Two dimensional (2D) materials are poised to revolutionize the future of optics and electronics. The past decade saw intense research centered around graphene. More recently, the tide has shifted to a bigger class of two-dimensional materials including graphene but more expansive in their capabilities. The so called ‘2D material zoo’ includes metals, semi-metals, semiconductors, superconductors and insulators. The possibility of mixing and matching 2D materials to fabricate heterostructures with desirable properties is very exciting. To make devices with superior electronic, optical and thermal properties, we need to understand how the electrons, phonons and other quasi particles interact with each other and exchange energy in the femtosecond and nanosecond timescales. To measure the timescales of energy distribution and dissipation, I used ultrafast pump-probe spectroscopy to perform time-domain measurements of optical absorption. This approach allows us to understand the impact of manybody interactions on the bandstructure and carrier dynamics of 2D materials. After a brief introduction to femtosecond laser spectroscopy, I will explore the transient absorption dynamics of three classes of 2D materials: intrinsic graphene, graphene-hBN heterostructures and Transition Metal Dichalcogenides (TMDs). We will see that using pumpprobe measurements around the high energy M-point of intrinsicgraphene, we can extract the value of the acoustic deformation potential which is vital in characterizing the electron-acoustic phonon interactions. In the next part of the thesis, I will delineate the role of the substrate in the cooling dynamics in graphene devices. We will see that excited carriers in graphene on hBN substrates cool much faster that on SiO2 substrates due to faster decay of the optical phonons in graphenehBN heterostructures. These results show that graphene-hBN heterostructures can solve the hot phonon bottleneck that plagues graphene devices at high power densities. In the last part, I will demonstrate the role of phonon induced bandgap renormalization in the carrier dynamics of TMD materials and measure the timescale of phonon decay through the generation of low-energy phonons and transfer to the substrate. This study will help us understand carrier recombination in TMD devices under high-bias conditions which show great potential in opto-electronic applications such as photovoltaics, LEDs etc.

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.

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.

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<p>The Fenna-Matthews-Olson (FMO) complex is a photosynthetic pigment-protein complex that has been the subject of study of decades of research, both experimental and theoretical. The FMO complex is small enough that computational modeling is feasible, while the rich excitonic interactions between the pigments give rise to absorption and circulardichroism (CD) spectra with many interesting details. This makes FMO an excellent testing ground for new predictive modeling techniques.</p> <p><br></p> <p>In this work we model the FMO complex from first-principles, wherein the only input is the X-ray crystal structure of the protein. We compute steady-state absorption and CD spectra of wild-type (WT) FMO as well as two mutants, Y16F and Q198V, in which amino acid residues near pigment 3 and pigment 7 are replaced respectively. CD spectra contain extra structural information and thus provide another avenue of investigation into the electronic properties of the FMO complex. We find that while there are large structural changes in the mutants, not all of the structural changes produce significant spectral changes. We conclude that the primary contributor to the spectral changes in Y16F is the breaking of a hydrogen bond between the nearby tyrosine and pigment 3. On the other hand, the spectral changes in Q198V are due to a collection of effects cancelling one another out to varying degrees, all induced by widespread structural changes as a result of the mutation.</p> <p><br></p> <p>We then perform time-resolved absorption and CD spectroscopy measurements on WT, Y16F, and Q198V FMO to provide a high quality set of experimental data against which the first-principles spectra can be validated. We find that in order to accurately model the triplet energy transfer dynamics in FMO two effects must be accounted for in the modeling: (1) the Stark shift caused by the rotation of the bacteriochlorophyll’s permanent dipole moment upon entering a triplet state, and (2) decays must be modeled as Boltzmann populations rather than individual pigments.</p>

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