-top strong field physics studies such as above threshold ionization (ATI), non-sequential double ionization (NSDI), high order harmonic generation (HHG), etc.. Among these strong laser-matter interactions, high order harmonic generation, which combines many photons of the fundamental laser field into a single photon, offers a unique way to generate light sources in the vacuum ultraviolet (VUV) or extreme ultraviolet (EUV) region. High order harmonic photons are emitted within a short time window from a few tens of femtoseconds down to a few hundreds of attoseconds (10^-18 second). This highly coherent nature of HHG allows it to be synchronized with an infrared (IR) laser pulse, and the pump-probe technique can be adopted to study ultrafast dynamic processes in a quantum system. The major work of this thesis is to develop a table-top VUV(EUV) light source based on HHG, and use it to study dynamic processes in atoms and small molecules with the VUV(EUV)-pump IR-probe method. A Cold Target Recoil Ion Momentum Spectroscopy (COLTRIMS) apparatus is used for momentum imaging of the interaction products. Two types of high harmonic pump pulses are generated and applied for pump-probe studies. The first one consists of several harmonics forming a short attosecond pulse train (APT) in the EUV regime (around 40 eV). We demonstrate that, (1) the auto-ionization process triggered by the EUV in cation carbon-monoxide and oxygen molecules can be modified by scanning the EUV-IR delay, (2) the phase information of quantum trajectories in bifurcated high harmonics can be extracted by performing an EUV-IR cross-correlation experiment, thus disclosing the macroscopic quantum control in HHG. The second type of high harmonic source implemented in this work is a single harmonic in the VUV regime (around 15 eV) filtered out from a monochromator. Experiments on D_2 molecules have been conducted using the 9th or the 11th harmonic as the pump pulse. Novel dissociative ionization pathways via highly excited states of D_2 have been revealed, thus suggesting potential applications for time-resolved studies and control of photochemistry processes.

Biochemische Prozesse treten in wässriger Umgebung auf und Wechselwirkungen der Wasserhülle mit Biomolekülen spielt eine Schlüsselrolle für deren Struktur und Funktion. In dieser Arbeit wird die Strukturdynamik der Wassermoleküle und Gegenionen in der umgebenden Wasserhülle der DNA mit der Methode der zweidimensionalen Infrarotspektroskopie (2D IR) sowie Anrege-Abfrage-Spektroskopie untersucht. Die Ergebnisse der vorliegenden Arbeit zeigt das starke Potenzial von Schwingungsmoden an Grenzflächen für die Abbildung und das Verständnis von Wechselwirkungen zwischen Biomolekülen und ihrer Wasserhülle. In Zukunft soll dieses Konzept auch auf andere Biomoleküle angewendet werden.
Biochemical processes occur in an aqueous environment and interactions of the water shell with biomolecules play a key role for their structure and function. In this thesis, the structural dynamics of water molecules and counterions in the hydration shell of DNA is investigated by two-dimensional infrared (2D IR) spectroscopy and pump-probe transient spectroscopy. 2D IR spectroscopy is a powerful technique that can track molecular couplings between different vibrational modes and structural fluctuations of the chemical environment on a femto- to picosecond time scale. In the present study, vibrational modes of the DNA backbone serve as probes located at the DNA-water interface. The results of this thesis demonstrate the strong potential of interfacial vibrational modes for mapping and understanding interactions between biomolecules and their water shell. In future, this concept will be applied to other biomolecular systems.

Thesis advisor: Torsten Fiebig
This dissertation introduces a new field of DNA photonics centering on the electronic properties of DNA, which emerges after the initial controversies regarding the long-range conductivity and wire-type behavior of DNA have been widely settled. DNA photonics study is not solely focused on charge transfer phenomena but encompasses all possible photophysical processes and their potentially complex interplays. For instance, ultrafast electronic energy migration, dissipation, and (de)localization on the femtosecond time scale are shown to be crucial for the description of light-induced dynamics in DNA and have been thoroughly investigated in this dissertation. In addition to measurements on natural single and double-stranded DNA, this dissertation also presents experimental data on a series of functionalized DNA systems (derivatized by stilbene, ethidium, 2-aminopurine, etc.), obtained by state-of-the-art femtosecond broadband pump–probe spectroscopy. The results illustrate the distance dependence of charge transfer, emphasize the role of the initial electronic excitation on energy transfer dynamics, and highlight the influence of structural factors on both processes in DNA. Finally, as one initial step towards DNA electronics application, a DNA mimicking system of tertiary arylureas were employed to demonstrate molecular wire behavior, implying its potential use in molecular electronics. Thus, both the experimental and theoretical research accumulated for DNA π–π coupling can be translated into designing and testing various molecular systems with similar π-stacked structures
Thesis (PhD) — Boston College, 2008
Submitted to: Boston College. Graduate School of Arts and Sciences
Discipline: Chemistry

