Die Arbeit behandelt die vielseitigen Möglichkeiten im Bereich der Kristallstrukturanalyse mit Röntgenstrahlung, welche sich zusätzlich bei resonanter Anregung von Elektronenübergängen ergeben. Existierende resonante Methoden aus diesem Bereich werden im materialwissenschaftlichen Kontext neu dargelegt und ausgebaut. Zudem werden neue Methoden zur Strukturverfeinerung vorgestellt, welche darauf zielen, mithilfe resonanter Anregung kleine Abweichungen von der Idealstruktur oder aber Phasenumwandlungen zu beschreiben. Im Vordergrund steht dabei die hier erstmals ausgearbeitete Methode der Unterdrückung von Beugungsintensität durch Variation der atomaren Streufaktoren über gezieltes Einstellen der Röntgenenergie. Dies ist stark abhängig von internen Strukturparametern und ermöglichte so eine pikometergenaue Bestimmung von Atompositionen in einer neuen, polaren Oberflächenschicht des Strontiumtitanats. Weitere Anwendungen auf verschiedene Klassen kristalliner Materialien werden vorgestellt und basieren auf unterschiedlichen Aspekten resonanter Beugung wie zum Beispiel verbotenen Reflexen.

The thesis entitled “Towards the Design of Functional Materials: Evaluation based on Crystal Structure, Photocatalysis and Conductivity Measurements” consist of six chapters. A short introductory note outlines the basis of designing functional materials, different synthetic procedures, characterization techniques and properties such as photocatalysis and ionic conductivity. Chapter 1 describes the effect of Ti doping on photocatalytic activity in orthorhombic perovskite type LnVO3. All the compounds were synthesized by solid state method. Rietveld refinement with high resolution PXRD reveals that the substituent Ti occupies V site rather than Ln Site. Ti substituted compound showed higher photocatalytic activity than the unsubstituted compound and is comparable with that of commercial catalyst. These classes of compounds showed specific degradation towards chlorinated compounds. Chapter 2 discusses the solution combustion synthesis of γ(L)-Bi2MoO6 and its photocatalytic activity under solar radiation. The particle sizes were in the range 300–500 nm with a band gap of 2.51 eV. The degradation of wide variety of cationic and anionic dyes was investigated under solar radiation. Despite the low surface area (<1 m2/g), γ(L)-Bi2MoO6 showed higher photocatalytic activity under solar radiation due to its electronic and morphological properties. Chapter 3 presents a series of visible light photocatalyst M2Ce2O7, synthesized via solution combustion method and characterized by powder X-ray diffraction, solid-state UV-Visible diffuse reflectance spectra, SEM and TEM. The structure of Bi2Ce2O7 has been determined using laboratory as well as synchrotron PXRD. It crystallizes in a disordered F-type structure. The particle sizes are in the range 5–6 nm, band gaps lie within the range 1.7 to 3.2 eV. Bi2Ce2O7 shows high photocatalytic activity, comparable to the commercial Degussa P-25 TiO2 under solar radiation. Chapter 4 examines the effect of Bismuth substitution on crystal chemistry, photocatalysis and conductivity in Sr3V2O8, a variant of palmierite class. These compounds were synthesized by ceramic method and powder X-ray data reveals the limit of the Bi substitution in Sr3-xBi2x/3V2O8 is x=0.4. Single crystal study followed by careful difference Fourier analysis shows that Bi occupies a unique 18h position which is different than Sr1 and Sr2 position. The experimental band gap for Sr3V2O8 was calculated to be 3.45 eV and upon substitution band gap of the material decreases and reaches a value 3.15 eV for the composition x=0.4. Compound exhibits photocatalytic activity specifically towards anionic dyes. However, Bi Substitution leads to lower photocatalytic activity. Chapter 5 describes synthesis, structure, phase transition and ionic conductivity in scheelite type Li0.5Ce0.5MoO4. The compound was synthesized by ceramic method and single crystal study reveals that it crystallizes in the space group I41/a and exhibits conductivity of ~10-3 Ohm-1cm-1 at elevated temperature( 700 °C). It undergoes a first order phase transition around 510 °C. The nature of this transition has been evaluated