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Al, Otaify Ali Abdullah. "Ultrafast charge dynamics in novel nanoparticles." Thesis, University of Manchester, 2015. https://www.research.manchester.ac.uk/portal/en/theses/ultrafast-charge-dynamics-in-novel-nanoparticles(ec75ab4e-71cd-4051-8683-be3c724746c5).html.
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The ultrafast charge dynamics in a number of nanostructured materials relevant to the production of renewable energy are investigated using ultrafast transient absorption spectroscopy. The materials include mercury telluride and cadmium mercury telluride quantum dots, and gold nanoparticles loaded on titanium dioxide colloidal spheres. The analysis of the resultant pump-induced transmittance change spectra and transients allow the determination of charge relaxation routes including multiple exciton generation, trion formation and direct-surface trapping. The investigation of HgTe QDs passivated with thioglycerol, mercaptopropionic acid and dodecanethiol ligands suggests that mercaptopropionic acid ligand results in better passivation of HgTe QDs due to its carboxylic acid group. It allows more electron density donation to the QD surface to passivate the traps related with unsaturated Hg bonds and hence supresses the associated non-radiative processes. The decay lifetimes of the thioglycerol/dodecanethiol-capped QDs in addition to the photo-induced absorption feature in their spectra, are found to be consistent with surface charge trapping observed in CdSe QDs. In comparison, the transients obtained for mercaptopropionic acid passivated QDs coupled with the pump-induced transmittance change spectrum show no sign of any surface-related processes. Therefore, our analyses allow the determination of multiple exciton generation for the first time in these QDs with a quantum yield of 1.36 ± 0.04 when photo-exciting with photons of energy 3.1 times the band gap. Such result should turn researchers’ attention to those ligands which could improve the QD solar cell field. The study of exciton dynamics in CdxHg(1-x)Te alloy QDs is also presented here. Their pump-induced transmittance change spectrum show two bleaches: at the shoulder position of the steady state absorption and at the PL peak. The exciton dynamics of these materials are studied using four different wavelengths, two of them are above the MEG threshold. The resultant transmittance transients and the pump-induced transmittance change spectrum are free of any photo-induced absorption or long-lived surface trapping. Hence, the decay of the transients obtained above the MEG threshold for well-stirred samples at low pump fluences is attributed to biexciton recombination. The assessment of multiple exciton generation reveals a quantum yield value of 1.12 ± 0.01 when photo-exciting with 2.6 times the band gap. Finally, the investigation of the recovery of the plasmon bleach in TiO2 colloidal spheres decorated with different sizes of Au NPs is presented in this thesis. The pump-induced transmittance change spectra obtained for two different wavelengths show bleaches at the plasmon band maximum superimposed with two wings of absorption features at shorter and longer wavelengths. The resultant transmittance transients for these samples are well-described by bi-exponential decay with a very quick decline of a few ps associated with electron–phonon scattering, followed by a slower decay over a few 10s of ps associated with heat dissipation. Only the heat dissipation rate is found to be dependent on the size of the Au NPs as it rises from 49 ± 3 ps to 128 ± 6 ps when the diameter of the Au NPs is increased from 12.2 ± 2.2 nm to 24.5 ± 2.8 nm, respectively.
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Lambright, Scott. "Ultrafast Charge Carrier Dynamics in Au/Semiconductor Nanoheterostructures." Bowling Green State University / OhioLINK, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1404741549.
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Cadirci, Musa. "Ultrafast charge dynamics in novel colloidal quantum dots." Thesis, University of Manchester, 2014. https://www.research.manchester.ac.uk/portal/en/theses/ultrafast-charge-dynamics-in-novel-colloidal-quantum-dots(865aba90-9d60-478d-8f49-ad4785516688).html.
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In this thesis ultrafast exciton dynamics of several colloidal quantum dots have been studied using visible transient absorption spectroscopy. The resultant transient decays and differential transmission spectra were analysed to determine the ultrafast relaxation channels, multiple exciton generation (MEG) efficiency and multi-exciton interactions in the observed materials. All QDs were preliminarily optically characterized using steady state absorption and photoluminescence spectroscopies. In addition, a high repetition infrared femtosecond pump probe experiment was designed and built to detect the picosecond intraband carrier relaxations in quantum dots. Picosecond carrier dynamics of type-II ZnTe/ZnSe and of CuInSe2 and CuInS2 type-I quantum dots were investigated. The common feature of these materials is that they are eco-friendly materials, being alternatives to the toxic Cd- and Pb- based materials. It was found that surface trapping occurred in both cases for electrons in the hot states, and in the minimum of the conduction band for ZnTe/ZnSe core/shell materials. Trion formation was observed in ZnTe/ZnSe core/shell dots at high power and unstirred conditions. The hot and cold electron trapping processes in type-II dots and CuInS2 and CuInSe2 dots shifted, distorted and moderately cancelled the bleach features. In addition, intra-gap hole trapping was observed in CuInS2 and CuInSe2 dots which results in a long decay feature in the recorded transients. MEG competes with Auger cooling, surface mediated relaxation and phonon emission. To enhance the MEG quantum yield, the rival mechanisms were suppressed in well-engineered CdSe/CdTe/CdS and CdTe/CdSe/CdS core/shell/shell and CdTe/CdS core/shell type-II quantum dots. The MEG slope efficiency and threshold for a range of different core size and shell thickness were found to be (142±9)%/Eg and (2.59±0.16)Eg, respectively. The observed threshold was consistent with the literature, whereas, the obtained slope efficiency was about three times higher than the previously reported values. The biexciton interaction energy of the dots stated in the previous paragraph was also studied. To date, time-resolved photoluminescence (TRPL) has been employed to study exciton interactions in type-II quantum dots and large repulsive biexciton interaction energy values between 50-100 meV have been reported. However, unlike the TRPL method, the TA experiment ensures that only two excitons remain in the band edge of the dot. Using this method, large attractive biexciton interaction energies up to ~-60 meV was observed. These results have promising implications regarding enhancing the MEG quantum yield.
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Peckus, Domantas. "Ultrafast exciton and charge carrier dynamics in nanostructured molecular layers." Doctoral thesis, Lithuanian Academic Libraries Network (LABT), 2013. http://vddb.library.lt/obj/LT-eLABa-0001:E.02~2013~D_20131220_150447-81409.
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Due to their unique properties organic semiconductors may be used for various applications in organic optoelectronic devices: light emitting devices, lasers, field-effect transistors, photovoltaic cells and etc. Despite high perspectives of organic semiconductors they are still upstaged by their inorganic counterparts. Development of organic electronics requires better understanding of electrooptical properties of organic semiconductors and relationships between their structure and functions.
The main goal of this thesis is a detailed investigation of ultrafast exciton and charge carrier processes in pure organic semiconductors and their blends with fullerene derivatives. Investigated organic or silicon organic semiconductors were poly-di-n-hexylsilane (PDHS), polyfluorenes F8BT and PSF-BT, merocyanine MD376. C60 fullerene and its derivative PCBM were used in blends. Ultrafast transient absorption, fluorescence, and integral mode photocurrent measurements were used for investigations.
The investigation of PDHS nanocomposites revealed that PDHS incorporation into nanopores can be used for improvement of fluorescence properties.
Formation of intramolecular charge transfer state was proposed for PSF-BT neat films. Charge transfer scheme of the formation of long-lived charge pair state in PSF-BT/PCBM blend was presented.
The charge pair and free charge carrier generation scheme in merocyanine blends with fullerene derivatives were discussed in detail.
Analysis of measurement... [to full text]Dėl savo unikalių savybių organiniai puslaidininkiai gali būti plačiai pritaikyti įvairiuose optoelektroniniuose prietaisuose: organiniuose šviestukuose, organiniuose lazeriuose, organiniuose tranzistoriuose ir organiniuose šviesos elementuose. Visi šie pritaikymai yra galimi dėl organinių molekulių laidumo. Nepaisant didelių organinių puslaidininkių perspektyvų, jie vis dar yra nukonkuruojami neorganinių puslaidininkių. Pagrindinis šių tezių tikslas yra detaliai ištirti eksitonų ir krūvininkų dinamikos procesus grynuose organiniuose puslaidininkiuose ir jų mišiniuose su fulereno dariniais. Buvo matuoti organiniai ir silicio organiniai puslaidininkiai: poli-di-n-heksilsilanas (PDHS), polifluoreno dariniai F8BT ir PSF-BT, merocianinas MD376. Mišiniuose naudoti fulerenai buvo C60 ir jo darinys PCBM. Tyrimams buvo naudoti ultraspartūs skirtuminės sugerties, fluorescencijos ir integralinės fotosrovės matavimai. PDHS tyrimai atskleidė, kad neorganinės matricos sumažina nespindulinį relaksacijos kanalą. PDHS nanokompozitai gali būti naudojami polimero fluorescencijos savybių: stabilumo, kvantinio našumo pagerinimui. Polifluorenų F8BT ir PSF-BT grynų plėvelių tyrimų metu nustatyti eksitonų-eksitonų anihiliacijos ir eksitonų migracijos skirtumai. Vidumolekulinės krūvio pernašos būsenos formavimasis buvo pasiūlytas PSF-BT grynoms plėvelėms. Pristatyta ilgi gyvuojančių krūvininkų porų formavimosi schema PSF-BT/PCBM mišiniuose. Krūvio pernašos būsenų formavimasis buvo ištirtas... [toliau žr. visą tekstą]
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Rivett, Jasmine Pamela Helen. "Charge carrier dynamics of lead halide perovskites probed with ultrafast spectroscopy." Thesis, University of Cambridge, 2018. https://www.repository.cam.ac.uk/handle/1810/275095.
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In this thesis, we investigate the nature of charge carrier generation, relaxation and recombination in a range of lead halide perovskites. We focus on understanding whether the photophysical behaviour of these perovskite materials is like that of highly-ordered inorganic crystalline semiconductors (exhibiting ballistic charge transport) or disordered molecular semiconductors (exhibiting strong electron-phonon coupling and highly localised excited states) and how we can tune these photophysical properties with inorganic and organic additives. We find that the fundamental photophysical properties of lead halide perovskites, such as charge carrier relaxation and recombination, arise from the lead halide lattice rather than the choice of A-site cation. We show that while the choice of A-site cation does not affect these photophysical properties directly, it can have a significant impact on the structure of the lead halide lattice and therefore affect these photophysical properties indirectly. We demonstrate that lead halide perovskites fabricated from particular inorganic and organic A-site cation combinations exhibit low parasitic trap densities and enhanced carrier interactions. Furthering our understanding of how the photophysical properties of these materials can be controlled through chemical composition is extremely important for the future design of highly efficient solar cells and light emitting diodes.
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Tiwana, Priti. "Ultrafast charge dynamics in mesoporous materials used in dye-sensitized solar cells." Thesis, University of Oxford, 2013. http://ora.ox.ac.uk/objects/uuid:ba3cbbce-3119-4043-a499-c0ca74287d42.
