All-optical time-resolved measurement techniques provide a powerful tool for investigating critical parameters that determine the performance of infrared photodetector and emitter semiconductor materials. Narrow-bandgap InAs/GaSb type-II superlattices (T2SLs) have shown great promise as next generation materials, due to superior intrinsic properties and versatility. Unfortunately, InAs/GaSb T2SLs are plagued by parasitic Shockley-Read-Hall recombination centers that shorten the carrier lifetime and limit device performance. Ultrafast pump-probe techniques and time-resolved differential-transmission measurements are used here to demonstrate that "Ga-free" InAs/InAs₁₋xSbx T2SLs and InAsSb alloys do not have this same limitation and thus have significantly longer carrier lifetimes. Measurements of unintentionally doped MWIR and LWIR InAs/InAs₁₋xSbx T2SLs demonstrate minority carrier (MC) lifetimes of 18.4 µs and 4.5 µs at 77 K, respectively. This represents a more than two order of magnitude increase compared to the 90 ns MC lifetime measured in a comparable MWIR and LWIR InAs/GaSb T2SL. Through temperature-dependent differential-transmission measurements, the various carrier recombination processes are differentiated and the dominant recombination mechanisms identified for InAs/InAs₁₋xSbx T2SLs. These results demonstrate that these Ga-free materials are viable options over InAs/GaSb T2SLs and potentially bulk Hg₁₋xCdxTe photodetectors. In addition to carrier lifetimes, the drift and diusion of excited charge carriers through the superlattice layers (i.e. in-plane transport) directly aects the performance of photo-detectors and emitters. All-optical ultrafast techniques were successfully used for a direct measure of in-plane diffusion coeffcients in MWIR InAs/InAsSb T2SLs using a photo-generated transient grating technique at various temperatures. Ambipolar diffusion coefficients of approximately 60 cm²/s were reported for MWIR InAs/InAs₁₋xSbxT2SLs at 293 K.

Les nanoparticules plasmoniquespossèdent des propriétés intéressantes grâce àla résonance de plasmon de surface localisé. Enplus de leur grande efficacité de conversionphotothermique due au plasmon, leconfinement de l’échauffement peut êtremodulé par le type de source lumineuseutilisée (impulsionnelle ou continue). Cespropriétés font des nanoparticulesplasmoniques une solution potentielle pour lathérapie contre le cancer par hyperthermie.Afin de développer une telle applicationbiomédicale, il est nécessaire d'optimiserl'absorption de l'énergie lumineuse et le ciblagedes nanoparticules sur la tumeur considérée.Dans cette thèse, l'influence des électronschauds photo-générés sur l'absorptiond’impulsions laser ultracourtes par lesnanoparticules est d'abord étudiée. Ensuite, untravail effectué avec des chimistes, biologisteset médecins pour l'application desnanoparticules d’or irradiées par impulsionslaser ultracourtes à la thérapie contre le cancerest présenté. Enfin, nous présentons une étudepréliminaire sur la photoluminescence denanoparticules plasmoniques, dont l'origine estencore controversée, en appliquant un modèleprenant en compte la nature non thermale dela distribution d’électrons chauds. / Plasmonic nanoparticles possessinteresting properties thanks to the localizedsurface plasmon resonance. In addition totheir high photothermal conversion efficiency,the heat release confinement can bemodulated by the type of light source used(pulsed or continuous laser). These propertiesmake the plasmonic nanoparticles a potentialsolution for cancer therapy by hyperthermia.In order to develop such a biomedicalapplication, it is necessary to optimize theabsorption of light energy and the targeting ofnanoparticles on the tumor considered.In this thesis, the influence of the photogeneratedhot electrons on the absorption ofultrashort laser pulses by nanoparticles is firststudied. Then, a work carried out withchemists, biologists and physicians for theapplication of gold nanoparticles irradiated byultrashort laser pulses to cancer therapy isdescribed. Finally, we present a preliminarystudy on the photoluminescence of plasmonicnanoparticles, the origin of which is stillcontroversial, by applying a model accountingfor the non-thermal nature of the hot electrondistribution.