Fast carrier cooling is important for high power graphene based devices. Strongly coupled optical phonons play a major role in the relaxation of photo-excited carriers in graphene. Heterostructures of graphene and hexagonal boron nitride (hBN) have shown exceptional mobility and high saturation current, which makes them ideal for applications, but the effect of the hBN substrate on carrier cooling mechanisms is not understood. We track the cooling of hot photo-excited carriers in graphene-hBN heterostructures using ultrafast pump-probe spectroscopy. We find that the carriers cool down four times faster in the case of graphene on hBN than on a silicon oxide substrate thus overcoming the hot phonon bottleneck that plagues cooling in graphene devices. (C) 2017 Author(s).

An ultrafast UV-visible spectrometer was designed and implemented. An optical parametric amplifier was constructed to be used as a pump source for the spectrometer. Using nonlinear optical processes and an 800 nm ultrashort pulses, tunable infrared(IR) light was produced with a wavelength range of ∼.1 mum to 3 mum. The IR light was then mixed with 800 nm light to produce tunable visible light with a wavelength range of 466 nm to 600 nm. Supercontinuum (SC) was used as the probe pulse of the spectrometer, providing a large observation bandwidth. Commercially purchased fast spectrometers were used as the detection mechanism. The characterization of the set up, as well the observation of some ultrafast molecular dynamics observed in 8-hydroxy-1,3,6-pyrenetrisulfonic acid, are presented.

In this dissertation, we develop pump probe spectroscopy as a method to differentiate different chemical varieties of melanin, a common biopigment, and exploit these differences to improve the accuracy of melanoma diagnosis. This method gives insight into the chemical makeup and secondary structure of melanins. Pump probe spectroscopy is implemented in a scanning laser microscope as a form of multiphoton imaging, where it is used to image biopsies of human pigmented cutaneous lesions. Melanoma diagnosis is clinically challenging: the accuracy of visual inspection by dermatologists is highly variable and heavily weighted toward false positives. Even the current gold standard of biopsy results in varying diagnoses among pathologists. Using pump probe imaging, significant chemical and morphological changes were found between melanoma and melanocytic nevi, including increased eumelanin content, chemical heterogeneity and general pigmentation. Signal processing methods revealed further differences between melanoma and melanocytic nevi on the cellular scale. Pump probe imaging directly in H&E stained biopsy samples allows integration of this technique with existing histopathology protocols. High resolution imaging found chemical heterogeneity of melanin within pigmented cells. We show that oxyhemoglobin and deoxyhemoglobin may also be differentiated by pump probe imaging. Epi mode imaging of eumelanin, pheomelanin and microvasculature is demonstrated in vivo in human xenograft mouse models of melanoma.

Dissertation

碩士
國立交通大學
電子物理學系
83
We have successfully built up a femtosecond pump-probe system to measure the relaxation behaviors of photoexcited carriers in both superconducting and semiconducting thin films. The laser source is a home-made passively mode-locked Ti: sapphire laser producing pulses with pulsewidth of about 150 fs and average power of about 400 mW. The output beam is guided into a home- made pump-probe system which can detect the change of reflectivity as small as 5*10^-5. Lock-in and differential detection techniques also have been used to obtain the measurement results with better signal to noise ratio. We have performed a series of femtosecond reflectivity measurements on both high Tc superconducting YBCO thin films with different oxygen contents and semiconducting GaAs thin films with different manufacturing processes and annealing conditions. We have found qualitatively different behaviors in the sign, magnitude and temporal response as various manufacturing processes of these thin films. Detailed explanation of the experimental results can be obtained by further improving the resolution of the pump-probe system and by measuring the electrical properties of these thin films.