by laboratory and synchrotron PXRD, DSC, dielectric spectroscopy and variable temperature Raman spectroscopy. The phase transition is shown to be characterized by an iso-structural phase transition which is first example in literature for temperature induced Cowley’s “Type Zero” phase transition. Chapter 6 discusses a new methodology for generating functional materials for fast ion conductors. Several varients of hydrated sodium cadmium bisulfate, Na2Cd2(SO4)3⋅3H2O, Na2Cd(SO4)2⋅2H2O and Na2Cd(SO4)2⋅4H2O have been synthesized and their thermal properties followed by phase transitions have been invesigated. Na2Cd2(SO4)3⋅3H2O (space group P3c). Na2Cd2(SO4)3⋅3H2O loses water completely when heated to 250 °C and transforms to a dehydrated phase (I⎯43d ) whose structure has been established using abinitio powder diffration techniques. Na2Cd(SO4)2⋅2H2O (P21/c) transforms to α−Na2Cd(SO4)2 (space group C2/c) on heating to 150 °C which is a known high ionic conductor. However, when α−Na2Cd(SO4)2 is heated to 570 °C followed by sudden quenching in liquid nitrogen, β−Na2Cd(SO4)2 (P21/c) is formed. β−Na2Cd(SO4)2 takes up water from the atmosphere and gets converted completely to the Kröhnkite type mineral. Further, β−Na2Cd(SO4)2 has a conductivity behavior comparable to α form up to 280 °C, the temperature required for the transformation of β to α form.

Transition metals (TMs) are ‘elements whose atoms have partially filled d-shell, or which can give rise to cations with an incomplete d-shell’. In TMs, the d-shell overlaps with next higher s-shell. Most of the TMs exhibit more than one (multiple) oxidation states. Some TMs, such as silver and gold, occur naturally in their metallic state but, most of the TM minerals are generally oxides. Most of the minerals on the planet earth are metal oxides, because of large free energies of formation for the oxides. The thermodynamic stability of the oxides is determined from the Ellingham diagram. Ellingham diagram shows the temperature dependence of the stability (free energy) for binaries such as metal oxides. Ellingham diagram also shows the ease of reducibility of metal oxides. TM oxides of general formulas MO, M2O3, MO2, M2O5, MO3 are known to exist, many of them being the ultimate products of oxidation in air in their highest oxidation states. In addition, TM oxides also exist in lower oxidation states which are prepared under controlled conditions. The nature of bonding in these oxides varies from mainly ionic (e.g. NiO, CoO) to mainly covalent (e.g. OsO4). Simple binary oxides of the compositions, MO, generally possess the rock salt structure (e.g. NiO), while the dioxides, MO2, possess the rutile structure (e.g. TiO2); many sesquioxides, M2O3, possess the corundum structure (e.g. Cr2O3). TMs form important ternary oxides like perovskites (e.g. CaTiO3), spinels (e.g. MgFe2O4) and so on. In TM oxides, the valence (outer) d-shell could be empty, d0 (e. g. TiO2), partially filled, dn (1≤ n≤ 9) (e.g. TiO, VO, NiO etc.) or completely filled, d10 (e.g. ZnO, CdO, Cu2O etc.). The outer d electrons in TM oxides could be localized or delocalized. Localized outer d electrons give insulators/semiconductors, while delocalized/itinerant d electrons make the TM oxide ‘metallic’ (e.g. ReO3, RuO2). Partially filled dn states are normally expected to give rise to itinerant (metallic) electron behaviour. But most of TM oxides with partially filled d shell are insulators because of special electronic energy (correlation energy) involved in d electron transfer to adjacent sites. Such insulating TM oxides are known as Mott insulators (e. g. NiO, CoO etc.). Certain TM oxides are known to exhibit both localized (insulating) and itinerant (metallic) behaviour as a function of temperature or pressure. For example, VO2 shows a insulator–metal transition at ~340K. Similar transitions are also known for V2O3, metal-rich EuO and so on. The chemical composition and bonding of TM oxides, which determine the crystal and electronic structures, give rise to functional properties. Table 1 gives representative examples. Properties like ionic conductivity and diffusion are governed by both the crystal structure and the defect structure (point defects), whereas