La précision des calculs théoriques d'électrodynamique quantique dans l'atome d'hydrogène est actuellement limitée par la constante de Rydberg et la distribution de charge du proton. La comparaison entre ces calculs et les mesures expérimentales de deux fréquences de transition dans l'hydrogène permet d'extraire ces deux constantes. La mesure de la transition 1S-2S est la plus précise à ce jour avec une incertitude relative de 10-15. L'objectif de mon travail de recherche est d'améliorer la précision de mesure de la fréquence de la transition 1S-3S, pouvant être utilisée comme la deuxième mesure nécessaire.La transition 1S-3S est sondée par une excitation à deux photons à 205 nm, permettant de s'affranchir de l'effet Doppler du 1er ordre. Ce faisceau UV est produit par somme de fréquence dans un cristal non linéaire. L'onde lumineuse délivrée par un laser Titane-saphir à 894 nm est sommée avec un faisceau à 266 nm produit par doublage d'un laser Nd-YO4. Cette somme de fréquence délivre un faisceau continu à 205 nm d'une puissance de 15 mWLa distribution de vitesse du jet atomique, dont la connaissance est indispensable pour évaluer l'effet Doppler du 2ème ordre, est déterminée grâce à l'effet Stark motionnel où l'action d'un champ magnétique produit un décalage en fréquence quadratique en vitesse.Les fréquences des deux lasers sources sont mesurées à l'aide un peigne de fréquence optique.La fréquence de la transition 1S-3S est finalement déterminée avec une incertitude relative de 10-12. Sa valeur conduit à une valeur préliminaire du rayon du proton qui serait en contradiction avec celle préconisée par le CODATA. / The uncertainty of the Quantum Electrodynamics calculations for hydrogen atom is currently limited by the knowledge of the Rydberg constant and the proton charge radius. Those two quantities can be extracted from the comparison between the theoretical predictions and two different frequency measurements on hydrogen.The 1S-2S transition frequency is one measured with the highest resolution with a relative uncertainty of 10-15. The aim of this thesis is to improve the determination of the 1S-3S transition, which can be used as the second precise measurement. The 1S-3S two-photon transition is excited at 205 nm. This UV light beam is generated by frequency mixing in a non-linear crystal. An 894 nm light delivered by a Ti:Sa laser is mixed with a 266 nm light beam generated by a quadrupled Nd:YVO4 laser. A reliable 15 mW continuous radiation at 205 nm is then produced. The frequencies of both lasers are measured simultaneously using an optical frequency comb referenced to a cesium clock. To evaluate the second-order Doppler effect, the velocity distribution of the atomic beam is determined thanks to a motional Stark effect. This effect is realized with a static magnetic field which induces a velocity-dependent quadratic frequency shift. Finally, the frequency of the 1S-3S transition is determined with a relative uncertainty of 10-12 which is accurate enough to contribute to the “proton size puzzle”. However, depending on the velocity distribution used in the analysis, the obtained value agrees or not with the present recommended CODATA value.

