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Angle resolved photoemission spectroscopy study of the three-layered strontium ruthenate Sr₄Ru₃O₁₀Ngabonziza, Prosper 05 November 2012 (has links)
M.Sc. / This dissertation presents experimental data on the near Fermi-level electronic structure of Sr₄Ru₃O₁₀. This summary gives a review of the facts that have been observed in the analysis of the data taken, and directions for future work are suggested. The first part of this dissertation (from chapter 1 to chapter 3) is dedicated to a review on the studied system and the experimental technique exploited in this study. In fact, chapter 1 gives a review of the general physical properties of different members of the Ruddlesden Popper strontium ruthenate family Srn+1RunO3n+1, focusing on the trilayered Sr4Ru3O10 in particular. Furthermore, chapters 2 and 3 discuss some essential features of the theoretical and experimental aspects of angle resolved photoemission spectroscopy (ARPES), respectively. In the second part of the dissertation (chapter 4), the fi rst experimental ARPES data on band dispersions and Fermi surface maps of Sr4Ru3O10, are presented and discussed. The experiment was performed at the beamline Cassiopee of the Soleil synchrotron radiation facility in Paris (France). The study has provided the first information on the near Fermi-level band dispersions and Fermi surface of Sr4Ru3O10, the effect of changing different matrix elements on electronic band dispersions and Fermi surface maps of Sr4Ru3O10, and electronic correlations effects present in this compound. Remarkably, low temperature ( 5 K) ARPES data presented in this study suggest that there is only a 45 rotation of the square unit cell of Sr4Ru3O10, due to correlated rotations about the c-axis of the RuO6 octahedra, but no elongation of the sides of this unit cell; and consequently in reciprocal space the square BZ, determined by considering the symmetry of the Fermi surface sheets, is only rotated by 45 but its size is unchanged with respect to the non-distorted situation. However, this is not what is expected. Using room temperature lattice parameters from ref. [17], the BZ of this compound would be 45 rotated and reconstructed into a square twice smaller, a situation that was also previously observed in band structure calculations and ARPES data of Sr3Ru2O7 from ref. [4]. This behaviour was ascribed to the fact that the structure of this system is possibly not the same at room temperature as at low temperatures (down to 5 K), where the ARPES data of this work were acquired. Therefore low temperature (<100 K) X-ray diffraction data of Sr4Ru3O10 are needed in order to determine low temperature lattice parameters and compare them with room temperature ones so as to verify whether the structure of Sr4Ru3O10 is not the same at room and low temperatures.
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In-situ Photoemission Spectroscopy Characterization of Electronic States in Semiconductor InterfacesJanuary 2018 (has links)
abstract: The electronic states of semiconductor interfaces have significant importance for semiconductor device performance, especially due to the continuing miniaturization of device technology.
The application of ultra high vacuum (UHV) enables the preparation and characterization of fresh and cleaned interfaces. In a UHV environment, photoemission spectroscopy (PES) provides a non-destructive method to measure the electronic band structure, which is a crucial component of interface properties.
In this dissertation, three semiconductor interfaces were studies to understand different effects on electronic states. The interfaces studied were freshly grown or pre-treated under UHV. Then in-situ PES measurements, including x-ray photoemission spectroscopy (XPS) and ultra-violet photoemission spectroscopy (UPS), were conducted to obtain electronic states information.