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This thesis is concerned with measuring ultrafast electron dynamics taking place in dye-sensitized mesoporous semiconductor films employed as working electrodes in dye-sensitized solar cells (DSCs). An understanding of these ultrafast charge transfer mechanisms is essential for designing efficient photovoltaic (PV) devices with high photon-to-current conversion efficiency. Optical-pump terahertz-probe (OPTP) spectroscopy is a sub-picosecond resolution, non-contact, photoconductivity measurement technique which can be used to directly measure charge carrier dynamics within nanostructured materials without the need for invoking complex modelling schemes. A combination of OPTP and photovoltaic measurements on mesoporous TiO2 films show an early-time intra-particle electron mobility of 0.1 cm2/(Vs). This value is an order of magnitude lower than that measured in bulk TiO2 and can be partly explained by the restricted electron movement because of geometrical constraints and increased trap sites in the nanostructured material. In addition, the mesoporous film behaves like a nanostructured composite material, with the TiO2 nanoparticles embedded in a low dielectric medium (air or vacuum), leading to lower apparent electron mobility. THz mobility measured in similar mesoporous ZnO and SnO2 films sensitized with the same dye is calculated to be 0.17 cm2/(Vs) for ZnO and 1.01 cm2/(Vs) for SnO2. Possible reasons for the deviation from mobilities reported in literature for the respective bulk materials have been discussed. The conclusion of this study is that while electron mobility values for nanoporous TiO2 films are approaching theoretical maximum values, both intra- and inter-particle electron mobility in mesoporous ZnO and SnO2 films offer considerable scope for improvement. OPTP has also been used to measure electron injection rates in dye-sensitized TiO2, ZnO and SnO2 nanostructured films. They are seen to proceed in the order TiO2 >SnO2 >ZnO. While the process is complete within a few picoseconds in TiO2/Z907, it is seen to extend beyond a nanosecond in case of ZnO. These measurements correlate well with injection efficiencies determined from DSCs fabricated from identical mesoporous films, suggesting that the slow injection components limit the overall solar cell photocurrent. The reasons for this observed difference in charge injection rates have been explored within. It is now fairly common practice in the photovoltaic community to apply a coating of a wide band-gap material over the metal-oxide nanoparticles in DSCs to improve device performance. However, the underlying reasons for the improvement are not fully understood. With this motivation, OPTP spectroscopy has been used to study how the conformal coating affects early-time mechanisms, such as electron injection, trapping or diffusion length. The electron injection process is unaffected in case of TiCl4-treated TiO2 and MgO-treated ZnO, while it becomes much slower in case of MgO-treated SnO2. Finally, a light-soaking effect observed in SnO2-based solid-state DSCs has been examined in detail using THz spectroscopy and transient PV measurement techniques. It is concluded that continued exposure to light results in a rearrangement of charged species at the metal-oxide surface. This leads to an increase in the density of acceptor states or a lowering of the SnO2 conduction band edge with respect to the dye excited state energy level, ultimately leading to faster electron transport and higher device photocurrents.
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Prince, Beth Marie. "Vibrational dynamics of excited states probed by fs/ps CARS simulations and applications to ultrafast charge transfer dynamics /." [Ames, Iowa : Iowa State University], 2008.
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Erasmus, Nicolas. "Ultrafast structural dynamics in 4Hb-TaSe2 observed by femtosecond electron diffraction." Thesis, Stellenbosch : Stellenbosch University, 2013. http://hdl.handle.net/10019.1/79934.
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Thesis (PhD)--Stellenbosch University, 2013.ENGLISH ABSTRACT: In this thesis the structural dynamics, upon photo-excitation, of the charge-densitywave (CDW) material 4Hb-TaSe2 is investigated on the time-scale of atomic motion and simultaneously on the spatial-scale of atomic dimensions. CDW materials have been of interest since their discovery in the 1970’s because of their remarkable non-linear and anisotropic electrical properties, gigantic dielectric constants, unusual elastic properties and rich dynamical behaviour. Some of these exotic properties were extensively investigated in thermal equilibrium soon after their discovery but only recently have ultrafast techniques like femtosecond spectroscopy become available to study their out-of-equilibrium behaviour on the time-scale of atomic motion. By studying their behaviour on this time-scale a more in-depth understanding of their macroscopic properties can be gained. However, to do investigations on the atomic time-scale and simultaneously directly observe the evolution of the atomic arrangements is another challenge. One approach is through the previously mentioned technique of femtosecond pump-probe spectroscopy but converting the usual ultrashort optical probing source to an ultrashort electron or x-ray source that can diffract off the sample and reveal structural detail on the atomic level. Here, the femto-to-picosecond out-of-equilibrium behaviour upon photo-excitation in 4Hb-TaSe2 is investigated using an ultrashort electron probe source. Two variations of using an electron probe source are used: conventional scanning Femtosecond Electron Diffraction (FED) and a new approach namely Femtosecond Streaked Electron Diffraction (FSED). The more established FED technique, based on femtosecond pumpprobe spectroscopy, is used as the major investigating tool while the FSED technique, based on ultrafast streak camera technology, is an attempt at broadening the scope of available techniques to study structural dynamics in crystalline material on the subpicosecond time-scale. With these two techniques, the structural dynamics during the phase transition from the commensurate- to incommensurate-CDW phase in 4Hb-TaSe2 is observed through diffraction patterns with a temporal resolution of under 500 fs. The study reveals strong coupling between the electronic and lattice systems of the material and several time-constants of under and above a picosecond are extracted from the data. Using these time-constants, the structural evolution during the phase transition is better understood and with the newly gained knowledge, a model of all the processes involved after photo-excitation is proposed.
AFRIKAANSE OPSOMMING: In hierdie tesis word die strukturele dinamika van die lading-digtheid-golf (LDG) materiaal 4Hb-TaSe2 ondersoek op die tydskaal van atomiese bewegings en gelyktydig op die ruimtelikeskaal van atomiese dimensies. LDG materie is al van belang sedert hul ontdekking in die 1970’s as gevolg van hul merkwaardige nie-lineêre en anisotrope elektriese eienskappe, reuse diëlektriese konstantes, ongewone elastiese eienskappe en ryk dinamiese gedrag. Sommige van hierdie eksotiese eienskappe is omvattend ondersoek in termiese ewewig kort na hul ontdekking, maar eers onlangs is dit moontlik deur middle van ultravinnige tegnieke soos femtosekonde spektroskopie om hulle uit-ewewigs gedrag te bestudeer op die tydskaal van atomiese beweging. Deur die gedrag op hierdie tydskaal te bestudeer kan ’n meer insiggewende begrip van hul makroskopiese eienskappe verkry word. Om ondersoeke in te stel op die atomiese tydskaal en gelyktydig direk die evolusie van die atoom posisie te waarneem is egter ’n moeilike taak. Een benadering is deur middle van femtosekonde “pump-probe” spektroskopie maar dan die gewone optiese “probe” puls om te skakel na ’n electron of x-straal puls wat van die materiaal kan diffrak en dus strukturele inligting op die atomiese vlak kan onthul. Hier word die femto-tot-pico sekonde uit-ewewig gedrag in 4Hb-TaSe2 ondersoek met behulp van elektron pulse. Twee variasies van die gebruik van ’n elektron bron word gebruik: konvensionele “Femtosecond Electron Diffraction” (FED) en ’n nuwe benadering, naamlik, “Femtosecond Streaked Electron Diffraction” (FSED). Die meer gevestigde FED tegniek, wat gebaseer is op femtosekonde “pump-probe” spektroskopie, word gebruik as die hoof ondersoek metode terwyl die FSED tegniek, wat gebaseer is op die ultra vinnige “streak camera” tegnologie, ’n poging is om beskikbare tegnieke uit te brei wat gebruik kan word om strukturele dinamika in materie te bestudeer op die sub-picosekonde tydskaal. Met behulp van hierdie twee tegnieke, word die strukturele dinamika tydens die fase oorgang van die ooreenkomstige tot nie-ooreenkomstige LDG fase in 4Hb-TaSe2 deur diffraksie patrone met ’n tydresolusie van minder as 500 fs waargeneem. Die studie toon ’n sterk korrelasie tussen die elektroniese sisteem en kristalrooster. Verskeie tydkonstantes van onder en bo ’n picosekonde kon ook uit die data onttrek word en gebruik word om die strukturele veranderinge beter te verstaan. Hierdie nuwe kennis het ons in staat gestel om ’n model van al die betrokke prosesse voor te stel.
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Aytac, Yigit. "Time-resolved measurements of charge carrier dynamics in Mwir to Lwir InAs/InAsSb superlattices." Diss., University of Iowa, 2016. https://ir.uiowa.edu/etd/2039.
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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.
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Yong, Chaw Keong. "Ultrafast carrier dynamics in organic-inorganic semiconductor nanostructures." Thesis, University of Oxford, 2012. http://ora.ox.ac.uk/objects/uuid:b2efdc6a-1531-4d3f-8af1-e3094747434c.
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This thesis is concerned with the influence of nanoscale boundaries and interfaces upon the electronic processes that occur within the inorganic semiconductors. Inorganic semiconductor nanowires and their blends with semiconducting polymers have been investigated using state-of-the-art ultrafast optical techniques to provide information on the sub-picosecond to nanosecond photoexcitation dynamics in these systems. Chapters 1 and 2 introduce the theory and background behind the work and present a literature review of previous work utilising nanowires in hybrid organic photovoltaic devices, revealing the performances to date. The experimental methods used during the thesis are detailed in Chapter 3. Chapter 4 describes the crucial roles of surface passivation on the ultrafast dynamics of exciton formation in gallium arsenide (GaAs) nanowires. By passivating the surface states of nanowires, exciton formation via the bimolecular conversion of electron-hole plasma can observed over few hundred picoseconds, in-contrast to the fast carrier trapping in 10 ps observed in the uncoated nanowires. Chapter 5 presents a novel method to passivate the surface-states of GaAs nanowires using semiconducting polymer. The carrier lifetime in the nanowires can be strongly enhanced when the ionization potential of the overcoated semiconducting polymer is smaller than the work function of the nanowires and the surface native oxide layers of nanowires are removed. Finally, Chapter 6 shows that the carrier cooling in the type-II wurtzite-zincblend InP nanowires is reduced by order-of magnitude during the spatial charge-transfer across the type-II heterojunction. The works decribed in this thesis reveals the crucial role of surface-states and bulk defects on the carrier dynamics of semiconductor nanowires. In-addition, a novel approach to passivate the surface defect states of nanowires using semiconducting polymers was developed.
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Rehman, Waqaas. "Ultrafast spectroscopy of charge-carrier dynamics and stability in lead-halide perovskites for thin-film photovoltaics." Thesis, University of Oxford, 2017. https://ora.ox.ac.uk/objects/uuid:9bded808-276d-4ca5-bac9-d66cd99b67f5.