In donor-acceptor systems, ultrafast interfacial charge transfer (CT), charge separation (CS) and charge recombination (CR), are among the key factors in determining the overall efficiency of the optoelectronic devices. In this regime, precise knowledge of the mechanisms of these processes on the femtosecond scale is urgently required. In this dissertation, using femtosecond transient absorption and mid-Infrared spectroscopies along with steady-state absorption and emission measurements, we are not only able to address the fundamental understanding of these ultrafast dynamical processes, but also control them at various inter- and intramolecular electron donor-electron acceptor systems. In the photoinduced intermolecular charge transfer systems, where donor and acceptor are separated from each other, three systems have been investigated; cationic poly[(9,9-di(3,3′-N,N′-trimethylammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) conjugated polymer donor with 1,4-dicyanobenzene (DCB) acceptor, negatively charged porphyrin (POS) donor with positively charged (PFN) acceptor, and finally, positively charged (PFN) donor with negatively charged graphene carboxylate (GC) acceptor. Based on studying these three systems, we were able to explore some important factors and deriving forces including chemical structure, electrostatic interactions, energy band alignment, hydrogen bonding and solvents with different polarities and capabilities for hydrogen bonding that influence the rate and efficiency of the charge transfer at the interfaces of these donor-acceptor systems. For instance, unlike the conventional understanding of the key role of hydrogen bonding in promoting the charge-transfer process, our results reveal that the hydrogen-bonding increases the spacing between the donor and acceptor units which significantly hinders the charge-transfer process. On the other hand, in the photoinduced intramolecular charge transfer systems, where donor and acceptor are chemically attached to each other, we investigate the effects of conjugation length on photoinduced charge transfer in π-conjugated oligomers naphthalene diimide (NDI) end-capped oligo(phenylene ethynylene)s (PEn-NDI), and poly-(phenylene ethynylene) (PPE) donor backbone with (NDI) acceptor end-caps (PPE-NDI-n) systems. The results of femtosecond transient absorption and mid-IR spectroscopies show that the charge separation occurs on the 1-10 ps time scale with the rates decreasing as oligomer length increases in PEn-NDI system. In addition, in PPE-NDI-n system, the fluorescence quenching measurements indicate very efficient photoinduced electron transfer from the PPE backbone to the NDI end-groups, and the transfer efficiency increases with decreasing the number of units. Finally, the new physical insights reported in this thesis provide an understanding of several key variable components involved, thus paving the way toward the exploitation of efficient charge transfer at donor-acceptor interfaces, which is the key element and urgently required for optimal optoelectronic-device performance.

Optoelectronics in the deep-ultraviolet (DUV) regime is still a growing research field that requires significant effort to understand the material properties and optimize the device structures to realize efficient DUV devices. Aluminum gallium nitride (AlGaN) is perhaps the most studied semiconductor to replace the environmentally hazardous mercury lamps; however, the external quantum efficiency of AlGaN based DUV devices is insufficient to replace the existing old-fashioned mercury UV lamps. Despite the tunability in the bandgap of AlGaN, the excessive strain accumulation associated with increased alloying of Al in AlGaN and the poor dopant activation due to the relatively large ionization energy of the donors and acceptors are not favorable for realizing efficient DUV emitters. In addition, the crossover among the light hole, heavy hole and split-off bands in the valance band for Al-rich AlGaN suppresses the transverse-electric polarization, which further worsens the external quantum efficiency. Furthermore, for DUV photodetection, commercially available Si-photodetectors suffer from poor responsivity for wavelengths shorter than 400 nm in contrast to the visible spectrum. Hence, the-state-of-art photodetectors in the DUV regime also need a significant upgrade, particularly for high-speed applications. Firstly, we utilized the high quantum confinement in plasma-assisted MBE grown ultrathin GaN QDisks to realize DUV (λ ≈ 260 nm) emission using a binary compound (GaN) in contrast to conventionally used ternary compound (AlGaN). More importantly, we experimentally demonstrated TE-dominant DUV emission, unlike Al-rich AlGaN, illustrating a unique pathway for realizing efficient DUV vertical emitters. Secondly, inspired by the light manipulation technique practiced in nature, we presented iridocytes on giant clams (Tridacna maxima), known for their symbiotic relationship with algae as a color downconverting material for DUV photodetection. Investigating the structural and optical properties of iridocytes found in Tridacna maxima, we established a robust UV communication allowing the data transfer rate of 100 Mbit/s within the forward error correction limit for modulated 375 nm-laser diode. Using a similar matrix implemented to 375 nm-laser, with high-power UV-C LED (λ ≈ 278 nm), we could establish an optical wireless communication that could allow a data-transmission rate of tens of Mbit/s within the forward error correction limit.