First, the CdTe/InSb (100) heterointerface was employed as a model interface for II-VI and III-V heterojunctions. It was suggested that an interface layer formed, which consisted of In-Te bonding. The non-octal bonding between In and Te atoms has donor-like behavior, which was proposed to result in an electron accumulation layer in InSb. A type-I heterointerface was observed. Second, Cu/ZnO interfaces were studied to understand the interface bonding and the role of polarization on ZnO interfaces. It was shown that on O-face ZnO (0001) and PEALD ZnO, copper contacts had ohmic behavior. However, on Zn-face ZnO (0001), a 0.3 eV Schottky barrier height was observed. The lower than expected barrier heights were attributed to oxygen vacancies introduced by Cu-O bonding during interface formation. In addition, it is suggested that the different barrier heights on two sides of ZnO (0001) are caused by the different behavior for the ZnO (0001) faces. Last, a pulse mode deposition method was applied for P-doped diamond growth on (100) diamond surfaces. Pretreatment effects were studied. It is suggested that an O/H plasma treatment or a short period of H-plasma and CH4/H2 plasma could yield a higher growth rate. PES measurements were conducted on H-terminated intrinsic diamond surface and P-doped/intrinsic diamond (100) interfaces. It was suggested that electronic states near the valence band maximum caused Fermi level pinning effects, independent of the diamond doping. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2018
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Photoemission spectra of nanostructured solar cell interfaces from first principlesPatrick, Christopher Edward January 2013 (has links)
Photovoltaic (PV) technologies could provide abundant, clean and secure energy through the conversion of sunlight into electricity, but currently are too expensive to compete with conventional sources of power. Novel PV devices incorporating nanostructured materials, such as the dye-sensitized solar cell (DSC), have been identified as viable, low-cost alternatives to traditional solar cell designs. In spite of technological progress in the field over the last twenty years, the underlying physics governing DSC operation is still not well understood. In this thesis, first-principles (i.e. parameter-free) calculations are performed with the aim of connecting experimentally-measured photoemission data to the underlying atomistic and electronic structure of interfaces found in DSCs. The principal system under study is the interface between anatase titanium dioxide (TiO<sub>2</sub>) and the "N3" dye molecule, one of the most widely-investigated device designs in DSC research. Atomistic models of the interface are determined within density-functional theory. Core-level spectra of these interface models are then calculated using a ∆SCF approach. Comparison of the calculations to published experimental data finds that intermolecular interactions have a significant effect on the spectra. Next, the electronic structure of bulk TiO<sub>2</sub> and of isolated N3 molecules is calculated using the GW approximation and ∆SCF method respectively. For the former, it is shown that including Hubbard U corrections in the initial Hamiltonian reduces the GW gap by 0.4 eV. These calculations are then used to determine the valence photoemission spectrum of the full interface. By including image-charge effects, thermal broadening and configurational disorder, quantitative agreement with experimentally-measured spectra is demonstrated. In addition to the N3/TiO<sub>2</sub> system, calculations of the core-level spectra of the interfaces between TiO<sub>2</sub> and H<sub>2</sub>O and bi-isonicotinic acid are also presented. The thesis concludes with a study of the X<sub>2</sub>Y<sub>3</sub>/TiO<sub>2</sub> interfaces (X=Sb, Bi; Y=S, Se) found in recently-developed semiconductor-sensitized solar cells.
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Characterization of Heterojunctions via X-Ray and UV Photoemission Spectroscopy: Energy Level Implications for Single and Mixed Monolayer SAMs, CdSe Nanoparticle Films, and Organic Semiconductor Depositions.Graham, Amy L. January 2010 (has links)
This work has centered on the interface dipoles arising at heterojunctions between metals, semiconductor nanoparticles, self-assembled monolayers, and organic semiconductor materials. Alkanethiol self-assembled monolayers, CdSe nanocrystals, and the organic semiconductors zinc phthalocyanine (ZnPc) and Buckminster fullerene (C60) were the basis of these investigations. UV photoemission spectroscopy has proven to be an invaluable tool to observe the vacuum level shifts for these analyses while using XPS to corroborate surface structure. With a full evaluation of these surfaces, the shifts in the vacuum level, valence ionizations, and core ionizations, the impact of these interfaces, as well as their influence on the subsequent deposition of organic semiconductor layers is established.Alkanethiols possessing varying dipole moments were examined on gold and silver substrates. The viability of these alkanethiols was demonstrated to predictively adjust the work function of these metals as a function of their intrinsic dipole moments projected to surface normal, and established differences between Ag--S and Au--S bonds. The capability of the SAMs to modify the work function of gold provided an opportunity for mixed monolayers of the alkanethiols to produce a precise range of work functions by minimal adjustments of solution concentration, which were examined with a simple point dipole model.Photoemission spectroscopy offers a thorough analysis of CdSe nanoparticle films. Despite a plethora of research on these nanocrystals, there still is controversy on the magnitude of the shift in the valence band with diameter. In our research we found the majority of the valence band shift could be attributed to the interface dipole, ignored previously. Meanwhile, the valence band tethered films was obscured by the sulfur of the thiol tether.Finally, organic semiconductor layers deposited on SAMs on gold exhibited various interface dipole effects at these heterojunctions. Charge transfer states of ZnPc did not favor energy level alignment on the SAM/Au substrates used; C60 demonstrated vacuum level shifts on C15 and C12ph alkanethiol monolayers consistent with the interface charge transfer (ICT) model. These results provide credibility to models recently demonstrated in the literature for other passivated metal surfaces, and include the viability of SAMs in these discussions.