properties such as magnetism and electron transport mainly arise from the electronic structures of the materials. Accordingly, TM oxides provide a platform for exploring functional materials properties. Among the various functional materials properties exhibited by transition metal oxides, the present thesis is devoted to investigations of lithium ion battery cathodes, inorganic pigments and magnetic perovskites. Over the years, most of the lithium containing first row transition metal oxides of rock salt derived structure have been investigated for possible application as cathode materials in lithium ion batteries (LIBs). First major breakthrough in LIBs research was achieved by electrochemically deinserting and inserting lithium in LiCoO2. A new series of cathode materials for LIBs were prepared by incorporating excess lithium into the transition metal containing layered lithium oxides through solid solution formation between Li2MnO3–LiMO2 (M = Cr, Mn, Fe, Co, Ni), known as lithium-rich layered oxides (LLOs). LLOs exhibit improved electrochemical performance as compared to the corresponding end members and hence received significant attention as a potential next generation cathode materials for LIBs in recent times. LiCoO2 (R-3m) crystallizes in the layered α-NaFeO2 structure with the oxygens in a ccp arrangement. Li+ and Co3+ ions almost perfectly order in the octahedral sites (3a and 3b) to give alternating (111) planes of LiO6 and CoO6 octahedra. Table 1. Materials properties exhibited by representative TM oxides. Property Example(s) Ferroelectricity BaTiO3, PbTiO3, Bi4Ti3O12 Nonlinear Optical Response LiNbO3 Multiferroic response BiFeO3, TbMnO3 Microwave dielectric properties Ba3ZnTa2O9 Relaxor Dielectric Properties Pb3MgNb2O9, Colossal Magnetoresistance Tl2Mn2O7 Metallic ‘Ferroelectricity’ Cd2Re2O7 Superconductivity AOs2O6(A = K, Rb, Cs) Redox deinsertion/insertion of LiCoO2 lithium Photocatalysis/water splitting TiO2 Pigment Ca(1-x)LaxTaO(2-x)N1+x (yellow-red), YIn1-xMnxO3 (blue) Metallic Ferromagnetism CrO2 Antiferromagnetism NiO, LaFeO3 Zero thermal expansion ZrW2O8 The reversible capacity of LiCoO2 in common LIBs is relatively low at around 140 mA h g-1 (half of theoretical capacity), corresponding to: LiCo3+O2 → Li0.5Co3+0.5Co4+0.5O2 + 0.5Li+ + 0.5e– . Substitution of one or more transition metal ions in LiCOO2 has been explored to improve the electrochemical performance. The structure of LLOs is described as a solid solution or nano composite of Li2MnO3 (C2/m) and LiMO2 (R-3m). The electrochemical deinsertion/insertion behaviour of LLOs is complex and also not yet understood completely. The present thesis consists of four parts. After a brief introduction (Part 1), Part 2 is devoted to materials for Li-ion battery cathode, consisting of three Chapters 2.1, 2.2 and 2.3. In Chapter 2.1, we describe the synthesis, crystal structure, magnetic and electrochemical characterization of new LiCoO2 type rock salt oxides of formula, Li3M2RuO6 (M = Co, Ni). The M =Co oxide adopts the LiCoO2 (R-3m) structure, whereas the M = Ni oxide also adopts a similar layered structure related to Li2TiO3. Magnetic susceptibility measurements reveal that in Li3Co2RuO6, the oxidation states of transition metal ions are Co3+, Co2+ and Ru4+, whereas in Li3Ni2RuO6, the oxidation states are Ni2+ and Ru5+. Li3Co2RuO6 orders antiferromagnetically at ~10K. On the other hand, Li3Ni2RuO6 presents a ferrimagnetic behaviour with a Curie temperature of ~100K. Electrochemical Li-deinsertion/insertion studies show that high first charge capacities (between ca.160 and 180 mA h g−1) corresponding to ca.2/3 of theoretical capacity are reached albeit, in both cases, capacity retention and cyclability are not satisfactory. Chapter 2.2 presents a study of new ruthenium containing LLOs, Li3MRuO5 (M = Co and Ni). Both the oxides crystallize in the layered LLO type LiCoO2 (α-NaFeO2) structure consisting of Li[Li0.2M0.4Ru0.4]O2 layers. Magnetic susceptibility data suggest that the oxidation states of transition metals are Li3Co3+Ru4+O5 for the M = Co compound and Li3Ni2+Ru5+O5 for the M = Ni compound. Electrochemical investigations of lithium deintercalation–intercalation behaviour reveal that