This diploma thesis deals with the structural and optomechanical design of automatization of focusing laser beam for a remote laser spectroscopy device. The chosen solution uses an active rangefinder and a rotary unit to control the change of the focus plane of the device's optic system. The dependence of the focus plane’s change on the shift of lens in the focus plane was practically measured. For proper control of the rotary unit, this dependency is needed. Structural parts were made based on the created drawing documentation. The structural parts were mounted in the existing assembly of the device together with the purchased components. The proposed solution enables a change of the optical system, for example, in order to obtain a more appropriate range of focal planes.

Title: Dynamics of photoexcited charge carriers in diamond Author: Bc. Tomas Popelar Department: KCHFO MFF UK Supervisor: prof. RNDr. Petr Maly DrSc., KCHFO MFF UK Abstract: In this work we examine the luminescence from diamond in the strong excitation regime by one-photon or two-photon absorption of femtosecond laser beam. Measured sample was very pure type IIa diamond prepared by CVD method which was held in cryostat in order to measure temperature dependant luminescence in range from 12 K to 300 K. The signal was collected and analyzed either by spectrograph or streak camera so we gained time-integrated and time-resolved results. We analyzed only the part of the spectrum containing contributions from electron-hole liquid (for low temperatures), free excitons and probably exciton complexes. For higher temperatures where the condensation is not possible the contribution from e-h plasma was too weak compared to free excitons and was only detectable by time-resolved measurements. Other time-dependant results were obtained by pump and probe experiment with which we examined a change of life- times based on mode of excitation (one-photon or two-photon one) and also an influence of other beams on the condensation into electron-hole drops. Keywords: CVD diamond, dynamics, e-h liquid, excitons

Due to its extraordinary features and wide bandwidth (5.47 eV), diamond is a very promising material in the field of optoelectronics. By absorbing ultraviolet light, excited charge carriers - electrons and holes - are created in the diamond, which can create excitons due to mutual Coulomb interaction. For low temperatures and high concentrations of photoexcitated carriers, carriers can condense into electron-hole droplets and form an electron-hole liquid. The aim of this diploma thesis is to follow up with previous research at the department and to examine the dynamics of electron-hole liquid in bulk diamond at low temperatures. Using femtosecond laser spectroscopy, we investigate the influence of excitation wavelengths on the dynamics of electron-hole liquid condensation.