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Hybrid metal halide perovskites have emerged as an important new class of materials for photovoltaics. For their integration in tandem solar cells, optimised photocurrent matching between top and bottom cells requires careful control over bandgap energy and charge transport properties, for which tunable mixed bromide-iodide lead perovskites are the most prominent contenders. This thesis investigates photophysical properties of highly tunable mixed-halide and mixed-cation perovskite films with the aim of correlating their optoelectronic parameters with crystal phase changes induced by compositional variations. Firstly, the compositional variation of mixed-halide FAPb(BrxI(1-x))3 perovskites is explored. Bimolecular and Auger charge-carrier recombination rate constants strongly correlate with the bromide content, x, suggesting a link with electronic structure. With rising x, the constants increase by up to an order of magnitude, yet still remain significantly below the Langevin limit. FAPbBr3 and FAPbI3 exhibit charge-carrier mobilities of 14 and 27 cm2 V-1 s-1 and diffusion lengths exceeding 1 μm, while mobilities across the mixed bromide-iodide system depend on crystalline phase disorder. Particularly, the mid-bandgap and bromide rich regions are found to be disordered and prone to photo-induced halide segregation. Subsequently, a highly crystalline mid-bandgap mixed-cation lead mixed-halide FA0.83Cs0.17Pb(Br0.4I0.6)3 perovskite is developed and investigated with focus on understanding the impact of adding caesium to the A-cation site in the lattice. Compared to single-cation FAPb(Br0.4I0.6)3, the crystal phase is stable and the chargecarrier mobility measured from THz spectroscopy reaches 21 cm2 V-1 s-1 resulting in a diffusion length of 3 μm. With photoinduced halide segregation being inherently suppressed, another benefit of controlled A-cation mixing could be revealed. In an aging-study, the correlation between the colloids concentration present in the precursor solution of FA0.83Cs0.17Pb(I0.8Br0.2)3 and nucleation stages for the crystallization of perovskite is explored. Having direct impact on morphology and photophysical properties, charge-carrier mobilities are reported to correlate with colloid concentration reaching > 20 cm2 V-1 s-1 for an optimum concentration. Ultimately, the full parameter space of mixed-cation (0 < y < 1) lead mixedhalide (0 < x < 1) CsyFA(1-y)Pb(BrxI(1-x))3 perovskites is examined, where crucial links between crystal phase stability, photo-stability and optoelectronic properties are highlighted. Finely tuning the caesium cation in the lattice yields excellent structural stability and charge-carrier transport properties for the parameter space between 0.1 < y < 0.3. For an optimized caesium content, the orthogonal halide-variation parameter space for Cs0.17FA0.83Pb(BrxI(1-x))3 achieves charge-carrier mobilities of 11 -40 cm2 V-1 s-1 and diffusion lengths of 0.8-4.4 μm.
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Ottosson, Niklas. "Aqueous Solutions as seen through an Electron Spectrometer : Surface Structure, Hydration Motifs and Ultrafast Charge Delocalization Dynamics." Doctoral thesis, Uppsala universitet, Yt- och gränsskiktsvetenskap, 2011. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-151435.
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In spite of their high abundance and importance, aqueous systems are enigmatic on the microscopic scale. In order to obtain information about their geometrical and electronic structure, simple aqueous solutions have been studied experimentally by photo- and Auger electron spectroscopy using the novel liquid micro-jet technique in conjunction with synchrotron radiation. The thesis is thematically divided into three parts. In the first part we utilize the surface sensitivity of photoelectron spectroscopy to probe the distributions of solutes near the water surface. In agreement with recent theoretical predictions we find that large polarizable anions, such as I- and ClO4-, display enhanced surface propensities compared to smaller rigid ions. Surface effects arising from ion-ion interactions at higher electrolyte concentrations and as function of pH are investigated. Studies of linear mono-carboxylic acids and benzoic acid show that the neutral molecular forms of such weak acids are better stabilized at the water surface than their respective conjugate base forms. The second part examines what type of information core-electron spectra can yield about the chemical state and hydration structure of small organic molecules in water. We demonstrate that the method is sensitive to the protonation state of titratable functional groups and that core-level lineshapes are dependent on local water hydration configurations. Using a combination of photoelectron and X-ray absorption spectroscopy we also show that the electronic re-arrangement upon hydrolysis of aldehydes yields characteristic fingerprints in core-level spectra. In the last part of this thesis we study ultrafast charge delocalization dynamics in aqueous solutions using resonant and off-resonant Auger spectroscopy. Intermolecular Coulombic decay (ICD) is found to occur in a number of core-excited solutions where excess energy is transferred between the solvent and the solute. The rate of ultrafast electron delocalization between hydrogen bonded water molecules upon oxygen 1s resonant core-excitation is found to decrease upon solvation of inorganic ions. The presented work is illustrative of how core-level photoelectron spectroscopy can be valuable in the study of fundamental phenomena in aqueous solutions.
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Villamil, Franco Carolina. "Ultrafast dynamics of excitons and charge carriers in colloidal perovskite nanostructures studied by time-resolved optical spectroscopies." Thesis, université Paris-Saclay, 2020. http://www.theses.fr/2020UPASF012.
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Les matériaux semiconducteurs de pérovskite halogénée se sont révélés très prometteurs en raison de leurs propriétés exceptionnelles et de leur capacité d’élaboration à faible coût. Malgré les progrès réalisés, une meilleure compréhension des dynamiques de relaxation et de recombinaison dans ces matériaux photo-actifs est nécessaire afin d’améliorer les performances des dispositifs opto-électroniques. Cette thèse porte sur la relaxation des porteurs de charge/excitons « chauds » après excitation au-dessus de la bande interdite, et la recombinaison Auger advenant après une excitation de forte puissance ou à haute énergie. La spectroscopie de fluorescence résolue en temps et d'absorption transitoire (AT) femtoseconde sont utilisées afin d’étudier les effets du confinement et de la composition sur ces processus, en particulier dans les nanoplaquettes (NPLs) colloïdales de pérovskite bidimensionnelles (2D), dont la synthèse a été développée et optimisée au préalable. Les dynamiques de relaxation ont été étudiées par AT en utilisant une méthode d'analyse globale où l'évolution temporelle des différentes compositions spectrales est modélisée suivant une cinétique de réactions séquentielles. Cette méthode a pu être appliquée afin de décrire efficacement la relaxation progressive dans les nanostructures de FAPbI₃ (FA= formamidinium) faiblement confinées, et a permis de dissocier les processus de retardement de relaxation à haute puissance d’excitation dus aux effets de « hot phonon bottleneck » et de ré-excitation par recombinaison Auger (RA). Par ailleurs, l'analyse globale de l’évolution spectrale a été essentielle afin d’examiner les dynamiques de relaxation dans les NPLs 2D à fort confinement quantique et diélectrique, présentant des effets Stark importants et une transition de bord de bande excitonique discrète. Comme dans les systèmes faiblement confinés, le taux de relaxation dans les NPLs diminue avec la puissance d'excitation. Cependant, il est plus rapide dans les systèmes présentant un confinement plus important, mettant alors en évidence l'absence de ”phonon bottleneck” intrinsèque. La nature des cations internes (FA, MA=méthylammonium ou Cs) n’influe pas ce taux, ni son évolution en puissance. Toutefois, les mesures dans les films de pérovskite 2D présentant une épaisseur de puits quantique équivalente, suggèrent un rôle des ligands de surface dans la capacité à libérer l'excès d'énergie dans l'environnement. Ensuite, les recombinaisons multi-excitoniques dominées par la RA non radiative ont été étudiées dans les NPLs de pérovskite 2D fortement confinées. Dû à la géométrie asymétrique de ces nanostructures et de la délocalisation limitée de l'exciton, le temps de RA dépend fortement de la densité d'excitons via la distance inter-exciton moyenne : A faible puissance d’excitation, la RA est limitée par la diffusion de l'exciton dans le plan 2D et se produit sur plusieurs centaines de picosecondes (dépendant ainsi de la géométrie de l'échantillon). En revanche, une puissance d'excitation élevée produit des excitons dont les fonctions d’onde se recouvrent spatialement, entraînant des temps de RA inférieurs à 10 ps. Finalement, les dynamiques excitoniques dans les NPLs 2D ont été mesurées par AT après excitation dans l’ultraviolet afin d'observer le processus de multiplication d’excitons. Ce dernier implique la génération de plusieurs excitons “géminés”, et donc proches spatialement, suite à l'absorption d'un unique photon de haute énergieHalide perovskites have emerged as very promising photoactive materials due to their outstanding optoelectronic properties combined with low-cost processability. In spite of their successful implementation in photovoltaic or light-emitting devices, a deep understanding of the dynamics of relaxation and recombination is still missing in order to enhance the device performances. This thesis focuses on the study of two major fundamental processes occurring in colloidal halide perovskite nanostructures: the hot charge carrier/exciton relaxation (“cooling”), after excitation above the optical bandgap, and the non-radiative Auger recombination, taking place after high-fluence or high-photon energy excitation. In particular, time-resolved photoluminescence and femtosecond transient absorption spectroscopy were used to investigate the confinement and composition effects in strongly confined two-dimensional (2D) lead iodide perovskite nanoplatelets (NPLs), that were synthesized following the development and optimizations of colloidal methods. For the investigation of the cooling dynamics, a global analysis method based on single value decomposition was used, where the temporal evolution of the spectral lineshapes was modeled with a sequential kinetic scheme. This method was succesfully applied to effectively describe the continuous energy relaxation in weakly-confined thick FAPbI₃ nanoplates (FA=formamidinium) and allowed disantangleting the hot phonon bottleneck from the Auger reheating effects at high excitation fluence. Furthermore, the global analysis was essential to investigate the cooling dynamics in strongly confined 2D NPLs presenting large Stark effects and discrete excitonic band-edge transition far away from the continuum of states (exciton binding energy in several hundreds of meV). As in the weakly confined samples, the cooling rate of the NPLs decreases with the excitation fluence. However, it is faster in more-strongly confined samples, evidencing the absence of an intrinsic phonon bottleneck. Furthermore, the cooling rate and its evolution with the exciton density were found independent of the nature of the internal cations (FA, MA=methylammonium and Cs=cesium). However, when comparing with the rate measured in 2D layered perovskite thin film with equivalent quantum well thickness, the results strongly suggest a role of the surface ligands in the possibility to release the excess energy to the surrounding environment. This ligand-mediated relaxation mechanism becomes dominent in the thinner NPL samples with enhanced exciton/ligand vibrational mode coupling. Then, the multiple exciton recombination dominated by non-radiative Auger recombination (AR) was studied in the strongly-confined 2D perovskite NPLs. Due to the large asymmetric geometry and the limited exciton wavefunction delocalization, the AR rate strongly depends on the exciton density via the initial average inter-exciton distance. At low fluence, this distance is in several tens of nanometers such as the AR is limited by the exciton diffusion in the 2D plane. It thus occurs on a timescale of several hundreds of picoseconds and depends on the sample dimensionality (thickness and lateral sizes). In contrast, high excitation fluences produce “overlapping” excitons with inter-exciton distances of only a few times the exciton Bohr radius, resulting in AR times of less than 10 ps and independent of the NPL composition nor geometry. Finally, the exciton population dynamics of 2D NPLs after excitation in the ultraviolet was measured. The strong dependence of the AR with the inter-exciton distance allows the identification of multiple exciton generation (MEG), which involves the reaction of “geminate biexcitons” produced by the absorption of a single high-energy photon
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Suleiman, Aminat Oyiza. "Structural dynamics of 1T-TiSe2 using femtosecond electron diffraction." Thesis, Stellenbosch : Stellenbosch University, 2014. http://hdl.handle.net/10019.1/95990.
