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, Cinq composants sont nécessaires: La composante du volume associée au c-Si (B), une composante associée aux liaisons pendantes (S1), une composante associée aux atomes de Si lièsà un H (S2), une composante associée aux atomes de Si liès au C (S3) et une composante associée au SiO 2 (S4). (d) Comparaison de la DOS expérimentale de hétérostructures irradiées (courbe rouge) et non irradiées (courbe bleue) dans des (f) d'hétérojonctions de 10 nm de a-Si: H mesuréesà uneénergie de photon de 5 keV, Décomposition du niveau de coeur Si 2p pour les hétérostructures non irradiées et (b) irradiées. Mesures e?ectuéeà uneénergie de photon de 3 keV (c)
,
, x 6 (a) Schéma de la structure de bande simulée pour la comparaison avec nos résultats expérimentaux. Les coupes verticales fournissent la dispersion en function de k || . Les coupes horizontales fournissent des coupes d'énergie constantes. b) La photoémission inverse (IPES) et la photoémission (PES) permettent d'obtenir les bandes de conduction et de valence respectivement
, Esquisse des principales bandes attendues dans le plan MXM. (b) Coupe dans le plan GXMà 300 meV en dessous du maximum de la bande de valence. (c) Coupe d'énergie constante calculéeà 500 meV en dessous du maximum de la bande de valence, Les zones de Brillouin cubiques sont représentées par des carrés rouges
, Lesétoiles sont une aide pour la comparaison entre théorie et expérience, p.9
, Carte d'intensité de photoélectrons en fonction de l'énergie cinétique et du retard de la pompe-sonde de (a) unéchantillon non recuit et deséchantillons recuitsà (b) 100 C et (c) 200 C
, Solar spectrum of minimum losses of not absorbed, thermalization, and extraction losses based on SQ limit, representing an upper limit for a single-junction silicon solar cell
, Light management" relates to the capability of light capturing and it is related to the short circuit current J sc , while the "Carrier management" is related to carriers collection, and can be quantified by the product of the fill factor F F and the open circuit voltage V oc, The theoretical SQ detailed-balance e ciency limit for di?erent solar cell technologies, along with their record e ciencies. The SQ limit of di?erent technologies depends on the band gap of the absorber material, vol.4
, Best research-cell e ciency of di?erent PV technologies as a function of year
, A schematic diagram of HIT solar cells. TCO stands for transparent conducting oxide
, E c is the minimum of the conduction band, and E v is the maximum of the valence band. A larger band o?set of a-Si raises the rear-side field and helps di?using electrons and holes in the solar cells
, The defect gives rise to an excess of density of states shown in red. (b) Density of states corresponding to the system in (a). The gray states correspond to the defects, vol.23
,
, Schematic band diagram of hydrogenated amorphous silicon (a-Si:H) in the amphoteric model
, Structural evolution of perovskite solar cells from sensitization to meso-superstructure, mesoscopic, and planar structures. HTM stands for the hole transport material and ETM for the electron transport material
, Atomic structure of hybrid organic-inorganic perovskites
, Optical band gap of FAPbI y Br 3 y as a function of its lattice parameter. (a) Depending on the y content of iodine in the material, the lattice parameter varies and the band gap changes accordingly. (b) Photographs of di?erent perovskites with increasing y iodine content from left to right, p.14
, The theoretical electronic band structures of 4F-PEPI
, PbI 4 ) (a) without and (b) with spin-orbit coupling (SOC) calculated by DFT [36]
, Br, I), in di?erent crystallographic phases (cubic, tetragonal) and for calculations from di?erent studies, E?ective masses of electrons and holes in di?erent perovskite materials, namely di?erent methylammonium lead halides (Cl
, Typical timescales (bottom axis) and energy scales (top axis) of coherent phonons, electron-electron (e-e) interaction, electron-phonon (e-ph) interaction and ph-ph interaction in correlated metals. The green and blue line indicate the temporal duration of our pump and probe pulses, respectively