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Electronic Structure and Dynamics at Organic Semiconductor / Inorganic Semiconductor InterfacesKelly, Leah L. January 2015 (has links)
In this dissertation, I present the results of my research on a prototypical interface of the metal oxide ZnO and the organic semiconductor C₆₀. I establish that the physics at such oxide / organic interfaces is complex and very different from the extensively investigated case of organic semiconductor / metal interfaces. The studies presented in this dissertation were designed to address and improve the understanding of the fundamental physics at such hybrid organic / inorganic interfaces. Using photoemission spectroscopies, I show that metal oxide defect states play an important role in determining the interfacial electronic properties, such as energy level alignment and charge carrier dynamics. In particular, I show that for hybrid interfaces, electronic phenomena are sensitive to the surface electronic structure of the inorganic semiconductor. I also demonstrate applications of photoemission spectroscopies which are unique in that they allow for a direct comparison of ultrafast charge carrier dynamics at the interface and the electronic structure of defect levels. The research presented here focuses on a achieving a significant understanding of the realistic and device relevant C₆₀ / ZnO hybrid interface. I show how the complex surface structure of ZnO can be modified by simple experimental protocols, with direct and dramatic consequences on the interfacial energy level alignment, carrier dynamics and carrier collection and injection efficiencies. As a result of this careful study of the electronic structure and dynamics at the C₆₀ / ZnO interface, a greater understanding of the role of gap states in interface hybridization and charge carrier localization is obtained. This dissertation constitutes a first step in achieving a fundamental understanding of hybrid interfacial electronic properties.
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Electronic Structure Studies Using Resonant X-ray and Photemission SpectroscopyMagnuson, Martin January 1999 (has links)
This thesis addresses the electronic structure of molecules and solids using resonant X-ray emission and photoemission spectroscopy. The use of monochromatic synchrotron radiation and the improved performance of the instrumentation have opened up the possibility of detailed analyses of the response of the electronic systems under interaction with X-rays. The experimental studies are accompanied by numerical ab initio calculations in the formalism of resonant inelastic scattering. The energy selectivity has made it possible for the first time to study how the chemical bonds in a molecule break up during resonant inelastic X-ray scattering. In the conjugated polymer systems, the element selectivity of the X-ray emission process made it possible to probe the different atomic elements separately. The X-ray emission technique proved to be useful for extracting isomeric information, and for measuring the change in the valence levels at different degrees of doping. In this thesis, spectral satellite features in transition metals were thoroughly investigated for various excitation energies around a core-level threshold. By measuring the relative spectral intensity of the satellites it was possible to extract information on the partial core-level widths. Using the nickel metal system as an example, it was shown that it is possible to probe the different core-excited states close toshake-up thresholds by measuring the relative spectral intensity variation of the Auger emission.Resonant photoemission measurements showed unambiguous evidence of interference effects. Theseeffects were also thoroughly probed using angle-dependent measurements. The combination of X-rayemission and absorption were useful for studying buried layers and interfaces due to the appreciable penetration depth of soft X-rays. X-ray scattering was further found to be useful for studying low-energy excited states of rare earth metallic compounds and transition metal oxides.