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Thesis (MSc)--Stellenbosch University, 2014.ENGLISH ABSTRACT: Trilayered transition metal dichalcogenides such as our sample (1T-TiSe2) have been studied for many years as systems with strong electron-electron and electron-phonon correlations. The main attraction to this family of compound is its potential to exhibit ground state phenomena known as charge density waves whose detailed physical origin has been controversially determined. In this study, we have used an ultrafast femtosecond laser based on a pump-probe technique, namely ultrafast electron diffraction, to investigate these exotic features associated with the crystal. A pump laser pulse photo-excites the crystal from its ground state and the probe pulse (ultrashort electron pulse) takes the snapshot of the evolution of the lattice generating an electron diffraction pattern of the crystal. Hence the dynamical structural behaviour can be observed in time with a subpicosecond temporal resolution. As a hexagonal close-packed structure, its signature is expected to be seen in the diffraction pattern in both a steady-state and electron time-resolved femtosecond electron diffraction. In addition, simulations of electron diffractions pattern for room and low temperature structural data via a software called Simulation and Analysis of Electron diffraction (SAED) have been carried out. Clear signatures of charge density waves were seen at low temperature.
AFRIKAANSE OPSOMMING: Drie-laag oorgangsmetaal dikhalkogeniedes soos ons voorbeeld (1T-TiSe2), word reeds vir baie jare bestudeer as sisteme met sterk elektron-elektron en elektron-fonon korrelasies. Die hoof aantrekkingskrag van hierdie sisteme is die verskynsel van ladingdigtheidsgolwe in die grondtoestand. Die fisiese oorsprong van hierdie ladingdigtheidsgolwe was bepaal te midde van verskeie teenstrydighede. In hierdie studie, maak ons gebruik van die ultravinnige femtosekonde laser gebaseerde aktiveer-interogeer tegniek, genaamd ultravinnige elektron diffraksie (UED) om unicke eienskappe wat met die kristal geassosieer is te bestudeer. In UED wek ’n ultravinnige laserpuls (aktivering) die kristal op vanaf die grondtoestand waartydens n ultravinnige elektronpuls (interogering) ’n foto neem van die evolusie van die elektron diffraksiepatroon wat deur die kristalrooster gegenereer word. Hierdie wisselwerking van die interogerings elektronpuls en die sisteem kan gevolglik teen verskeie vasgetelde tye toegelaat word. Dus kan die dinamiese strukturele gedrag waargeneem word met ’n tydresolusie in die orde van die elektronpuls (sub-pikosekondes). Siende dat die kristal ’n diggepakte-heksagonale struktuur vorm, behoort die kenmerkende diffraksiepatroon daarvan waarneembaar te wees in beide die bestendige diffraksie en femtosekonde elektron diffraksie tegnieke. In hierdie konteks was duidelike tekens van ladingdigtheidsgolwe waargeneem. Benewens was daar ook simulasies uitgevoer om die elektron diffraksiepatrone asook die strukturele data by kamer en lae temperature vas te pen. Die sagteware wat hiervoor gebruik word is genaamd Simulasie en Ontleding van Elektronendiffraksie (SAED) - Simulation and Analysis of Electron Diffraction (SAED).
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Wehrenfennig, Christian. "Ultrafast spectroscopy of charge separation, transport and recombination processes in functional materials for thin-film photovoltaics." Thesis, University of Oxford, 2014. http://ora.ox.ac.uk/objects/uuid:1f812413-4a2f-418f-a7fd-d749e88cc2e1.
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Dye-sensitized solar cells (DSSCs) and perovskite solar cells are emerging as promising potential low-cost alternatives to established crystalline silicon photovoltaics. Of the employed functional materials, however, many fundamental optoelectronic properties governing photovoltaic device operation are not sufficiently well understood. This thesis reports on a series of studies using ultrafast THz and photoluminescence spectroscopy on two classes of such materials, providing insight into the dynamics of charge-transport and recombination processes following photoexcitation. For TiO2-nanotubes, which have been proposed as easy-to-fabricate electron transporters for DSSCs, fast, shallow electron trapping is identified as a limiting factor for efficient charge collection. Trapping lifetimes are found to be about an order of magnitude shorter than in the prevalently employed sintered nanoparticles under similar excitation conditions and trap saturation effects are not observed, even at very high excitation densities. In organo-lead halide perovskites - specifically CH3NH3PbI3 and CH3NH3PbI3-xClx, which have only recently emerged as highly efficient absorbers and charge transporters for thin-film solar cells, carrier mobilities and fundamental recombination dynamics are revealed. Extremely low bi-molecular recombination rates at least four orders of magnitude below the prediction of Langevin's model are found as well as relatively high charge-carrier mobilities in comparison to other solution-processable materials. Furthermore a very low influence of trap-mediated recombination channels was observed. Due to a combination of these factors, diffusion lengths reach hundreds of nanometres for CH3NH3PbI3 and several microns for CH3NH3PbI3-xClx. These results are shown to hold for both, solution processed and vapour-deposited CH3NH3PbI3-xClx and underline the superb suitability of the materials as absorbers in solar cells, even in planar heterojunction architectures. The THz-frequency spectrum of the conductivity of the investigated perovskites is consistent with Drude-like charge transport additionally exhibiting weak signatures of phonon coupling. These coupling effects are also reflected in the luminescence of CH3NH3PbI3-xClx, where they are believed to be the cause of the observed homogeneous spectral broadening. Further photoluminescence measurements were performed at temperatures between 4 K and room temperature to study the nature of recombination pathways in the material.
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Acharya, Snigdhatanu [Verfasser], Gerhard [Akademischer Betreuer] Seifert, Wolf [Akademischer Betreuer] Widdra, and Carsten [Akademischer Betreuer] Ronning. "Ultrafast charge carrier dynamics of ZnO thin films and BaTiO3-ZnO heterostructures / Snigdhatanu Acharya. Betreuer: Gerhard Seifert ; Wolf Widdra ; Carsten Ronning." Halle, Saale : Universitäts- und Landesbibliothek Sachsen-Anhalt, 2013. http://d-nb.info/1033789968/34.
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Chen, Jinghao [Verfasser], and Uwe [Akademischer Betreuer] Bovensiepen. "Ultrafast charge and spin dynamics at solid interfaces : Investigated with femtosecond time-resolved second harmonic spectroscopy / Jinghao Chen ; Betreuer: Uwe Bovensiepen." Duisburg, 2021. http://d-nb.info/1233966588/34.
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ALMEIDA, Euclides Cesar Lins. "Ultrafast dynamics of nanoscale systems: NaNbO3 nanocrystals, colloidal silver nanoparticles and dye functionalized TiO2 nanoparticles." Universidade Federal de Pernambuco, 2012. https://repositorio.ufpe.br/handle/123456789/18659.
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CNPQ
O principal objetivo deste trabalho foi investigar fenômenos ópticos ultrarrápidos em sistemas nanoestruturados empregando diferentes técnicas espectroscópicas não lineares, tanto no domínio do tempo quanto no domínio da frequência. Para fornecer uma base adequada que permita entender os experimentos feitos nessa tese, os princípios físicos das espectroscopias ópticas não lineares são apresentados. Inicialmente é apresentada uma descrição da função resposta não linear no domínio do tempo. A evolução temporal da polarização óptica, que gera o sinal espectroscópico, é descrita em detalhes usando uma teoria de perturbação diagramática. Técnicas ópticas não lineares são apresentadas, tais como eco de fótons, bombeamento-e-sonda e hole burning, assim como o comportamento dinâmico de um material pode ser interpretado a partir do sinal gerado. A técnica de mistura degenerada de quatro ondas com luz incoerente foi usada para investigar, pela primeira vez, o defasamento ultrarrápido de éxcitons em uma vitrocerâmica contendo nanocristais de niobato de sódio. O tempo de defasamento medido (T2 = 20 fs) indica qu empregada para investigar processos de transferência de carga em colóides com nanopartículas de TiO2 e rodamina 6G. O comportamento do sinal de depleção transiente é comparado com o observado para a rodamina livre suspensa em etanol. A análise dos resultados permitiu atribuir o comportamento de depleção à transferência de carga de estados excitados termalizados das moléculas de corante para a banda de condução do semicondutor e a transferência no sentido inverso do semicondutor para as moléculas.
The main objective of this work was the investigation of ultrafast optical phenomena in selected nanostructured systems employing different nonlinear spectroscopic techniques, either in the time or the frequency domain. To provide an appropriate background to understand the performed experiments the principles of nonlinear optical spectroscopies are presented. Initially a description of the nonlinear optical response function in the time domain is given. The time evolution of the optical polarization, that gives rise to the spectroscopic signal, is described in detail using a diagrammatic perturbation theory. Nonlinear optical techniques are discussed such as photon echoes, pump-and-probe and hole-burning, as well as how the dynamical behavior of a material can be interpreted from the generated signals. The degenerate four-wave mixing technique with incoherent light was used to investigate for the first time the ultrafast dephasing of excitons in a glass-ceramic containing sodium niobate nanocrystals. The short dephasing time measured (T2 = 20 fs) indicates that different dephasing channels contribute for the excitonic dephasing, namely: electron-electron scattering, electron-phonon coupling and fast trapping of electrons in defects on the nanocrystals interface. Low-temperature luminescence experiments were also performed to measure excitonic and trap states lifetimes. The persistent spectral holeburning technique was applied to measure localized surface plasmons dephasing times in colloidal silver nanoparticles capped with different stabilizing molecules. The dependence of T2 with three different stabilizers was demonstrated and theoretically analyzed. The results show that the dephasing times are shorter than the theoretically calculated T2 using the bulk dielectric functions of the metal. This discrepancy is attributed to changes in the electronic density of states at the nanoparticles interface caused by the presence of the stabilizers. Ab-initio calculations based on the Density Functional Theory were performed to further understand the interaction between the nanoparticles and stabilizing agents. The femtosecond transient absorption technique was employed to study the ultrafast dynamics of in-gap states in a glassceramics containing sodium niobate nanocrystals. Two main temporal components were found for the excited state absorption signal: a fast component, with decay time of ≈ 1 ps, and a slower component which is attributed to deep trap states. This slower component is responsible for the excited state absorption contribution in optical limiting experiments previously reported in the literature. The dynamics of the optical limiting in this sample was also studied, in the millisecond range, exciting the sample with a train of femtosecond pulses. The optical limiting behavior reflects the dynamics of population in the excited and trap states and this dynamics was modeled using rate equations for the electronic states’ populations. Finally, the pump-andprobe transient absorption technique was employed to investigate charge-transfer processes in colloids with rhodamine 6G and TiO2 nanoparticles. The transient bleaching signal behavior is compared with the one observed for unlinked rhodamine 6G dissolved in ethanol. The analysis of the results allowed the attribution of the bleaching behavior to charge-transfer from thermalized excited states of the dye molecules to the semiconductor conduction band and to the back charge-transfer from the semiconductor to the molecules.
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Pecourt, Jean-Marc L. "Femtosecond pump-probe investigation of excited state dynamics in liquids : intramolecular charge transfer in dimethylaminobenzonitrile and ultrafast internal conversion in nucleic acid components /." The Ohio State University, 2000. http://rave.ohiolink.edu/etdc/view?acc_num=osu1488203857248598.
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Storeck, Gero [Verfasser], Claus [Akademischer Betreuer] Ropers, Claus [Gutachter] Ropers, and Stefan [Gutachter] Mathias. "Non-equilibrium structural Dynamics of incommensurate Charge-Density Waves : Diffractive Probing with a micron-scale ultrafast Electron Gun / Gero Storeck ; Gutachter: Claus Ropers, Stefan Mathias ; Betreuer: Claus Ropers." Göttingen : Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2020. http://d-nb.info/1213096286/34.