both Co and Ni phases exhibit attractive specific capacities of ca. 200 mA h g-1 at an average voltage of 4 V, that has been interpreted as due to the oxidation of Co3+ and Ru4+ in Li3CoRuO5 and Ni2+ to Ni4+ in the case of Li3NiRuO5. Thus, we find that ruthenium plays a favourable role in LLOs than in non-LLOs in stabilizing higher reversible electrochemical capacities. In Chapter 2.3, we describe the synthesis, crystal structure and lithium deinsertion–insertion electrochemistry of two new LLOs, Li3MRuO5 (M=Mn, Fe) which are analogs of the oxides described in Chapter 2.2. The Li3MnRuO5 oxide adopts a structure related to Li2MnO3 (C2/m), while the Li3FeRuO5 oxide adopts a near-perfect LiCoO2 (R-3m) structure. Lithium electrochemistry shows typical behaviour of LLOs for both oxides, where participation of oxide ions in the electrochemical processes is observed. A long first charge process with capacities of 240 mA h g-1 (2.3 Li per f.u.) and 144 mA h g-1 (1.38 Li per f.u.) is observed for Li3MnRuO5 and Li3FeRuO5, respectively. Further discharge–charge cycling points to partial reversibility. X-ray photoelectron spectroscopy (XPS) characterisation of both pristine and electrochemically oxidized Li3MRuO5 reveals that in the Li3MnRuO5 oxide, Mn3+ and Ru4+ are partially oxidized to Mn4+ and Ru5+ in the sloping region at low voltage, while in the long plateau, O2- is also oxidized. In the Li3FeRuO5 oxide, the oxidation process appears to affect only Ru (4+ to 5+ in the sloping region) and O2- (plateau), while Fe seems to retain its 3+ state. Another characteristic feature of TMs is formation of several coloured solid materials where d–d transitions, band gap transitions and charge transfer transitions are involved in the colouration mechanism. Coloured TM oxides absorbing visible light find important applications as visible light photocatalyst (for example, yellow BiVO4 for solar water splitting and red Sr1-xNbO3 for oxidation of methylene blue) and inorganic pigments [for example, Egyptian blue (CaCuSi4O10), Malachite green (Cu2CO3(OH)2), Ochre red (Fe2O3)]. Pigments are applied as colouring materials in inks, dyes, paints, plastics, ceramic glazers, enamels and textiles. In this thesis, we have focused on the coloured TM oxides for possible application as inorganic pigments. Generally, colours arise from electronic transitions that absorb visible light. Colours of the inorganic pigments arise mainly from electronic transitions involving TM ions in various ligand fields and charge transfer transitions governed by different selection rules. The ligand field d–d transitions are parity forbidden but are relaxed due to various reasons, such as distortion (absence of center of inversion) and vibronic coupling. The d-electrons can be excited by light absorption in the visible region of the spectrum imparting colour to the material. Charge transfer transitions in the visible region are not restricted by the parity selection rules and therefore give intense colours. Here we have investigated the colours of manganese in unusual oxidation state (Mn5+) as well as the colours of different 3d-TM ions in distorted octahedral and trigonal prismatic sites in appropriate colourless crystalline host oxides. These results are discussed in Part 3 of the thesis. In Chapter 3.1, we describe a blue/green inorganic material, Ba3(P1−xMnxO4)2 (I) based on tetrahedral Mn5+O4 :3d2 chromophore. The solid solutions (I) which are sky-blue and turquoise-blue for x ≤ 0•25 and dark green for x ≥ 0•50, are readily synthesized in air from commonly available starting materials, stabilizing the Mn5+O4 chromophore in an isostructural phosphate host. We suggest that the covalency/ionicity of P–O/Mn–O bonds in the solid solutions tunes the crystal field strength around Mn(V) such that a blue colour results for materials with small values of x. The material could serve as a nontoxic blue/green inorganic pigment. In Chapter 3.2, an experimental investigation of the stabilization of the turquoise-coloured Mn5+O4 chromophore in various oxide hosts, viz., A3(VO4)2 (A = Ba, Sr, Ca), YVO4, and Ba2MO4 (M = Ti, Si), has been carried out. The results reveal that substitution of Mn5+O4 occurs in Ba3(VO4)2 forming