, Time-resolved 2PPE working principle (left) and experimental scheme (right)
, h? 1 is the pump excitation energy and h? 2 is the probe photon energy, p.44
, FemtoARPES experimental setup showing the laser source (left) the optics for generating UV pulses (middle) and the ARPES setup (right), p.45
, Photoluminescence measurements on the non-irradiated, irradiated, and irradiated + annealed samples (adapted from [39]). Here, TA stands for transverse acoustic phonons and TO for transverse optical phonons, p.50
, Simulation of the Inelastic Mean Free Path of Si2p (solid line) and C1s (dotted line) for di?erent layers (L1: red, L2: green, and S: blue) as a function of photon energy. Background colors represent the depth of each layer in the heterostructure (right axis) (b) The photoexcited electrons can be extracted from di?erent depths of the heterojunction with di?erent photon energies, p.52
, Si 2p core level measured under di?erent photon energy for (a) a non-irradiated sample and (b) an irradiated sample. The binding energy is relative to the binding energy of the bulk component (99.4 eV). The increase of Si 4+ component towards the surface shows its surface sensitive (also surface reactivity) property. On the other hand, the bulk component of Si 2p shows a bulk-like behavior at high photon energy since the feature of the Si 2p splitting becomes more evident due to the presence of a unique major component, p.53
, The binding energy is relative to the binding energy of the bulk component (283.0 eV). . . 55 photon energy. Dark blue shows the bulk component with the two spin-orbit splitted peaks (Si 2p 3/2 and Si 2p 1/2 ) appearing at binding energies of 99.4 eV (set as the reference: 0 eV) and 99.9 eV (0.5 eV relatively). The orange component associated to Si 4+ (SiO 2 ). Red circles highlight the spectra regions that are not satisfactorily described with a single component. (b) The final core level fitting of Si 2p with two additional components, C 1s Core level decomposition for irradiated and non-irradiated heterostructures, as a function of the photon energies (3 keV and 5 keV)
, sputtered heterostructure measured at 800 eV and (b) the Ar-irradiated heterostructure consisting of 7 nm a-Si:H and 3 nm a-SiC:H measured under 3 keV
, Si 2p core level decomposition for the non-irradiated and the irradiated heterostructures measured at photon energies 3 keV, 5 keV and 8 keV. Five components are necessary: a bulk component which is meanly from c-Si (B), a dangling bond component (S1), a Si-H bond component (S2), a Si-C component (S3), and a Si 4+ component that is associated to SiO 2 (S4), p.60
, Intensity evolution as a function of the photon energy (shown in axis above) and the escape depth (shown in axis below) of (a) S1 component associated to dangling bonds and (b) S2 component associated to Si-H bonds, p.61
, nm of a-Si:H and 2 nm of a-SiC:H) measured at 3 keV (a) valence band normalized to the density of states and (b) density of states
, Comparison the experimental DOS between irradiated (red curve) and nonirradiated (blue curve) heterostructures on the 10nm a-Si:H heterojunction sample (see the insert). The left panel shows the whole valence band, and the right panel shows the zoom close to the VBM. The defect states
, The mechanism of the photoluminescence presented by band diagrams of c-Si and a-Si:H represented with the defect states
, Vertical slices provide the dispersion vs k || . Horizontal slices provide constant energy cuts. (b) IPES and PES experimental techniques allow to obtain both conduction and valence bands, A schematic of the whole simulated band structure
, 2 (a) Scanning electron microscope image of a thin film of 4F-PEPI. (b) Auger spectra of 4F-PEPI thin films after annealing at di?erent temperatures, p.72
, with a size of about 2.5 mm by 3 mm. (b) Sample mounted on a sample holder with a top post attached, which is used to cleave the sample in ultra-high vacuum
, h0l) plane of the reciprocal space of PEPI measured at room temperature by X-ray di?raction, indicating the projection of the reciprocal unit cells (in red). (b) Refined structure