京都大学 / 新制・課程博士 / 博士(医学) / 甲第23073号 / 医博第4700号 / 新制||医||1049(附属図書館) / 京都大学大学院医学研究科医学専攻 / (主査)教授 溝脇 尚志, 教授 黒田 知宏, 教授 増永 慎一郎 / 学位規則第4条第1項該当 / Doctor of Medical Science / Kyoto University / DGAM

Organic photovoltaics has emerged as a promising technology for electricity generation. The essential component in an organic solar cell is the bulk heterojunction absorber layer, typically a blend of an electron donor and an electron acceptor. Efforts have been made to design new materials such as donor polymers and novel acceptors to improve the power conversion efficiencies. New fullerene free acceptors providing low cost synthesis routes and tenability of their optoelectronic and electrochemical properties have been designed. Despite the efforts, still not much is known about the photopysical processes in these blends that limit the performance. In this respect, time-resolved spectroscopy such as transient absorption and time-resolved photoluminescence, can provide in-depth insight into the various (photo) physical processes in bulk heterojunction solar cell. In this thesis, PCE10 was used as donor and paired with different non fullerene acceptors. In the first part of this thesis the impact of the core structure (cyclopenta-[2, 1-b:3, 4-b’]dithiophene (CDT) versus indacenodithiophene (IDTT)) of malononitrile (BM)-terminated acceptors, abbreviated as CDTBM and IDTTBM, on the photophysical characteristics of BHJ solar cells is reported. The IDTT-based acceptor achieves power conversion efficiencies of 8.4%, higher than the CDT-based acceptor (5.6%), due to concurrent increase in short-circuit current and open-circuit voltage. Using (ultra)fast transient spectroscopy we demonstrate that reduced geminate recombination in PCE10: IDTTBM blends is the reason for the difference in short-circuit currents. External quantum efficiency measurements indicate that the higher energy of interfacial charge-transfer states observed for the IDTT-based acceptor blends is the origin of the higher open-circuit voltage. In the second part of this thesis, I report the impact of acceptor side chains on the photo-physical processes of BHJ solar cells using three different IDT-based acceptors, namely O-IDTBR, EH-IDTBR and O-IDTBCN blended with PCE10. Power conversion efficiencies as high as 10 % were achieved. The transient absorption spectroscopy experiments provide insight into sub-picosecond exciton dissociation and charge generation which is followed by nanosecond triplet state formation in PCE10:O-DTBR and PCE10:EH-IDTBR blends, while in O-IDTBCN triplets are not observed. Time delayed collection field experiments (TDCF) were performed to address the charge carrier generation and examine its dependence on the electric field.

Balancing increased safety against detonation performance is paramount for new explosive energetic materials in the development process. Often these two requirements are in opposition to each other. Sensitivity tests to external stimuli are used to determine how safe an energetic material is to phenomena such as impact, heat, or friction. Meanwhile, detonation performance is assessed by the maximum pressure and shock velocity induced from chemical reactions. Tailoring the performance while maintaining safety of the explosive would be possible with knowledge of the chemical reactions that functional groups provide during detonation. Current knowledge of the chemical reactions that occur during detonation is limited. Several mechanisms have been suggested for first step reactions throughout the detonation process for energetic molecules; however, no single chemical pathway has been irrefutably substantiated by experiments. Alternatively, models can provide insight into the types of reactions that may transpire, but lack direct experimental comparisons. If experiments and models could be compared at the equivalent time and length scales, then measurements could guide the physics and chemistry assumptions present in models. Experiments presented in this document bridge that gap by using an ultrafast laser system to generate shocks in samples and spectroscopically probe vibrational and electronic absorption changes that occur during shock compression. A review of how to turn a benchtop chirped pulse amplifier into a shock physics and chemistry laboratory is first presented. Applications of the spectroscopic techniques developed were then applied to trinitrotoluene (TNT) and pentaerythritol tetranitrate (PETN) during shock compression. Mid-infrared absorption results for shock compressed TNT and PETN were compared to current suggestions on chemical pathways and inconsistencies were present for both materials. It is suggested that a carbon-carbon bond breaking mechanism is present for PETN, and a hydrogenic stretch like hydroxyl or amide bond formation mechanism is suggested for TNT based on the MIR absorption measurements. Recommendations for future experimental thrusts are also provided. The results provided in this document could be directly compared to simulations to refine the assumptions present in models.