the entire solid solution series Ba3(V1−xMnxO4)2 (0 < x ≤ 1.0), while, with the corresponding strontium derivative, only up to about 10% of Mn5+O4 substitution is possible. Ca3(VO4)2 and YVO4 do not stabilize Mn5+O4 at all. With Ba2MO4 (M = Ti, Si), we could prepare only partially substituted materials, Ba2M1−xMn5+xO4+x/2 for x up to 0.15, that are turquoise-coloured. We rationalize the results that a large stabilization of the O 2p-valence band states occurs in the presence of the electropositive barium that renders the Mn5+ oxidation state accessible in oxoanion compounds containing PO43−, VO43−, etc. By way of proof-of-concept, we synthesized new turquoise-coloured Mn5+O4 materials, Ba5(BO3)(MnO4)2Cl and Ba5(BO3)(PO4)(MnO4)Cl, based on the apatite – Ba5(PO4)3Cl – structure. Chapter 3.3 discusses crystal structures, and optical absorption spectra/colours of 3d-transition metal substituted lyonsite type oxides, Li3Al1-xMIIIx(MoO4)3 (0< x ≤1.0) (MIII = Cr, Fe) and Li3-xAl1-xMII2x(MoO4)3 (0< x ≤1.0) (MII = Co, Ni, Cu). Crystal structures determined from Rietveld refinement of PXRD data reveal that in the smaller trivalent metal substituted lyonsite oxides, MIII ions occupy the octahedral (8d, 4c) sites and the lithium ions exclusively occur at the trigonal prismatic (4c) site in the orthorhombic (Pnma) structure; on the other hand, larger divalent cations (CoII/CuII) substituted derivatives show occupancy of CoII/CuII ions at both the octahedral and trigonal prismatic sites. We have investigated the colours and optical absorption spectra of Li3Al1-xMIIIx(MoO4)3 (MIII = Cr, Fe) and Li3-xAl1-xMII2x(MoO4)3 (MII = Co, Ni, Cu) and interpreted the results in terms of average crystal field strengths experienced by MIII/MII ions at multiple coordination geometries. We have also identified the role of metal-to-metal charge transfer (MMCT) from the partially filled transition metal 3d orbitals to the empty Mo – 4d orbitals in the resulting colours of these oxides. B The ABO3 perovskite structure consists of a three dimensional framework of corner shared BO6 octahedra in which large A cation occupies dodecahedral site, surrounded by twelve oxide ions. The ideal cubic structure occurs when the Goldschmidt’s tolerance factor, t = (rA + rO)/{√2(rB + rO)}, adopts a value of unity and the A–O and B–O bond distances are perfectly matched. The BO6 octahedra tilt and bend the B – O – B bridges co-operatively to adjust for the non-ideal size of A cations, resulting deviation from ideal cubic structure to lower symmetries. Ordering of cations at the A and B sites of perovskite structure is an important phenomenon. Ordering of site cations in double (A2BB'O6) and multiple (A3BB'2O9) perovskites give rise to newer and interesting materials properties. Depending upon the constituent transition metals and ordering, double perovskite oxides exhibit a variety of magnetic behaviour such as ferromagnetism, ferrimagnetism, antiferromagnetism, spin-glass magnetism and so on. We also have coupled magnetic properties such as magnetoresistance (Sr2FeMoO6), magnetodielectric (La2NiMnO6) and magnetooptic (Sr2CrWO6) behaviour. Here we have investigated new magnetically frustrated double perovskite oxides of the formula Ln3B2RuO9(B = Co, Ni and Ln = La, Nd). The Chapter 4.1 describes Ln3B2RuO9 (B = Co, Ni and Ln = La, Nd) oxides (prepared by a solid state metathesis route) which adopt a monoclinic (P21/n) A2BB'O6 double perovskite structure, wherein the two independent octahedral 2c and 2d sites are occupied by B2+ and (B2+1/3Ru5+2/3) atoms, respectively. Temperature dependence of the molar magnetic susceptibility plots obtained under zero field cooled (ZFC) condition exhibit maxima in the temperature range 25–35K, suggesting an antiferromagnetic interaction in all these oxides. Ln3B2RuO9 oxides show spin-glass behavior and no long-range magnetic order is found down to 2 K. The results reveal the importance of competing nearest neighbour (NN), next nearest neighbor (NNN) and third nearest neighbour (third NN) interactions between the magnetic Ni2+/Co2+ and Ru5+ atoms in the partially ordered double perovskite structure that conspire to thwart the expected ferromagnetic order in these materials.