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Investigating the Effect of Nanoscale Changes on the Chemistry and Energetics of Nanocrystals with a Novel Photoemission Spectroscopy MethodologyLiao, Michael W., Liao, Michael W. January 2017 (has links)
This dissertation explores the effect of nanometer-scale changes in structure on the energetics of photocatalytic and photovoltaic materials. Of particular interest are semiconductor nanocrystals (NCs), which have interesting chemical properties that lead to novel structures and applications. Chief among these properties are quantum confinement and the high surface area-to-volume ratio, which allow for chemical tuning of the energetics and structure of NCs. This tunable energetic landscape has led to increasing application of NCs in various areas of research, including solar energy conversion, light-emitting diode technologies, and photocatalysis. However, spectroscopic methods to determine the energetics of NCs have not been well developed, due to chemical complexities of relevant NCs such as polydispersity, capping ligand effects, core-shell structures, and other chemical modifications. In this work, we demonstrate and expand the utility of photoelectron spectroscopy (PES) to probe the energetics of NCs by considering the physical processes that lead to background and secondary photoemission to enhance photoemission from the sample of interest. A new methodology for the interpretation of UP spectra was devised in order to emphasize the minute changes to the UP spectra line shape that arise from nanoscopic changes to the NCs. We applied various established subtractions that correct for photon source satellites, secondary photoelectrons, and substrate photoemission. We then investigated the effect of ligand surface coverage on the surface chemistry and density of states at the top of valence band (VB). We systematically removed ligands by increasing numbers of purification steps for two diameters of NCs and found that doing so increased photoemission density at the top of the VB, which is due to undercoordinated surface atoms. Deeper VB structure was also altered, possibly due to reorganization of the atoms in the NC. Using the new UPS interpretation methodology, we examined the evolution of the valence band energy (EVB) of CdSe NCs as it was modified from spherical NC to rod to Au-NP tipped nanorod (NR). We also employed potential-modulated attenuated total reflectance spectroscopy (PM-ATR) to probe the conduction band energy (ECB) of the series. The EVB decreased with each modification, which is predicted with a band-bending model. This trend was also observed in the ECB, as revealed by spectroelectrochemistry, along with the appearance of new metal-semiconductor states in the band gap. UPS was finally used to investigate the even more complex Pt-NP tipped CdSe@CdS core@shell NR heterostructure. The addition of the CdS shell decreases the EVB relative to CdSe, as expected from common cation II-VI compounds. The Pt-NC increases the EVB, which, like the Au-CdSe NR, is predicted by employing a band-bending model. XPS revealed that PtSx-like chemical states were formed near the CdS-Pt interface. These experiments, along with the improved UP spectra interpretation methodology, demonstrate the wealth of information regarding surface chemistry and energetics that can be obtained with PES which can be applied to not only NCs, but also to metal oxide or molecular thin films.
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SPECTROSCOPIE DE PHOTOEMISSION DANS LE DOMAINE DES RAYONS X MOUSVenturini, Federica 17 October 2005 (has links) (PDF)
La motivation principale de cette thèse a été de déterminer les avantages et les inconvénients de l'utilisation de la spectroscopie de photoémission résolue en angle dans le domaine des rayons X mous.<br />L'étude d'un système bien connu, Ag(001) nous permet de discuter plusieurs questions telles que le rôle de la quantité de mouvement du photon, la pertinence de l'approximation d'électron libre à l'état final, et le rôle des phonons. La polarisation de la lumière incidente a aussi été exploitée. En choisissant un tel système, nous avons aussi voulu comparer les résultats expérimentaux avec des spectres calculés de photoémission résolue en angle dans cette gamme d'énergie.<br />Le comportement à basse température atypique des composés de Cérium est généralement imputé à l'effet Kondo. Des résultats originaux ont été obtenus en étudiant la bande de valence de trois composés monocristallins iso-structuraux de Cérium, CeCu2Ge2, CeNi2Ge2 et CeCo2Ge2. La position du seuil d'absorption M5 du Cérium dans la bande d'énergie des rayons X mous est exploitée pour isoler la contribution 4f à ces spectres. De plus, l'utilisation de photons incidents d'énergie relativement élevée permet de minimiser les effets de surface. Les spectres de photoémission présentés dans cette thèse incluent des études de dépendance en température, des spectres à la résonance, des spectres résolus en angle ou bien intégrés angulairement. Les premiers sont en accord avec le modèle d'impureté unique d'Anderson, alors que les derniers suggèrent qu'il est important de prendre en compte le réseau cristallin.