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Rohwer, Egmont J. "Development of a non-collinearly phase matched optical parametric amplifier and application in pump-probe spectroscopy." Thesis, Stellenbosch : University of Stellenbosch, 2011. http://hdl.handle.net/10019.1/6607.
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Stingl, Johannes. "Untersuchung der ultraschnellen Polarisationsdynamik in Lithiumborhydrid mittels Femtosekunden Röntgenbeugung." Doctoral thesis, Humboldt-Universität zu Berlin, Mathematisch-Naturwissenschaftliche Fakultät I, 2013. http://dx.doi.org/10.18452/16847.
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In dieser Arbeit wird die ultraschnelle elektronische Polarisation in dem kristallinen Festkörper Lithiumborhydrid (LiBH4) untersucht. Das Material wird dabei mit einem femtosekundenlangen optischen Impuls angeregt und mit einem ebenso kurzen Röntgenimpuls abgetastet. Mithilfe der Röntgenbeugung kann die optisch induzierte räumliche Neuordnung elektronischer Ladung direkt mit atomarer räumlicher Auflösung abgebildet werden. Kupfer K-alpha Röntgenstrahlung für das Experiment wird im Labor aus einer Laser-Plasmaquelle mit 1 kHz Wiederholrate erzeugt. Diese Strahlung wird dann auf eine pulverisierte LiBH4-Probe fokussiert. Die Debye-Scherrer Ringe, die bei Pulverbeugung entstehen, werden mit einem großflächigen Detektor aufgezeichnet und zu Intensitätsprofilen aufbereitet. Mittels Anrege-Abtast-Technik wird die Änderung der Beugungsintensitäten, ausgelöst durch die optische Anregung mit einem optischen Femtosekunden-Impuls, zeitaufgelöst untersucht. Dabei ist die Zeitauflösung durch die Verzögerungzeit zwischen Anrege- und Abtastimpuls gegeben. Daraus ergibt sich ein Einblick in die dynamische elektronische Entwicklung des Systems. Intensitätsänderungen können dann mit Änderungen in der Ladungsdichte des Materials korreliert werden, um strukturelle Dynamik auf der Femtosekunden Zeitskala aufzuklären. Lithiumborhydrid wurde gewählt, weil es Eigenschaften aufweist, die für eine Erforschung der ultraschnellen elektronischen Polarisation notwendig sind. Bisher gibt es keine räumlich aufgelöste Untersuchung im Femtosekunden-Bereich, die zur Erklärung dieses elektronischen Phänomens beträgt. Diese Arbeit präsentiert die ultraschnelle Antwort von LiBH4 auf starke elektrische Felder bei optischen Frequenzen, die zu Ladungsumverteilung und damit einhergehende elektronische Polarisation führt.In this thesis the ultrafast electronic polarisation in the crystalline material lithium borohydride (LiBH4) is examined. The material is excited by a femtosecond long optical pulse and scanned by a likewise short x-ray pulse. Using x-ray scattering the optically induced spatial rearrangement of electronic charge can be directly mapped with atomic spatical resolution. Copper K-alpha x-rays for the experiment are produced in a laboratory table-top laserplasma source with 1 kHz repetition rate. This radiation is then focused on a powdered sample. Debye-Scherrer rings produced from powder diffraction are collected on a large area detector and processed to yield intensity profiles. Using pump-probe technique the change in diffracted intensity, triggered by excitation with a femtosecond optical pulse is examined. The temporal resolution is given by the delay between pump and probe pulse. This way insight is gained into the dynamic electronic evolution of the system. Intensity changes can be correlated to changes in charge density in the relevant material to elucidate structural dynamics on the femtosecond time scale. Lithium borohydride was chosen since it displays necessary characteristics for the exploration of ultrafast electronic polarisation. Up to date there has been no spatially resolved research in the femtosecond regime elucidating this electronic phenomenon. This work presents the ultrafast resonse in Lithiumborhydrid (LiBH4) to strong electronic fields with optical frequencies, which leads to charge relocation accompanied by electronic polarisation.
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Eftekharibafrooei, Ali. "Ultrafast Vibrational Spectroscopy and Dynamics of Water at Interfaces." Diss., Temple University Libraries, 2011. http://cdm16002.contentdm.oclc.org/cdm/ref/collection/p245801coll10/id/107351.
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ChemistryPh.D.
Over the past two decades, vibrational sum-frequency generation (VSFG) has been applied as a versatile technique for probing the structure and dynamics of molecules at surfaces and interfaces. The excellent surface specificity of the SFG allows for probing different kinds of liquid interfaces with no or negligible contribution from adjacent and much deeper bulk phase. VSFG spectroscopy has provided evidence that the structure of the water at interfaces is different from the bulk. With the ultrafast pulses, VSFG can also be used as a probe of ultrafast vibrational dynamics at interfaces. However, apart from a few pioneering studies, the extension of VSFG into time domain has not been explored extensively. Here VSFG is used as a probe of ultrafast vibrational dynamics of water at silica interfaces. Silica is an excellent model system for the solid phase where one can systematically vary the surface charge via bulk pH adjustment. The extension of the surface electric field, the interfacial thickness and surface accumulation of ions at a charged silica surface were studied using IR pump-VSFG probe spectroscopy. A vibrational lifetime (T1) of about 250 fs, similar to bulk H2O, was observed for the O-H stretch of H2O/silica interface when the silica surface is negatively charged. At the neutral surface, where the thickness of interfacial water is smaller than at the charged surface, the vibrational lifetime of O-H stretch becomes more than two times longer (T1~ 600 fs) due to the decreased number of neighboring water molecules, probed by SFG. The fast T1 at negatively charged surface begins to slow down by screening of the penetration of surface electric field via adding salt which suggests the primary reason for similar vibrational dynamics of water at charged interface with bulk water is the penetration of electric field. By decoupling of OH of HDO in D2O, a frequency dependent vibrational lifetime is observed with faster T1 at the red compared to the blue side of the hydrogen bond spectral region. This correlates with the redshift of the SFG spectra with increasing charged surface and is consistent with a theoretical model that relates the vibrational lifetime to the strength of the hydrogen bond network.
Temple University--Theses
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Aladool, Azzam Salahuddin Younus. "Investigation of crystallization dynamics in phase-change material using the Master rate equation at ultrafast heating rates." Thesis, University of Exeter, 2017. http://hdl.handle.net/10871/29434.
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Phase-change materials are widely used in non-volatile computer memories, and in arithmetic and logic processing applications. Phase-change based devices are also required to operate at different and high heating rates in response to electrical or optical excitations to achieve the required read-write rates. Crystallization is a fundamental and complex process involved in the phase transition operation in phase-change materials. It is sensitive to the nature of the phase-change material, its thermodynamic and kinetic parameters, geometric and interface effects, and thermal history. Thus, crystallization is the time limiting process in phase-change technologies. This work is concerned with theoretically understanding the crystallization dynamics of the Ge2Sb2Te5 (GST) phase-change material under different heating regimes and at the micro-structure level of the material to reduce crystallization times and increase the operating speed of phase-change devices and memories. A review and comparison of crystallization models was carried out to distinguish the more physically realistic Master rate equation method's ability to naturally trace both the nucleation and growth processes during crystallization, through the attachment and detachment of monomers to calculate the distribution of nano-cluster size distributions necessary to achieve the aims of this research. Full mathematical derivations and numerical implementation details of both the original discrete form of the Master rate equation and its approximate form were provided. Error analysis and computational experiments illustrated the limitations of the approximate form of the rate equation, and its detrimental sensitivity to the model parameters to justify the use of the discrete rate equation throughout this work. The crystallization rate is a strong function of the material's viscosity, and hence the physically realistic Mauro−Yue−Ellison−Gupta−Allan (MYEGA) model of the temperature dependence of viscosity was implemented in the Master rate equation. Crystallization simulations were carried out under ramped annealing conditions with heating rates from 50 K/s to 40,000 K/s to study the role of the viscosity model parameters (including the fragility index, glass transition temperature, and infinite temperature viscosity) on the crystallization dynamics. Those simulations showed, for high and low heating rates, the influence of the increasing fragility index on reducing the cluster nucleation time and increasing the crystallization speeds. Moreover, the increase of the glass transition temperature made a corresponding shift in crystallization temperature towards higher values. Furthermore, at low heating rates, infinite temperature viscosity parameter (i.e. extrapolated value of viscosity at temperature = ∞) has negligible effect on the crystallization dynamics while, at higher heating rates, smaller values of infinite temperature viscosity parameter increase the crystallization rate and final crystalline volume. Due to the relatively low computational cost of the Master rate equation method (compared to atomistic level computations), an iterative numerical algorithm was developed to fit Kissinger plots simulated with the Master rate equation system to experimental Kissinger plots from ultrafast calorimetry measurements at increasing heating rates. The simulations and analysis revealed the strong coupling between the glass transition temperature and fragility index, and highlighted the often ignored role of the dependence of the glass transition temperature on heating rate for the accurate estimation of the fragility index from analysis of experimental measurements. The extracted fragility indices in this work were lower than published values, highlighting the limitations of existing methods of extracting the viscosity parameters (using oversimplified analytical models with disparity in model parameters), and the importance of using detailed crystallization models for analysis of experimental measurements. Moreover, and for the first time, the variation of glass transition temperature with heating rate for GST was extracted from Kissinger measurements, in agreement with the values reported in the literature. The influence of the preparation conditions of amorphous GST on the crystallization dynamics was theoretically investigated using the Master rate equation by systematically implementing initial distributions of cluster sizes resulting from different thermal treatments such as melt-quenching and pre-annealing, and theoretical Gaussian initial cluster size distributions. Simulations of ramped pre-annealing to temperatures much lower than the crystallization temperature showed distributions of nano-clusters sizes of 2 - 8 nm in agreement with recently published high-resolution transmission electron microscopy measurements. Furthermore, the simulations explicitly showed the marked decrease in crystallization temperature (and therefore increase in crystallization speed) when there is predominately a narrow distribution of smaller crystalline clusters embedded in the initial amorphous phase.
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Zerdane, Serhane. "Exploring photoswitching pathways in photomagnetic materials with ultrafast optical and X-ray spectroscopies." Thesis, Rennes 1, 2017. http://www.theses.fr/2017REN1S150/document.
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Ce travail de thèse porte sur l’étude de la dynamique femtoseconde de photo-commutation de matériaux moléculaires bistables, à l’aide d’expériences pompe-sonde basées sur les spectroscopies optiques et rayons X. Une partie des expériences a été réalisée sur synchrotron et X-FEL (X-ray Free Electron Laser). La première partie de la thèse, qui est consacrée à l’étude de systèmes à transition de spin non-octaédriques, a révélé différents chemins de transformations sur la surface de potentiel, associés à différents mécanismes de changement d’état électronique et modulant la cohérence de la dynamique structurale pilotant le processus. La seconde partie porte sur l’étude d’analogues du bleu de Prusse (CoFe) où les expériences ultra-rapides ont permis de d’étudier les dynamiques de transformation autour des sites de fer et de cobaltThis thesis focuses on the study of the femtosecond photoswitching dynamic in the bistable molecular materials, using the pump-probe experiments which are based on the optical and x-ray spectroscopies. Part of these experiments was performed at synchrotron and X-FEL (X-ray Free Electron Laser). The first part of the thesis, which is devoted to the study of non-octahedral spin transition systems, revealed different pathways of transformation on the potential surface. The second part focuses on the study of the Prussian Blue Analogues (CoFe), where the ultra-fast experiments allowed to follow the dynamics around the two metal ions
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Bragaglia, Valeria. "Epitaxial Growth and Ultrafast Dynamics of GeSbTe Alloys and GeTe/Sb2Te3 Superlattices." Doctoral thesis, Humboldt-Universität zu Berlin, 2017. http://dx.doi.org/10.18452/18406.