Title: Study of semiconductors by methods of time resolved laser spectroscopy: Luminescence spectroscopy of nanocrystalline diamond Author: Branislav Dzurňák Department: Department of Chemical Physics and Optics Supervisor: doc. RNDr. František Trojánek, Ph.D. Abstract: The PhD thesis is focused on optical properties of nanocrystalline diamond prepared by chemical vapour deposition method. Photoluminescence of nanocrystalline diamond samples and effects of ambient temperature, pressure, pH and UV irradiation on it are studied by laser spectroscopy. Results suggest the keyrole of water and air adsorbates which affect the energy states in the sub-bandgap region of diamond. Photoluminescence decay of samples of different surface termination and structure and its dependency on ambient pressure and temperature is studied by methods of ultrafast (picosecond and nanosecond scale) laser spectroscopy. Results are analysed by power-law decay function which fits well the luminescence decay curves and also describes the dynamics of charge carriers in states localised within the bandgap. The model of interaction of nanocrystalline diamond with air adsorbates is proposed. Non-linear optical properties of nanocrystalline diamond are also studied, namely the generation of second and third harmonic frequency. The thesis...

Název práce: Optické vlastnosti křemíkových nanostruktur pro fotovoltaiku Autor: Bc. Jan Salava Katedra: Katedra chemické fyziky a optiky Vedoucí diplomové práce: doc. RNDr. František Trojánek, Ph.D., katedra chemické fyziky a optiky Abstrakt: V předložené práci jsou studovány křemíkové nanokrystaly umístěné v SiC matrici - jednotlivé vzorky se odlišují přidáním dopantu (boru) do příslušné vrstvy struktury během depozice metodou PECVD a pasivací vodíkem. Křemíkové nanokrystaly jsou významné zejména tím, že oproti své objemové verzi vykazují účinnou fotoluminiscenci a absorpci ve viditelné oblasti spektra. Změnami parametr· při přípravě lze ladit jejich vlastnosti s ohledem na konkrétní aplikaci. Základní myšlenka integrace křemíkových nanostruktur do solárních článk· spočívá ve zvýšení účinnosti konverze slunečního spektra kombinací několika tenkých vrstev s nanokrystaly a objemového Si článku tak, aby každá vrstva sluneční cely absorbo- vala určitou část spektra. Procesy, které se v těchto strukturách dějí krátce po excitaci nosič· náboje, však stále nejsou zcela popsány. Cílem práce je charakterizace těchto jev· metodami ča- sově rozlišené spektroskopie. Dalším úkolem je popsat vliv dopování jednotlivých částí materiálu a jeho pasivace ve vodíkové atmosféře na chování fotoexcitovaných nosič· a intenzitu...

In this work we investigate changes in dynamics of CdSe nanocrystalline films caused by different annealing temperatures and different conditions during films growth. We use methods of time-resolved laser spectroscopy like time-resolved pump and probe and streak camera to study these dynamics. We also measured linear absorption and luminiscence. Our goal is to match measured dynamics with dynamics of other samples with different annealing temperatures and discuss the microscopic origin of these dynamics. Powered by TCPDF (www.tcpdf.org)