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Angle-resolved Photoemission Studies on Hole Doped Iron Pnictides Ba1-xKxFe2As2Xu, Yiming January 2010 (has links)
Thesis advisor: Hong Ding / Thesis advisor: Ziqiang Wang / The discovery of the high-T<sub>c</sub> superconductivity in iron-arsenic materials in 2008 immediately became one of the hottest topics in the condensed matter physics. This dissertation presents a systematic study on the pairing symmetry and electronic structure on the hole doped materials of BaFe<sub>2</sub>As<sub>2</sub> (so called “122”-system), by angle-resolved photoemission spectroscopy (ARPES). In the early ARPES studies on “122”-pnictides, we observed two hole-like Fermi surfaces (FSs) centered at the Brillouin zone (BZ) center, (Γ), and two electron-like FSs centered at the zone corner (M), which is (π, π) in the BZ or (π, 0) in the unfolded BZ. The size of these FS sheets can be changed by carrier doping, which causes change of the chemical potential. In the superconducting state, temperature (<italic>T</italic>) and momentum (<italic>k</italic>) dependence of ARPES measurements reveals the Fermi-surface-dependent nodeless superconducting gaps in this system and shows that an <italic>s</italic>-wave symmetry is the most natural interpretation for our findings in terms of the pairing order parameter. The ratio 2Δ/k<sub>B</sub>T<sub>c</sub> switches from weak to strong coupling on different FS sheets. Large superconducting gaps are observed with a strong coupling coefficient (2Δ/k<sub>B</sub>T<sub>c</sub>) on the near-nested FSs connected by the antiferromagnetic (AF) wave vector ((π, π) in the BZ or (π, 0) in the unfolded BZ). When T<sub>c</sub> is suppressed in the heavily overdoped materials, the near-nesting condition vanishes, or more precisely, the (π, π) inter-FS scattering disappears due to the absence of either the hole-like or the electron-like FS at the Fermi energy (E<sub>F</sub>). We have also performed ARPES measurements on k<sub>z</sub>-dependence of the superconducting gap and band structure of the optimally hole doped sample Ba<sub>0.6</sub>K<sub>0.4</sub>Fe<sub>2</sub>As<sub>2</sub>. By varying the photon energy, we can tune k<sub>z</sub> continuously. While significant k<sub>z</sub> dispersion of the superconducting gaps is observed on the hole-like bands, much weaker k<sub>z</sub> dispersion of the superconducting gaps is observed on the electron-like bands. Remarkably, we find that a 3D gap function based on short-range pairing can fit the superconducting gaps on all the FS sheets. Moreover, an additional hole-like FS (referred as the α<super>‘</super> FS) predicted by local density approximation (LDA) calculations is observed around the Z point. The disappearance of intensity of the α<super>‘</super> band near E<sub>F</sub> at k<sub>z</sub> = π/2 suggests that the α<super>‘</super> band could either sink below E<sub>F</sub> or be degenerate with the inner hole (α) band. The studies on the α<super>‘</super> band in the superconducting state reveal a nearly isotropic superconducting gap on this FS sheet. Underdoped samples Ba<sub>0.75</sub>K<sub>0.25</sub>Fe<sub>2</sub>As<sub>2</sub> are used to study how the AF fluctuations and superconductivity interplay in the underdoped regime that is closer to the AF phase. we observe that the superconducting gap of the underdoped pnictides scales linearly with T<sub>c</sub>. A distinct pseudogap develops upon underdoping and coexists with the superconducting gap. Remarkably, this pseudogap occurs mainly on the FS sheets that are connected by the AF wave vector, where the superconducting pairing is stronger as well. This suggests that both the pseudogap and the superconducting gap are driven by the AF fluctuations, and the long-range AF ordering competes with the superconductivity. The observed dichotomic behaviour of the pseudogap and the SC gap on different FS sheets in the underdoped pnictides shares similarities with those observed in the underdoped copper oxide superconductors, providing a possible unifying picture for both families of high-temperature superconductors. / Thesis (PhD) — Boston College, 2010. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.