Full textAbstract:
In dieser Arbeit wird das Wachstum von dünnen quasi-kristallinen Ge-Sb-Te (GST) Schichten mittels Molekularstrahlepitaxie demonstriert, die zu einer geordneten Konfiguration von intrinsischen Kristallgitterfehlstellen führen. Es wird gezeigt, wie es eine Strukturanalyse basierend auf Röntgenstrahlbeugungssimulationen, Dichtefunktionaltheorie und Transmissionselektronenmikroskopie ermöglicht, eine eindeutige Beurteilung der Kristallgitterlückenanordnung in den GST-Proben vorzunehmen. Das Verständnis für die Ordnungsprozesse der Gitterfehlstellen erlaubt eine gezielte Einstellung des Ordnungsgrades selbst, der mit der Zusammensetzung und der Kristallphase des Materials in Zusammenhang steht. Auf dieser Basis wurde ein Phasendiagramm mit verschiedenen Wachstumsfenstern für GST erstellt. Des Weiteren wird gezeigt, dass man eine hohe Ordnung der Gitterfehlstellen in GST auch durch Ausheizprozesse und anhand von Femtosekunden-gepulster Laserkristallisation von amorphem Material erhält, das zuvor auf einem als Kristallisationsgrundlage dienenden Substrat abgeschiedenen wurde. Diese Erkenntnis ist bemerkenswert, da sie zeigt, dass sich kristalline GST Schichten mit geordneten Kristallgitterlücken durch verschiedene Herstellungsprozesse realisieren lassen. Darüber hinaus wurde das Wachstum von GeTe/Sb2Te3 Übergittern durchgeführt, deren Struktur die von GST mit geordneten Gitterfehlstellen widerspiegelt.
Die Möglichkeit den Grad der Gitterfehlstellenordung in GST gezielt zu manipulieren wurde mit einer Studie der Transporteigenschaften kombiniert. Die Anwendung von großflächigen Charakterisierungsmethoden wie XRD, Raman und IR-Spektroskopie, erlaubte die Bestimmung der Phase und des Fehlstellenordnungsgrades von GST und zeigte eindeutig, dass die Fehlstellenordnung für den Metall-Isolator-Übergang (MIT) verantwortlich ist. Insbesondere wird durch das Vergleichen von XRD-Messungen mit elektrischen Messungen gezeigt, dass der Übergang von isolierend zu leitend erfolgt, sobald eine Ordnung der Kristallgitterlücken einsetzt. Dieses Phänomen tritt in der kubischen Kristallphase auf, wenn Gitterfehlstellen in GST von einem ungeordneten in einen geordneten Zustand übergehen. Im zweiten Teil des Kapitels wird eine Kombination aus FIR- und Raman-Spektroskopie zur Untersuchung der Vibrationsmoden und des Ladungsträgerverhaltens in der amorphen und der kristallinen Phase angewendet, um Aktivierungsenergien für die Elektronenleitung, sowohl für die kubische, als auch für die trigonale Kristallphase von GST zu bestimmen. Hier ist es wichtig zu erwähnen, dass, in Übereinstimmung mit Ergebnissen aus anderen Untersuchungen, das Auftauchen eines MIT beim Übergang zwischen der ungeordneten und der geordneten kubischen Phase beobachtet wurde.
Schlussendlich wurden verschiedene sogenannte Pump/Probe Technik, bei der man das Material mit dem Laser anregt und die Röntgenstrahlung oder Terahertz (THz)-spektroskopie als Sonde nutzt, angewandt. Dies dient um ultra-schnelle Dynamiken zu erfassen, die zum Verständnis der Umschaltmechanismen nötig sind. Die Empfindlichkeit der THz-Messungen hinsichtlich der Leitfähigkeit, sowohl in GST, als auch in GeTe/Sb2Te3 Übergittern zeigte, dass die nicht-thermische Natur der Übergitterumschaltprozesse mit Grenzflächeneffekten zusammenhängt und . Der Ablauf wird mit beeindruckender geringer Laser-Fluenz erreicht. Dieses Ergebnis stimmt mit Berichten aus der Literatur überein, in denen ein Kristall-zu Kristallwechsel von auf Übergittern basierenden Speicherzellen für effizienter gehalten wird als GST Schmelzen, was zu einen ultra-schwachen Energieverbrauch führt.The growth by molecular beam epitaxy of Ge-Sb-Te (GST) alloys resulting in quasi-single-crystalline films with ordered configuration of intrinsic vacancies is demonstrated. It is shown how a structural characterization based on transmission electron microscopy, X-ray diffraction and density functional theory, allowed to unequivocally assess the vacancy ordering in GST samples, which was so far only predicted. The understanding of the ordering process enabled the realization of a fine tuning of the ordering degree itself, which is linked to composition and crystalline phase. A phase diagram with the different growth windows for GST is obtained. High degree of vacancy ordering in GST is also obtained through annealing and via femtosecond-pulsed laser crystallization of amorphous material deposited on a crystalline substrate, which acts as a template for the crystallization. This finding is remarkable as it demonstrates that it is possible to create a crystalline GST with ordered vacancies by using different fabrication procedures. Growth and structural characterization of GeTe/Sb2Te3 superlattices is also obtained. Their structure resembles that of ordered GST, with exception of the Sb and Ge layers stacking sequence. The possibility to tune the degree of vacancy ordering in GST has been combined with a study of its transport properties. Employing global characterization methods such as XRD, Raman and Far-Infrared spectroscopy, the phase and ordering degree of the GST was assessed, and unequivocally demonstrated that vacancy ordering in GST drives the metal-insulator transition (MIT). In particular, first it is shown that by comparing electrical measurements to XRD, the transition from insulating to metallic behavior is obtained as soon as vacancies start to order. This phenomenon occurs within the cubic phase, when GST evolves from disordered to ordered. In the second part of the chapter, a combination of Far-Infrared and Raman spectroscopy is employed to investigate vibrational modes and the carrier behavior in amorphous and crystalline phases, enabling to extract activation energies for the electron conduction for both cubic and trigonal GST phases. Most important, a MIT is clearly identified to occur at the onset of the transition between the disordered and the ordered cubic phase, consistently with the electrical study. Finally, pump/probe schemes based on optical-pump/X-ray absorption and Terahertz (THz) spectroscopy-probes have been employed to access ultrafast dynamics necessary for the understanding of switching mechanisms. The sensitivity of THz-probe to conductivity in both GST and GeTe/Sb2Te3 superlattices showed that the non-thermal nature of switching in superlattices is related to interface effects, and can be triggered by employing up to one order less laser fluences if compared to GST. Such result agrees with literature, in which a crystal to crystal switching of superlattice based memory cells is expected to be more efficient than GST melting, therefore enabling ultra-low energy consumption.
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Schill, Alexander Wilhem. "Interesting Electronic and Dynamic Properties of Quantum Dot Quantum Wells and other Semiconductor Nanocrystal Heterostructures." Diss., Georgia Institute of Technology, 2006. http://hdl.handle.net/1853/11514.
Full textAbstract:
Some interesting electronic and dynamic properties of semiconductor nanocrystal heterostructures have been investigated using various spectroscopic methods. Semiconductor nanocrystal heterostructures were prepared using colloidal synthesis techniques. Ultrafast transient absorption spectroscopy was used to monitor the relaxation of hot electrons in CdS/HgS/CdS quantum dot quantum wells. Careful analysis of the hot electron relaxation in CdS/HgS/CdS quantum dot quantum wells reveals an energy dependent relaxation mechanism involving electronic states of varying CdS and HgS composition. The composition of the electronic states, combined with the layered structure of the nanocrystal permits the assignment of CdS localized and HgS localized excited states. The dynamic effect of surface passivation is then shown to have the strongest influence on excited states that are localized in the HgS layer.
New quantum dot quantum well heterostructures of different sizes and compositions were also prepared and studied. The dynamic properties of CdS/CdSe/CdS colloidal quantum wells suggest simultaneous relaxation of excited electrons within the CdS core and CdSe shell on the sub-picosecond time scale. Despite the very different electronic structure of CdS/CdSe/CdS compared to CdS/HgS/CdS, the time scales of the relaxation and electron localization were very similar.
Enhancement of trap luminescence was observed when CdS quantum dots were coated with silver. The mechanism of the enhancement was investigated using time-resolved spectroscopic techniques.
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Sanches, Piaia Monica. "Femtosecond magneto-optical four-wave mixing in Garnet films." Thesis, Strasbourg, 2014. http://www.theses.fr/2014STRAE024/document.
Full textAbstract:
Un des objectifs du Femtomagnetisme est de contrôler l’aimantation des matériaux avec des impulsions laser femtoseconde. Il a été démontré qu’une réponse magnéto-optique (MO) cohérente a lieu avant la thermalisation des populations de spins dans une configuration pompe-sonde MOKE. Elle résulte du couplage cohérent spin-photon dû à l’interaction spin-orbite. Une description simplifiée de cet effet a été faite en tenant compte d’un système à huit niveaux couplés au champ laser. La cohérence MO est définie par le temps de déphasage dépendent du champ T2MO. Dans ce travail, il est montré que la réponse MO cohérente d’un grenat dopé au bismuth peut être mesurée directement avec différentes configurations de mélange à quatre ondes MO. L’importance de connaître la phase spectrale de l’impulsion pour obtenir T2MO a été étudié. Avec des impulsions de 10fs dans le proche infra-rouge, une mesure de T2MO donne (2.8+/-1)fs, c. à d., du même ordre de grandeur que le temps de déphasage des chargesOne of the goals of Femtomagnetism is to manipulate the magnetization of materials using femtosecond optical pulses. It has been shown in ferromagnetic films that a magneto-optical (MO) coherent response takes place before the thermalization of the spins populations in a pump and probe MOKE experiment. It results from the coherent spin-photon coupling mediated by the spin-orbit interaction. A simplified description of this effect has been made by considering an eight-level system coupled with the laser field. The MO coherence can be defined by the magnetic field dependent dephasing time T2MO. In the present work, it is shown that the coherent MO response of a bismuth-doped garnet can be directly measured in different degenerated MO four-wave mixing configurations. The importance of well-knowing the spectral phase of the pulse to measure T2MO was studied. Using 10fs near infra-red pulses, T2MO was shown to be (2.8+/-1)fs that is of the same order of the charges dephasing time
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Ahmed, Ghada H. "Tracking Ultrafast Charge Carrier Dynamics at the Interface of Semiconductor Nanocrystals." Diss., 2020. http://hdl.handle.net/10754/661839.
Full textAbstract:
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.