The content of this thesis is about preparation and processing of lead-free piezoceramic materials with perovskite structure. Potassium sodium niobate (KNN) powder was prepared by solid state reaction (SSR) and liquid phase reaction (sol-gel reaction). The powders were formed by uniaxial and isostatic pressing and further sintered. The density, grain size and morphology were determined on the sintered samples. The powder, synthesised by SSR and sintered in a conventional furnace, was chosen as a standard. The maximum density achieved on samples after optimization of sintering cycle was 93 %TD. The sintering optimization involved a homogenization step at 950 °C, which promotes the correct development of the phase composition and microstructure, followed by sintering at 1120 °C. The same approach and sintering cycle were used for sintering the samples, prepared by sol-gel synthesis. The maximum density of the samples prepared by sol-gel reaction and sintered in a conventional way, was 92 %TD. For further comparison, both of the synthesised powders were sintered using SPS (spark plasma sintering), which increased their final density up to 97 %TD. The approximate value of the piezoelectric coefficient d33 (pC/N) has been measured on selected SSR samples with pure phase composition ((K0,5Na0,5)NbO3). The best measured value of d33 was around 100 pC/N.

Solar cells based on organohalide perovskites (PSCs) have made rapid progress in recent years and are a promising emerging technology. An important next evolutionary step for PSCs is their up-scaling to commercially relevant dimensions. The main challenges in scaling PSCs to be compatible with current c-Si cells are related to the limited conductivity of the transparent electrode, and the processing of a uniform and defect-free organohalide perovskite layer over large areas. In this work we present a generic and simple approach to realizing efficient solution-processed, monolithic solar cells based on methylammonium lead iodide (CH₃NH₃PbI₃). Our devices have an aperture area of 25 cm² without relying on an interconnected strip design, therefore reducing the complexity of the fabrication process and enhancing compatibility with the c-Si cell geometry. We utilize simple aluminum grid lines to increase the conductivity of the transparent electrode. These grid lines were exposed to an UV-ozone plasma to grow a thin aluminum oxide layer. This dramatically improves the wetting and film forming of the organohalide perovskite junction on top of the lines, reducing the probability of short circuits between the grid and the top electrode. The best devices employing these modified grids achieved power conversion efficiencies of up to 6.8%.

Die Arbeit behandelt die vielseitigen Möglichkeiten im Bereich der Kristallstrukturanalyse mit Röntgenstrahlung, welche sich zusätzlich bei resonanter Anregung von Elektronenübergängen ergeben. Existierende resonante Methoden aus diesem Bereich werden im materialwissenschaftlichen Kontext neu dargelegt und ausgebaut. Zudem werden neue Methoden zur Strukturverfeinerung vorgestellt, welche darauf zielen, mithilfe resonanter Anregung kleine Abweichungen von der Idealstruktur oder aber Phasenumwandlungen zu beschreiben. Im Vordergrund steht dabei die hier erstmals ausgearbeitete Methode der Unterdrückung von Beugungsintensität durch Variation der atomaren Streufaktoren über gezieltes Einstellen der Röntgenenergie. Dies ist stark abhängig von internen Strukturparametern und ermöglichte so eine pikometergenaue Bestimmung von Atompositionen in einer neuen, polaren Oberflächenschicht des Strontiumtitanats. Weitere Anwendungen auf verschiedene Klassen kristalliner Materialien werden vorgestellt und basieren auf unterschiedlichen Aspekten resonanter Beugung wie zum Beispiel verbotenen Reflexen.