<p>The work presented here employs cryogenic ion spectroscopy for the study of protein structure, kinetics, and dynamics. The main technique used is IR-UV double resonance spectroscopy. Here peptide ions are generated through nano electrospray ionization, guided into a mass spectrometer, mass selected, and then guided into a cryogenically held octupole ion trap. Ions are subsequently cooled to their vibrational ground state through collisions with 5 K helium allowing for high resolution IR and UV spectra to be recorded. The IR spectra are highly sensitive to an ion’s conformation, and the well resolved UV spectra provides a means generate conformer specific IR spectra. With the use quantum mechanical calculations, it is possible to calculate the vibrational spectra of candidate structures for comparison with experimental spectra. Strong correlations between theory and experiment allow for unambiguous structural assignments to be made.</p> <p> Structural studies are performed on β-turn motifs and well as salt-bridge geometries. Beta-turns are a commonly occurring secondary structure in peptides and proteins. It is possible to artificially encourage the formation of this secondary structural element through the incorporation of the D-proline (^DP) stereoisomer followed by a gly or ala residue. Interestingly, the L-proline (^LP) stereoisomer is seen to discourage the formation of beta turn structure. Here were probe the inherent conformational preferences of the diastereomeric peptide sequences YA^LPAA and YA^DPAA. The findings agree with solution phase studies, the ^DP sequence is observed to adopt a beta turn however, the ^LP sequence is found to undergo a sterically driven <i>trans</i> à <i>cis</i> isomerization about the proline amide bond. We find the energetics associated with this unfavorable interaction and show the ability to reverse it by proper substitution of Ala₂ for a Gly.</p> <p>The studies directed towards gas phase salt bridges have been limited to single amino acids or dipeptides. Generally, these species are ionized using a metal ion or adducted with water or excess electrons in order to stabilize a zwitterionic motif. Here we take the first look at a salt bridge motif incorporated into polypeptide in order to understand how the solvation from the secondary structure can aid in stabilizing these motifs in non-polar environments. We find a unique salt bridge motif in the YGRAR sequence in which the tyrosine OH acts as a neutral bridge to form a network between the C-terminal arginine and the ion pair formed between the central arginine and C-terminal carboxylate group. This binding motif has not been discussed in literature and appears as an important structural element in non-polar environments as all salt bridge character is lost upon substituting Tyr for Phe. We are the process of mining the PDB for these types of interactions. </p> <p>To better understand how cryo-cooling impacts the resulting population distribution at 10 K we measured the distribution among the two major conformation of the YGPAA ion. This was carried out using population transfer spectroscopy. In this method conformational isomerization is induced vis single conformer infrared excitation. The change in population can be related to the final population distribution at 10 K. With this number, we were able to develop a cooling model to simulate the change in the distribution as a function of cooling. The cooling rates, were experimental established, and the isomerization rates and starting population were theoretically derived through RRKM and thermodynamic calculations. With these parameters and cooling model, we found that the room temperature population distribution is largely preserved. When isomerization events involve breaking a hydrogen bond, they become too slow to complete with the cooling time scale of the experiment, effectively freezing in the room temperature structures. These are important physical parameters to characterize when performing structural studies at 10 K.</p> <p>Finally, we demonstrate a 2-Color IRMPD technique that is able to generate linear spectra at varied temperatures. This is in sharp contrast to traditional IRMPD which results in non-linear and skewed spectra. The importance of generating linear spectra when making structural assignments is highlight by comparing the performance between both techniques. Furthermore, with this technique we show the ability to record the spectra of ion prepared with high internal energies. This provides spectroscopic snapshots of the unfolding events leading to dissociation. Overall, the versatility of this technique to record ground state spectra comparable to IR-UV DR, to record linear spectra at room temperature, and to probe dynamics proves this technique to be useful in the field of ion spectroscopy.</p>

Abstract: Understanding and controlling the ultrafast charge carrier and exciton dynamics at the interface of semiconductor nanocrystals (NCs) offer an excellent opportunity to improve the charge collection and the overall performance of many optoelectronic and energy-based devices. In this dissertation, we study how interfacial engineering of these materials can have a direct influence on controlling the charge transfer and the nonradiative losses in different donor-acceptor systems. The first introductory chapter provides an overview of all the fundamental photophysical processes controlling the interfacial phenomena. Then, the second chapter highlights all the chemicals and synthesis methods employed during this thesis. The subsequent two chapters discuss the detailed experimental studies and observations related to different materials and interfaces. First, it describes how we can dramatically tune the intersystem crossing (ISC) rate, the triplet state lifetime, turn on/off the electron injection at the CdTe-Prophyrin interface via tuning either the quantum dot size or the porphyrin molecular structure. Also, how the intermolecular distances, electronic coupling, and subsequently, the photoinduced charge transfer can be controlled by the interfacial electrostatic interactions at CdTe-Fullerene interfaces. Second, due to the promise that of perovskite NCs holds for improving many solar cell and optoelectronic applications, chapter 3 highlights the tremendous effect that the shape of perovskite nanocrystals has on the rate and the mechanism of charge transfer at the MAPbBr3- TCNE interface. Besides, it demonstrates how the confinement effect brought by changing the dimensionality influence the charge transfer dynamics at the MAPbBr3-BQ interface. Finally, it explains how the effective passivation of the surface defects and the subsequent suppression of the formation of surface nonradiative recombination centers in CsPbCl3 NCs controls the photoluminescence quantum yield and the photodetector performance.

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第19029号 / 農博第2107号 / 新制||農||1030(附属図書館) / 学位論文||H27||N4911(農学部図書室) / 31980 / 京都大学大学院農学研究科地域環境科学専攻 / (主査)教授 谷 誠, 教授 北山 兼弘, 教授 川島 茂人 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

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