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Cheng, Ting-Pu, and 鄭亭菩. "Ultrafast Time-Resolved Fluorescence Studies of Intermolecular Charge Transfer Dynamics in Olefin-Tetracyanoethylene Complexes." Thesis, 2018. http://ndltd.ncl.edu.tw/handle/48juvh.
Full textAbstract:
碩士國立清華大學
化學系所
106
We studied the charge-transfer (CT) state relaxation dynamics of a series of electron donor-acceptor (EDA) complexes with broadband ultrafast time-resolved fluorescence spectroscopy implemented by optical Kerr gating and transient absorption spectroscopy. The EDA complexes studied here are those containing various olefins (1-hexene, 2-hexene, 1-methylcyclohexene, 2,3-dimethyl-2-butene) as the donor and tetracyanoethylene (TCNE) as the acceptor. In our experiments, the CT state of the EDA complexes are directly reached by femtosecond laser excitation in either CH2Cl2 or CCl4 solutions, and the subsequent temporal evolution of the fluorescence spectra were measured to explore the charge recombination (CR) dynamics. EDA complexes with various arenes, including methyl substituted and non-methyl substituted benzenes, as the donor have been studied previously in our laboratory. We used the total fluorescence intensity function P(t) to analyze CT state relaxation and CR dynamics of EDA complexes. We found two different decay behaviors in these olefin-TCNE complexes. The faster component (<1 ps) was assigned to vibrational relaxation and solvation , the slower component was attributed to CR. We concluded that the most important difference between the olefin-TCNE and arene-TCNE complexes was the electronic coupling strength. The greater electronic coupling strength in the olefin-TCNE complexes extremely accelerates CR reactions and result in a weak dependence of ET rate on the driving-force.
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Yu, Chin Ann, and 于慶安. "Ultrafast Time-Resolved Fluorescence Studies of Intermolecular Charge Transfer Dynamics in Tetracyanoethylene-Methylbenzene Complexes." Thesis, 2015. http://ndltd.ncl.edu.tw/handle/39670260453970693098.
Full textAbstract:
碩士國立清華大學
化學系
103
This dissertation employed an ultrafast time-resolved fluorescence (TRFL) spectrometer implemented by optical Kerr gating (OKG) and density functional theory calculations implemented in the Gaussian 09 program to study electron transfer dynamics in tetracyanoethylene-methylbenzene (TCNE-MBZ) complexes (MBZ = Benzene, Toluene, p-Xylene) in two solvents (CH2Cl2, CCl4) of different polarities. We used femtosecond laser to excite the TCNE-MBZ complexes to the CT-states, and the resulting TRFL spectra were measured. Analyses of the total fluorescence intensity function P(t), which describes the temporal evolution of excited state population and transition dipole moment, revealed complex relaxations associated with charge recombination (CR). We found different decay behaviors in two solvents. The fastest component which are in the similar time scale (< 0.2 ps) for the three complexes is assigned to CT2→CT1 transition, and the slowest component is ascribed to CR. The CR time constants in CH2Cl2 for TCNE-p-Xylene, TCNE-Toluene, TCNE- Benzene are 0.5, 7 and 29 ps, respectively, The CR time constants in CCl4 for TCNE-p-Xylene, TCNE-Toluene, TCNE- Benzene are 290, 820 and 150 ps, respectively. We concluded that CR time constants are consisted with the behavior in the Marcus inverted region. However the CR rates in CCl4 is reverted when the driving force(-∆G0) increase in the case of TCNE-Benzene. We use the intersecting state model (ISM) to explain this unexpected behavior. ISM accounts for structural relaxation of complex which the Marcus theory does not consider. Finally, we found that the CR rates of complexes in polar solvent is faster than in nonpolar solvent, which is mostly due to solvation effet.
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Minda, Iulia. "Photoinduced charge dynamics in indoline-dye sensitised solar cells." Thesis, 2014. http://hdl.handle.net/10019.1/95760.
Full textAbstract:
Thesis (MSc)--Stellenbosch University, 2014.ENGLISH ABSTRACT: The demand for renewable energy sources has grown out of the humanity’s increasing need for electricity as well as depleting fossil fuel reserves. Organic-dye sensitised solar cells were developed as a green, cost-effective alternative to the market-dominating silicon solar cell technology. The field of photovoltaic devices and organic-DSSCs is interesting because we want to develop better, more efficient cells at lower costs using environmentally friendly materials. By studying the fundamental physics and chemistry processes occurring during and after the interaction of light with these devices, we create a window into the mechanism of photosynthesis. Our DSSCs were prepared by sensitisation of highly porous ZnO with different indoline dyes containing the same chromophore, but different alkyl chain lengths bonded to one of two carboxyl anchors as: DN91 (1 C) < DN216 (5 C) < DN285 (10 C). The role of the dye molecules is to absorb photons and donate electrons to the ZnO which acts as the charge acceptor, at the dye|ZnO interface. Through photoelectrochemical characterisation it was found that the structure of the dyes has an effect on the maximum current (JSC) produced by the cells: the shorter the alkyl chain, the higher the JSC. This macroscopic investigation was complimented by microscopic measurements in the form of transient absorption spectroscopy. This allows us to follow, in real time, the photoinduced oxidation of the dye and its regeneration occurring through desired and undesired pathways. It was found that the injection efficiencies of the dye molecules were directly responsible for the trend in the short circuit currents.
AFRIKAANSE OPSOMMING: Die aanvraag na die ontwikkeling van herwinbare energie bronne spruit voort uit die voorsienbare uitputting van fossiel brandstof bronne sowel as die groeiende behoefte om aan die mensdom se elektrisiteit behoeftes te voldoen. Kleurstof gesensitiseerde sonselle is ontwikkel as ’n groen, koste-effektiewe alternatief tot die silikon sonsel tegnologie wat die mark domineer. Die fotovoltaïse toestel veld, spesifiek organiese kleurstof gesensitiseerde sonselle is interessant omdat daar ruimte bestaan vir die ontwikkeling van beter meer effektiewe selle in terme van vervaardigings koste en prosesse wat omgewingsvriendelik is. Deur die fundamentele fisika en chemiese prosesse wat plaas vind tydens en na lig interaksie met hierdie selle te bestudeer gee dit insig oor die werkingsmeganisme van fotosintese. Ons kleurstof gesensitiseerde sonselle is voorberei deur sensitasie van hoogs poreuse ZnO met verskillende indolien kleurstowwe wat dieselfde kromofoor bevat wat met verskillende alkiel ketting lengtes verbind is aan een van twee karboksiel ankers as: DN91 (1 C) < DN216 (5 C) < DN285 (10 C). Die rol van die kleurstof molekules is om fotone te absorbeer en elektrone te doneer aan die ZnO wat as die lading akseptor dien by die kleurstof|ZnO intervlak. Deur fotoelektrochemiese karakterisasie is bevind dat die struktuur van die kleurstof ’n effek het op die maksimum stroom (JSC) wat die selle produseer: hoe korter die die akiel ketting, hoe hoër die JSC. Hierdie makroskopiese ondersoek is voltooi deur mikroskopiese metings in die vorm van tydopgelosde absorpsiespektroskopie. Dit laat ons toe om die fotogeinduseerde oksidasie asook regenerasie van die kleurstof te volg soos wat dit plaas vind deur gewenste sowel as ongewenste roetes. Dit is bevind dat die inspuitings effektiwiteit van die kleurstof molekules direk verantwoordelik is vir die waarneembare trajek in die kortsluitings stroom.
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Shaheen, Basamat S. "Real-Space Imaging of Charge Carrier Dynamics in Photoactive Materials by 40 Scanning Ultrafast Electron Microscopy." Diss., 2019. http://hdl.handle.net/10754/653701.
Full textAbstract:
Surfaces of photoactive materials play a pivotal role in determining the interfacial properties and the photoconversion efficiency of optoelectronic devices. On the other hand, the fundamental photophysical processes of photo-generated carriers and their transport and recombination occur at extremely short timescales ranging from femtoseconds to nanoseconds. In order to provide a complete picture about the best working conditions of photoactive materials to improve their device performance, it is very essential to explore and decipher the ultrafast surface dynamics at nanoscale or even atomic levels. Four-dimensional scanning ultrafast electron microscopy (4D S-UEM) is the sole technique capable of surface-selective visualization of light-triggered carrier dynamics at nanometer scale. Herein, 4D S-UEM is used to investigate the effect of several key factors on the surface charge carrier dynamics of a variety of photoactive materials: (1) surface passivation in lnGaN nanowires, (2) deposition method in PbS quantum dots,(3) thickness in CdSe thin films, (4) crystal orientation in CdTe single crystals and (5) native oxide layer in Si wafers. Besides the visualization of surface charge carrier dynamics in these materials, new surface features were discovered such as the superior charge carrier diffusion on the surfaces of CdTe single crystals ≈ 10^4 times larger than that in their crystal's bulk. Furthermore, utilizing 4D S-UEM at low accelerating voltage of 1 kV enables monitoring the diffusion from underneath the surface region and discovering the reason behind the energy loss mechanism and ultrafast carrier recombination of surface charge carriers in solar cell materials, unlocking their interfacial behaviors at the nanoscale level. These new findings are believed to provide the foundation for potential applications of 4D S-UEM to be the method of choice in studies of surface dynamics in chemistry, materials science, and other disciplines. Furthermore, the work presented here provides the key to unlocking further optimizations of the surfaces and interfaces of photoactive materials, thus paving the way for more efficient optoelectronic devices.
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Storeck, Gero. "Non-equilibrium structural Dynamics of incommensurate Charge-Density Waves." Doctoral thesis, 2020. http://hdl.handle.net/21.11130/00-1735-0000-0005-13F4-2.
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Chen, Guan-Shao, and 陳冠劭. "Ultrafast Time-Resolved Fluorescence Studies of Intermolecular Charge Transfer Dynamics in non-Methyl Substituted Benzene-Tetracyanoethylene Complexes." Thesis, 2017. http://ndltd.ncl.edu.tw/handle/bx3j2j.
Full textAbstract:
碩士國立清華大學
化學系所
106
Ultrafast dynamics of substituted benzene-TCNE complexes in two solvents (CH2Cl2, CCl4) was investigated in ultrafast time-resolved fluorescene (TRFL) spectrometer implemented by optical Kerr gating (OKG). We used femtosecond laser to excite the non-methyl substituted benzene-TCNE complexes to CT states, and the resulting TRFL spectra were measured. We used the total fluorescene (P(t)) to analyze the result which reveal complexes relaxations associated with charge recombination(CR). We found different decay behaviors in different solvents. The fastest component in the similar time scale (<0.2 ps) for three complexes (chlorobenzene(PhCl)-TCNE、fluorobenzene(PhF)-TCNE、benzonitrile(PhCN)-TCNE) is assigned to CT2→CT1 transition and the slowest component is ascribed to CR. The CR time constant in CH2Cl2 for PhCl-TCNE、PhF-TCNE、PhCN-TCNE are 45, 21 and29 ps, respectively. The CR time constant in CCl4 for PhCl-TCNE、PhF-TCNE、Tolunitrile-TCNE、PhCN-TCNE、4-chlorobenzonitrile-TCNE are 580, 470, 210, 140 and 280 ps, respectively. We concluded that no matter which solvents we used, CR time constants of methylbenzene-TCNE complexes are consisted with the behavior in the Marcus inverted region. However, the others violate the behavior. We use the intersecting state model (ISM) which accounts for structural relaxation of complex that the Marcus theory doesn’t consider to explain this unexpected behavior.