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Electronic Structure Characterization of Hybrid MaterialsLi, Zhi 03 February 2014 (has links)
In this dissertation, the studies aim to characterize the electronic structure at the internal interface of hybrid materials. The characterization challenge is originating from the spectral superposition of hybrid constituents. A characterization protocol based on photoemission spectroscopy (PES) was developed and applied to investigate the orbital alignment at the internal interface of the oligothiophene-TiO2 and ArS-CdSe hybrid materials by characterizing the individual constituents and the assembly hybrids respectively. Electrospray deposition technique was used to deposit targeting materials which enabled preparation of thin films in vacuum minimizing ambient contaminations while transmission electron microscopy (TEM) was used to investigate the morphology and the particle size of the pure nanoparticles and the hybrids. Ultraviolet-visible (UV-vis) spectroscopy was also used in the estimation of the optical band gap of the pure nanoparticles and the HOMO-LUMO gap of the organic ligands.
One of the hybrid materials studied in this dissertation is oligothiophene-TiO2 nanoparticle hybrids in which the oligothiophene ligands are bonded to the surface of TiO2 nanoparticles covalently. This hybrid system was used to develop and demonstrate a measurement protocol to characterize the orbital alignment at the internal interface. Low intensity X-ray photoemission spectroscopy (LIXPS) was used to determine the work function of the oligothiophene ligands and the TiO2 nanoparticles. In combination with the highest occupied molecular orbital (HOMO) cutoff and the valence band maximum (VBM) measured by ultraviolet photoemission spectroscopy (UPS), the ionization energies (IE) of these two constituents were determined. X-ray photoemission spectroscopy (XPS) was used to characterize the core level emissions of the constituents and the hybrid assembly, which were used to determine the charge injection barriers at the internal interface.
The results showed that there was an interface dipole at the internal interface between organic and inorganic constituents of the hybrid. The dipole was determined to be 0.61 eV and the hole injection barrier at the internal interface amounted to 0.73 eV. The electron injection barrier was estimated by taking into account the gap between highest occupied and lowest unoccupied molecular orbitals (HOMO, LUMO). The procedure followed only suggested the presence of an insignificant barrier in the oligothiophene-TiO2 nanoparticle hybrids.
Arylthiol functionalized Cadmium Selenide (ArS-CdSe) is a novel hybrid material which can be used in hetero-junction solar cells. The ArSH ligands are bonded on the surface of the CdSe nanoparticles covalently through sulfur atoms serving as anchors. The internal interface in the ArS-CdSe hybrids between the organic constituent and the inorganic constituent was studied by the same characterization protocol developed in this dissertation. Furthermore, a physisorbed interface between the ArSH ligands and the CdSe nanoparticles was created through multi-step in-vacuum deposition procedure. The electrospray deposition technique enabled the formation of a well-defined physisorbed interface which was characterized by LIXPS, UPS and XPS for each deposition step. Accordingly, the orbital alignment at the physisorbed interface was determined.
Based on the results obtained, detailed orbital alignments at the ArSH/CdSe physisorbed interface and the internal interface in the ArS-CdSe hybrid materials were delineated and discussed. The hole injection and electron injection barrier at the physisorbed ArSH/CdSe interface are 0.7 eV and 1.0 eV respectively. An interface dipole of 0.4 eV was observed at the interface. In the ArS-CdSe hybrid materials, the electronic system of the ArSH component shifts down due to the charge transfer induced by the covalent hybridization. The hybridization also shifts the electronic system of the CdSe constituent to a lower energy level due to saturation of the unoccupied bonds of the Cd atoms on the surface. The hole injection barrier and electron injection barrier were determined to be 0.5 eV and 1.2 eV respectively. A small interface dipole (0.2 eV) was observed at the internal interface as a result of the presence of covalent bonds.
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