In this dissertation, BaTiO3 nanocrystals, Bi4Ti3O12 nanostructured microspheres, and cosubstituted Bi4Ti3O12 nanoparticles and ceramics were prepared using solvothermal, hydrothermal and citrate-gel methods. The ferroelectric properties of the prepared cosubstituted Bi4Ti3O12 ceramics were studied using P–E hysteresis loop, leakage, and polarization fatigue measurements. A two-phase solvothermal synthesis approach for the preparation of hydrophobic BaTiO3 nanocrystals was developed. The two-phase method is based on the growth of nanocrystals at the oil/water interface by the reaction between metal surfactant complexes in the oil phase and a mineralizer in the water phase. Three kind of organic solvents, hexadecene, toluene, and heptane were used as the oil phase and compared to each other with respect to the product quality. The BaTiO3 particles are crystalline with a mean size of 3.7 nm and can be dispersed in a variety of organic solvents forming highly transparent dispersions. A hydrothermal method was developed for the synthesis of Bi4Ti3O12 nanostructured microspheres consisting of granular nanoparticles and nano-platelets. The precursor powder was prepared using a diethylene glycol mediated coprecipitation method. Tailoring of the morphology was achieved by changing the precursor quantity, sodium hydroxide concentration, and reaction time. The formation mechanism of the nanostructured microspheres probably involves aggregation, followed by dissolution and recrystallization. Bi3.25Pr0.75Ti2.97V0.03O12 (BPTV) and Bi3.25La0.75Ti3-xMxO12, (BLTMx, M = Mo, W, Nb, V, x = 0.0–0.12) ferroelectric nanoparticles and ceramics were synthesized using a modified citrate-gel method that has a crystallization temperature as low as 450 °C. The synthesized nanoparticles were spherical ranging from 30 to 100 nm. Except Nb5+, other donor cations were introduced using the corresponding oxides that have advantages in terms of high purity, low cost, and availability. The Bi3.25Pr0.75Ti2.97V0.03O12 ceramic is orthorhombic and its 2Pr and 2Ec values measured at 300 kV/cm were 35 μC/cm2 and 148 kV/cm respectively. The texture, microstructure, and ferroelectric properties of the prepared Bi3.25La0.75Ti3-xMxO12, (BLTMx, M = Mo, W, Nb, V, x = 0.0–0.12) ceramics depend on x. The maximum 2Pr (30–32 μC cm−2) was achieved at an optimum cosubstitution level (x = 0.025 for M6+, x = 0.03 for M5+). The high remanent polarization, low leakage current, and low polarization fatigue render the prepared ceramics promising for practical applications.

Über die besonders hohe Effizienz von Halid-Perowskit (HaP)-basierten optoelektronischen Bauteilen wurde bereits in der Literatur berichtet. Um die Entwicklung dieser Bauteile voranzutreiben, ist ein umfassendes und verlässliches Verständnis derer elektronischen Struktur, sowie der Energielevelanordnung (ELA) an HaP Grenzflächen von größter Bedeutung. Demzufolge beschäftigt sich die vorliegende Arbeit mit der Untersuchung i) der Bandstruktur von Perowskit-Einkristallen, um ein solides Fundament für die Darlegung der elektronischen Eigenschaften von polykristallinen Dünnschichten zu erarbeiten, und mit ii) den Einflüssen von Oberflächenzuständen auf die elektronische Struktur der Oberfläche, sowie deren Rolle bei der Kontrolle von ELA an HaP Grenzflächen. Die Charakterisierung erfolgt überwiegend mithilfe von Photoelektronenspektroskopie (PES) und ergänzenden Messmethoden wie Beugung niederenergetischer Elektronen an Oberflächen, UV-VIS-Spektroskopie, Rasterkraftmikroskopie und Kelvin-Sonde. Erstens weist die Banddispersion von zwei prototypischen Perowskit-Einkristallen eine starke Dispersion des jeweiligen oberen Valenzbandes (VB) auf, dessen globales Maximum in beiden Fällen am R-Punkt in der Brillouin-Zone liegt. Dabei wird eine effektive Lochmasse von 0.25 m0 für CH3NH3PbBr3, bzw. von ~0.50 m0 für CH3NH3PbI3 bestimmt. Basierend auf diesen Ergebnissen werden die elektronischen Spektren von polykristallinen Dünnschichten konstruiert und es wird dadurch aufgezeigt, dass eine Bestimmung der Valenzbandkantenposition ausgehend von einer logarithmischen Intensitätsskala aufgrund von geringer Zustandsdichte am VB Maximum vorzuziehen ist. Zweitens stellt sich bei der Untersuchung der elektronischen Struktur von frisch präparierten Perowskit-Oberflächen heraus, dass die n-Typ Eigenschaft eine Folge der Bandverbiegung ist, welche durch donatorartige Oberflächenzustände hervorgerufen wird. Des Weiteren weisen die PES-Messungen an Perowskiten mit unterschiedlichen Zusammensetzungen aufgrund von Oberflächenphotospannung eine Anregungslichtintensitätsabhängigkeit der Energieniveaus von bis zu 0.7 eV auf. Darüber hinaus wird die Kontrolle von ELA durch gezielte Variation der Oberflächenzustandsdichte gezeigt, wodurch sich unterschiedliche ELA-Lagen (mit Abweichungen von über 0.5 eV) an den Grenzflächen mit organischen Akzeptormolekülen erklären lassen. Die vorliegenden Ergebnisse verhelfen dazu, die starke Abweichung der in der Literatur berichteten Energieniveaus zu