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Vogelgesang, Simon. "Ultrafast low-energy electron diffraction at surfaces." Doctoral thesis, 2018. http://hdl.handle.net/11858/00-1735-0000-002E-E5A1-F.
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(6577541), Long Yuan. "Spatial and Temporal Imaging of Exciton Dynamics and transport in two-dimensional Semiconductors and heterostructures by ultrafast transient absorption microscopy." Thesis, 2019.
Find full textAbstract:
Recently, atomically thin two-dimensional (2D) layered materials such as graphene and transition metal dichalcogenides (TMDCs) have emerged as a new class of materials due to their unique electronic structures and optical properties at the nanoscale limit. 2D materials also hold great promises as building blocks for creating new heterostructures for optoelectronic applications such as atomically thin photovoltaics, light emitting diodes, and photodetectors. Understanding the fundamental photo-physics process in 2D semiconductors and heterostructures is critical for above-mentioned applications.
In Chapter 1, we briefly describe photo-generated charge carriers in two-dimensional (2D) transition metal dichalcogenides (TMDCs) semiconductors and heterostructures. Due to the reduced dielectric screening in the single-layer or few-layer of TMDCs semiconductors, Columbo interaction between electron and hole in the exciton is greatly enhanced that leads to extraordinary large exciton binding energy compared with bulk semiconductors. The environmental robust 2D excitons provide an ideal platform to study exciton properties in TMDCs semiconductors. Since layers in 2D materials are holding by weak van de Waals interaction, different 2D layers could be assembled together to make 2D heterostructures. The successful preparation of 2D heterostructures paves a new path to explore intriguing optoelectronic properties.
In Chapter 2, we introduce various optical microscopy techniques used in our work for the optical characterization of 2D semiconductors and heterostructures. These optical imaging tools with high spatial and temporal resolution allow us to directly track charge and energy flow at 2D interfaces.
Exciton recombination is a critical factor in determining the efficiency for optoelectronic applications such as semiconductor lasers and light-emitting diodes. Although exciton dynamics have been investigated in different 2D semiconductor, large variations in sample qualities due to different preparation methods have prevented obtaining intrinsic exciton lifetimes from being conclusively established. In Chapter 3, we study exciton dynamics in 2D TMDCs semiconductors using ultrafast PL and transient absorption microscopy. Here we employ 2D WS2 semiconductor as a model system to study exciton dynamics due to the low defect density and high quantum yield of WS2. We mainly focus on how the exciton population affects exciton dynamics. At low exciton density regime, we demonstrate how the interlayer between the bright and dark exciton populations influence exciton recombination. At high exciton density regime, we exhibit significant exciton-exciton annihilation in monolayer WS2. When comparing with the bilayer and trilayer WS2, the exciton-exciton annihilation rate in monolayer WS2 increases by two orders of magnitude due to enhanced many-body interactions at single layer limit.
Long-range transport of 2D excitons is desirable for optoelectronic applications based on TMDCs semiconductors. However, there still lacks a comprehensive understanding of the intrinsic limit for exciton transport in the TMDCs materials currently. In Chapter 4, we employ ultrafast transient absorption microscopy that is capable of imaging excitons transport with ~ 200 fs temporal resolution and ~ 50 nm spatial precision to track exciton motion in 2D WS2 with different thickness. Our results demonstrate that exciton mobility in single layer WS2 is largely limited by extrinsic factors such as charge impurities and surface phonons of the substrate. The intrinsic phonon-limited exciton transport is achieved in WS2 layers with a thickness greater than 20 layers.
Efficient photocarrier generation and separation at 2D interfaces remain a central challenge for many optoelectronic applications based on 2D heterostructures. The structural tunability of 2D nanostructures along with atomically thin and sharp 2D interfaces provides new opportunities for controlling charge transfer (CT) interactions at 2D interfaces. A largely unexplored question is how interlayer CT interactions contribute to interfacial photo-carrier generation and separation in 2D heterostructures. In Chapter 5, we present a joint experimental and theoretical study to address carrier generation from interlayer CT transitions in WS2-graphene heterostructures. We use spatially resolved ultrafast transient absorption microscopy to elucidate the role of interlayer coupling on charge transfer and photo-carrier generation in WS2-graphene heterostructures. These results demonstrate efficient broadband photo-carrier generation in WS2-graphene heterostructures which is highly desirable for atomically thin photovoltaic and photodetector applications based on graphene and 2D semiconductors.
CT exciton transport at heterointerfaces plays a critical role in light to electricity conversion using 2D heterostructures. One of the challenges is that direct measurements of CT exciton transport require quantitative information in both spatial and temporal domains. In order to address this challenge, we employ transient absorption microscopy (TAM) with high temporal and spatial resolution to image both bright and dark CT excitons in WS2-tetrance and CVD WS2-WSe2 heterostructure. In Chapter 6, we study the formation and transport of interlayer CT excitons in 2D WS2-Tetracene vdW heterostructures. TAM measurements of CT exciton transport at these 2D interfaces reveal coexistence of delocalized and localized CT excitons. The highly mobile delocalized CT excitons could be the key factor to overcome large CT exciton binding energy in achieving efficient charge separation. In Chapter 7, we study stacking orientational dependent interlayer exciton recombination and transport in CVD WS2-WSe2 heterostructures. Temperature-dependent interlayer exciton dynamics measurements suggest the existence of moiré potential that localizes interlayer excitons. TAM measurements of interlayer excitons transport reveal that CT excitons at WS2-WSe2 heterointerface are much more mobile than intralayer excitons of WS2. We attributed this to the dipole-dipole repulsion from bipolar interlayer excitons that efficiently screen the moiré potential fluctuations and facilitate interlayer exciton transport. Our results provide fundamental insights in understanding the influence of moiré potential on interlayer exciton dynamics and transport in CVD WS2-WSe2 heterostructures which has important implications in optoelectronic applications such as atomically thin photovoltaics and light harvesting devices.
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El, Demellawi Jehad K. "Active Control of Surface Plasmons in MXenes for Advanced Optoelectronics." Diss., 2020. http://hdl.handle.net/10754/666285.
Full textAbstract:
MXenes, a new class of two-dimensional (2D) materials, have recently demonstrated impressive optoelectronic properties associated with its ultrathin layered structure. Particularly, Ti3C2Tx, the most studied MXene by far, was shown to exhibit intense surface plasmons (SPs), i.e. collective oscillations of free charge carriers, when excited by electromagnetic waves. However, due to the lack of information about the spatial and energy variation of those SPs over individual MXene flakes, the potential use of MXenes in photonics and plasmonics is still marginally explored. Hence, the main objective of this dissertation is to shed the light upon the plasmonic behavior of MXenes at the nanoscale and extend their use beyond their typical electrochemical applications.
To fulfill our objective, we first elucidated the underlying characteristics governing the plasmonic behavior of MXenes. Then, we revealed the existence of various tunable SP modes supported by different MXenes, i.e. Ti3C2Tx and Mo2CTx, and investigated their energy and spatial distribution over individual flakes. Further, we fabricated an array of MXene-based flexible photodetectors that only operate at the resonant frequency of the SPs supported by MXenes. We also unveiled the existence of tunable SPs supported by another 2D nanomaterial (i.e. MoO2) and juxtaposed its plasmonic behavior with that of MXenes, to underline the uniqueness of the latter. Noteworthy, as in the case of MXenes, this was the first progress made on studying specific SP modes supported by MoO2 nanostructures. In this part of the dissertation, we were able to identify and tailor multipolar SPs supported by MoO2 and illustrate their dependence on their bulk band structure.
In the end, we show that, on the contrary, SPs in MXenes are mainly controlled by the surface band structure. To confirm this, we selectively altered the subsurface band structure of Ti3C2Tx and modulated its work function (from 4.37 to 4.81 eV) via charge transfer doping. Interestingly, thanks to the unchanged surface stoichiometry of Ti3C2Tx, the plasmonic behavior of Ti3C2Tx was not affected by its largely tuned electronic structure. Notably, the ability to attain MXenes with tunable work functions, yet without disrupting their plasmonic behavior, is appealing to many application fields.
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CHÁBERA, Pavel. "Excited state dynamics of carotenoids in solution and proteins." Doctoral thesis, 2010. http://www.nusl.cz/ntk/nusl-53736.
Full textAbstract:
Time resolved spectroscopy is one of the crucial methods used to study processes on molecular level in biological systems. It is useful especially for monitoring fast processes that take a place in photosynthetic apparatus of photosynthetic organisms, such as electron and energy transfer. The integral parts of photosynthetic apparatus are carotenoids, whose role in the photosynthetic apparatus is not as well explored as it is for chlorophylls. It was proved that carotenoids actively participate in energy transfer processes in photosynthetic antennas. They have a crucial role in protection against excess energy damage. They are also electron donors in both antennas and reaction centers. The fact that photo-physical properties of carotenoids are much different from properties of others organic pigments, complicates studies of their functions in photosynthesis as well as in other biological systems. This thesis employs advanced methods of femtosecond spectroscopy to obtain more information about carotenoid functions in some biological systems and in solution with special focus on carotenoids containing carbonyl group.
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Yang, Po-Chun, and 楊博竣. "Ultrafast Photoionization Induced Charge-Transfer Dynamic in 2-phenylethyl-N,N-dimethylamine Cation." Thesis, 2018. http://ndltd.ncl.edu.tw/handle/2qjfs4.
Full textAbstract:
碩士國立清華大學
化學系所
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We study the ultrafast charge transfer (CT) dynamics in the cations of 2-phenylethyl-N,N-dimethylamine (PENNA), N-methylphenethylamine (MPEA) and their non-methylated counterpart, 2-phenylethylamine (PEA) after photoionization using the femtosecond pump-probe photoionization-photofragmentation (fs-PIPF) spectroscopy. Neutral PENNA, MPEA, PEA seeded in a He free jet are photoionized by femtosecond 1+1 resonance-enhanced multiphoton ionization via their S1 state, and the subsequent dynamics occurring in the cations is probed by delayed pulses that result in ion fragmentation. Using a kinetics model to fit our transients, we obtained three time constants from the PENNA+, MPEA+ and PEA+ ion depletion transients. We ascribed the sub-picoseconds time constants of PENNA+ (0.2 ps), MPEA+ (0.3 ps) and PEA+ (0.1 ps) to the CT dynamics by comparing them with a non-CT system 2-phenylethyl alcohol cation. Our results are quite different from those reported by the Schlag group in 2005. Besides, we also find some much shower components with time constants of few to few tens of picoseconds. These slower components were attributed to conformational relaxation of cations after CT.
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Klopf, J. Michael. "Ultrafast carrier dynamics measured by the transient change in the reflectance of InP and GaAs films /." 2006. http://wwwlib.umi.com/dissertations/fullcit/3198431.
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Wagener, Philipp. "Photodissoziation von Polyhalogenmethanen in Fluiden: Kurzzeitdynamik und Mechanismen." Doctoral thesis, 2008. http://hdl.handle.net/11858/00-1735-0000-0006-ACB1-4.
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