In this work, optical pump – near-infrared probe and near-infrared pump – mid-infrared probe spectroscopy are used for the investigation of pressure-induced insulator-tometal transitions in transition metal oxide compounds. The materials under study are a-Fe₂O₃, also known as hematite, and VO₂. Both materials undergo pressureinduced metallization. However, the physical mechanisms of this phase transition are very different for these systems and have not been fully understood up to now. Using ultrafast pump-probe spectroscopy we obtain an insight into the evolution of the band structure and electron dynamics across the insulator-to-metal transition. In the case of VO₂, our near-infrared pump – mid-infrared probe experiments reveal a non-vanishing pumping threshold for photo-induced metallization even at our highest pressures around 20 GPa. This demonstrates the existence of localized charge carriers and the corresponding persistence of a band gap. Besides the threshold behaviour for photo-induced metallization, the carrier relaxation time scale, and the linear reflectivity and transmissivity have been studied under pressure increase. An anomaly in the threshold behaviour as well as the linear reflectivity and transmissivity at a critical pressure around 7 GPa indicates band gap filling under pressure. This is further supported by results obtained under decompression, where the changes of the linear reflectivity turned out to be almost fully reversible. The observations on VO₂ are highly reproducible and can be explained in terms of a pressure-induced bandwidth-driven insulator-to-metal transition. Fe₂O₃ has been studied via optical pump – near-infrared probe spectroscopy up to pressures of 60 GPa. In the pressure range up to 40 GPa, the changes of the response can be explained by photo-induced absorption and bleaching. The pressure-dependent study of the relaxation dynamics allows to identify cooling of the electron system as origin of the picosecond relaxation process.

Thulium (Tm) based high repetition rate compact optical frequency comb sources operating in the 2 µm regime with femtosecond pulse durations enable a wide range of applications such as precise micro-machining, spectroscopy and metrology. Applications such as metrology and spectroscopy rely on the stability of mode-locked lasers (MLLs) which provide extreme precision, yet, the complex dynamics of such highly nonlinear systems result in unstable events which could hinder the normal operation of a MLL. MLL as a nonlinear system inherently exists a wide variety of complex attractors, which are sets of states that the system tends to evolve toward, exhibiting unique behaviors. Complex phenomena including pulsating solitons, chaotic solitons, period-doubling, soliton explosion, etc., have been predicted theoretically and observed experimentally in the past decade. However, most experimental observations rely on conventional characterization methods, which are limited to the scanning speed of the spectrometer and the electronic speed of photodetector and digitizer, so that the details of the non-repetitive events can be buried. In recent years, a technique called dispersive Fourier transform (DFT) has been developed and allows consecutive recordings of the pulse-to-pulse spectral evolution of a femtosecond pulse train, opening a whole new world of nonlinear dynamics in MLL. In this dissertation, we first demonstrate the ability of scaling the repetition rate of a Tm MLL to repetition rate as high as 1.25 GHz through miniaturizing the cavity. Our approach of maintaining comparable pulse energies while scaling the repetition rates allows a high-quality femtosecond mode-locking performance with low noise performance in Tm soliton lasers. Then we experimentally study the transition dynamics between consecutive multi-pulsing states through adjusting pump power with a constant rate in an erbium-doped fiber laser, specifically the build-up and annihilation of soliton pulses between a double pulsing and a three-pulse state utilizing DFT. To investigate real-time laser dynamics in Tm based laser systems, we propose and develop a DFT system that up-converts the signal to the 1 µm regime via second harmonics generation (SHG) and stretches the signal in a long spool of single-mode fiber to realize DFT. This approach overcomes the limitation of bandwidth of 2 µm photodetector and high intrinsic absorption of 2 µm light in fused silica fibers. The SHG-DFT system is used to study dynamics of both explosions in a chaotic state between stable single-pulsing and double-pulsing state, and explosions induced by soliton collision in a dual-wavelength vector soliton state. We also study dynamics of transient regimes in a Tm-doped fiber ring laser that can be switched between conventional soliton and dissipative soliton, revealing how spectral filtering plays a role in obtaining stable stationary states. / 2022-11-23T00:00:00Z