, 5 (a) Spectrum of photoemission on PEPI before and after irradiation during 18 hours under 130 eV photons. Core levels of (b) Pb 5p, (c) I 4d, and (d) Pb
, Blue-dotted line shows the experimental DOS, green-solid line shows the calculations including the full structure, and the redsolid line shows the calculations without the organic molecules, LIST OF FIGURES 4.6 Density of states (DOS) of PEPI, p.75
, The di?erence of the states in between red and blue calculations, i.e. the organic states. Calculations were performed with Wien2k, Theoretical band structure of PEPI, by including a (a) full structure (red) and the structure without organic molecules (blue). (b)
, DOS of PEPI using (a) scalar relativistic (without SOC) and (b) fully relativistic (with SOC)
, 78 4.11 Y valence band dispersion of PEPI. (a) Raw ARPES data, along with its integration in angle, simulating a density of states, and (b) 2D curvature analysis. (c) ARPES data normalized to the density of states to get rid of the non-dispersing states from organic molecules, and (d) 2D curvature analysis to it. (e) Theoretical simulation of ARPES data, including SOC in a structure without organic molecules, with its angle-integrated spectrum artificially added. (f) Theoretical simulation of ARPES data, Theoretical band structure calculation of PEPI without organic molecules using SPRKKR code (a) with and (b) without SOC. The biggest di?erences are highlighted by the white rectangle, vol.78
, Raw IPES data. (b) IPES data normalized to the angle-integrated spectrum and with a 2D curvature analysis. The calculated ground-state bands superimposed. (c) Simulated IPES spectra including SOC in a structure without organic molecules (with SOC). The calculated ground-state bands are superimposed, Conduction band of PEPI along B . (a)
, Electronic dispersion as a function of the photon energy. Photoemission measurements along a direction containing the normal emission for photon energies of (a) 110 eV, (b) 112 eV and (c) 114 eV. Arrows highlight the evolution of the electronic states. Such an evolution corresponds to electronic states dispersing with k perpendicular to the surface, as expected for a 3D material, vol.85, p.134
, Constant energy cuts of the electronic structure measured (a) out-of-plane (2340 meV below the VBM for photon energies 74 eV < hv < 200 eV) and (b) in-plane (VBM at hv = 130 eV). The size of the lattice vectors for the cubic (red, C) and tetragonal structures (blue, T) are indicated. The spectral weight seems to follow the cubic periodicity
, 0 k l) planes at 200 K. The projected reciprocal unit cells for the tetragonal periodicity (in blue) and cubic periodicity (in red) are indicated with a space group of I4/mcm. The refined structure are projected on (c) the ac plane and (d) on the bc plane. In the tetragonal structure, a distortion of the octahedra lattice promotes a larger unit cell (in blue) with respect to the cubic one (in red). The crystallographic directions are indicated by the tetragonal (T) and cubic (C) lattice vectors, X-ray di?raction measurements of MAPI in the tetragonal phase in the (a) (h 0 l) and (b)
, Constant energy cut of the electronic structure in the GXM plane at a binding energy corresponding to (c) 100 meV, (d) 300 meV, (e) 2500 meV and (f) 2900 meV below the valence band maximum. Corresponding constant energy cuts calculated using the SPRKKR code shown for energies of (g) VBM, (h) 500 meV, (i) 2800 meV, and (j) 3400 meV below the valence band maximum. Cubic Brillouin zones are shown as red squares. The indicated stars are a guide for the comparison between theory and experiment, Constant energy cuts of the electronic structure of MAPI. (a)
, Electronic structure of MAPI hybrid perovskite with k-resolution. (a)Spectrum at normal emission in a wide binding energy range. (b) Integrated valence band in (a) compared to theoretical calculations
, 6 (a) Band structure of MAPI in the tetragonal phase performed with Wien2k by
, 93 LIST OF FIGURES 5.7 Electronic structure with k-resolution of MAPI measured at photon energy of 142 eV. (a) Constant energy cut at 300 meV below the valence band maximum. The cubic Brillouin zone (red rectangle) and the tetragonal Brillouin zone (blue rectangle) are shown together with the cuts along the high symmetry directions, ARPES simulation of tetragonal MAPI
, Simulated ARPES spectra of (b) (bands broadened by a factor of 14 with the density of states superimposed). (d) Second derivative of the raw data in (b)
, Calculated constant energy cut at 300 meV below the valence band maximum. (g) Photoemission measurement along X direction of the cubic phase, Simulated ARPES spectra along M M of the cubic phase. (f)
, Simulated ARPES spectra and (i) second derivative of the raw data in (g). (j) Simulated ARPES spectra along X X direction of the cubic phase. The high symmetry points of the tetragonal and the cubic Brillouin zones are indicated. The dotted rectangles indicate the agreements of the dispersions between the experiments and calculations
, Photoemission measurement along X direction of the cubic phase (cut B in Fig. 5.7). (b) Second derivative of the raw data in (a). (c) Simulated ARPES spectra along X of the cubic phase. (d) Photoemission measurement along M M direction of the cubic phase (cut A in Fig. 5.7). (e) Second derivative of the raw data in (d). (f) Simulated ARPES spectra along M M of the cubic phase, Electronic structure with k-resolution of MAPI measured close to the Fermi level. (a)
, 98 136 LIST OF FIGURES 5.11 (a) Photoelectron intensity map in the as-grown sample as a function of kinetic energy and pump-probe delay. (b) Energy distribution curves acquired at di?erent values of the pump-probe delay and normalized to their maximum value. (c) Evolution of the average kinetic energy as a function of time. The solid line is an exponential fit with time constant ? 1 = 0.25 ps, Phase transition of MAPI as a function of temperature shown in top views and side views. ? ab (=154±4) is the distortion angle in-plane and ? c (=164±4) is the distortion angle out-of-plane. At high temperature (above 330 K), MAPI is in the cubic with a space group Pm-3m, vol.3
, 13 (a) The integrated intensity of the 2PPE signal (black marks) as a function of time is compared with the di?usion model (red line). The dotted blue line at t = 3? 1 indicates the delay time when electrons have fully thermalized. (b) The density profile of photoexcited electrons is calculated by the di?usion model of, vol.5
, 4) for selected delay times
, Photoelectron intensity map of (a) a non-annealed sample, and samples annealed at (b) 100 C, and (c) 200 C, as a function of kinetic energy and pumpprobe delay
, 15 (a) Photoluminescence spectra acquired from non-annealed, annealed at 100 C, and annealed at 200 C samples. The dashed line shows the development of trapped states upon annealing. (b) Photoluminescence emitted in the visible spectral range from the sample annealed at 200 C and measured at 10 K. The peak located at 2.45 eV arises from carrier recombination in PbI 2 inclusions, p.105
, Temporal evolution of the integrated 2PPE signal in the non-annealed and annealed samples. The arrows indicate the characteristic time scale when electronic trapping takes place
, Inelastic Mean Free Path in the di?erent layers for di?erent photon energies determined from SESSA
, Fitting parameters of the bulk component of Si 2p
, S1(dangling bond), S2 (Si-H), vol.2, p.4
,
, Si-C), and S4 (Si 4+ ) related to the bulk component B. These are the binding energy shifts fitting to our experimental core levels of Si 2p measured in di?erent conditions. In general, dangling bond has a chemical shift around -0.3 eV, Si-H bond has a energy shift around 0, Chemical shift for S1(dangling bond), S2 (Si-H), vol.25
, Si 4+ has a chemical shift around 4.15 eV. The intensity of each peaks will be demonstrated in Fig. 3.8 later on
, Atomic structure of MAPI at, vol.87
, Atomic positions of MAPI at 200 K shown in reduced units, vol.87
, Thermal parameters of MAPI at 200 K. Thermal parameters, i.e. atomic displacement parameters, represent the temperature dependent vibration of different atoms within the crystalline lattice