erklären und somit ein verfeinertes Verständnis des Funktionsprinzips von perowskit-basierten Bauteilen zu erlangen. / Optoelectronic devices based on halide perovskites (HaPs) and possessing remarkably high performance have been reported. To push the development of such devices even further, a comprehensive and reliable understanding of their electronic structure, including the energy level alignment (ELA) at HaPs interfaces, is essential but presently not available. In an attempt to get a deep insight into the electronic properties of HaPs and the related interfaces, the work presented in this thesis investigates i) the fundamental band structure of perovskite single crystals, in order to establish solid foundations for a better understanding the electronic properties of polycrystalline thin films and ii) the effects of surface states on the surface electronic structure and their role in controlling the ELA at HaPs interfaces. The characterization is mostly performed using photoelectron spectroscopy, together with complementary techniques including low-energy electron diffraction, UV-vis absorption spectroscopy, atomic force microscopy and Kelvin probe measurements. Firstly, the band structure of two prototypical perovskite single crystals is unraveled, featuring widely dispersing top valence bands (VB) with the global valence band maximum at R point of the Brillouin zone. The hole effective masses there are determined to be ~0.25 m0 for CH3NH3PbBr3 and ~0.50 m0 for CH3NH3PbI3. Based on these results, the energy distribution curves of polycrystalline thin films are constructed, revealing the fact that using a logarithmic intensity scale to determine the VB onset is preferable due to the low density of states at the VB maximum. Secondly, investigations on the surface electronic structure of pristine perovskite surfaces conclude that the n-type behavior is a result of surface band bending due to the presence of donor-type surface states. Furthermore, due to surface photovoltage effect, photoemission measurements on different perovskite compositions exhibit excitation-intensity dependent energy levels with a shift of up to 0.7 eV. Eventually, control over the ELA by manipulating the density of surface states is demonstrated, from which very different ELA situations (variation over 0.5 eV) at interfaces with organic electron acceptor molecules are rationalized. Our findings further help to explain the rather dissimilar reported energy levels at perovskite surfaces and interfaces, refining our understanding of the operational principles in perovskite related devices.

In the last few years a renewed interest has reappeared in materials that were highly investigated in the 50s-70s, like manganese perovskites, spinel chalcogenides and vanadium oxides. The first two classes of materials are nowadays intensively studied due to the colossal magnetoresistance effect, which is the magnetoresistance associated with a ferromagnetic-paramagnetic transition. Vanadium oxides are known to form many compounds and most of them undergo metal-to-insulator phase transitions, with a high increase in the electrical conductivity (MIT). Many technological applications derive from the variation of the physical properties around the phase transition temperature. Although many efforts have been done in order to understand their electronic structures and to elucidate the MIT mechanisms, the vanadium oxides are still matter of debate in science.The present study has been performed in order to understand the electronic structure of these very intriguing materials. The role of different dopants that induce strong changes in the electronic and magnetic properties has been investigated making use of two spectroscopic techniques, namely X-ray photoelectron and X-ray emission spectroscopy.

<p dir="ltr">Photovoltaics are leading devices in green energy production. Understanding the fundamental physics behind energy transport in candidate materials for future photovoltaic and optoelectronic devices is necessary to both realize material limitations and improve efficiency. Excitons, which are bound electron-hole pairs, are central to determining how energy propagates throughout semiconductors. Exciton transport is greatly influenced by material dimensionality. In highly ordered quantum dot (QD) systems, electronic coupling between individual QDs can lead to coherent exciton transport, whereas in two-dimensional heterostructures, excitons can form at the interface of a heterojunction, creating charge-transfer excitons.</p><p dir="ltr">This dissertation is dedicated to summarizing the studies of exciton transport and behavior in two systems: perovskite QD superlattices and transition metal dichalcogenide (TMDC)/polyacene heterostructures. Chapter 1 provides readers with details on these materials in addition to information on the fundamental concepts (i.e., excitons, phonons, energy transfer) needed to best appreciate further chapters. Chapter 2 summarizes the spectroscopic techniques (photoluminescence and transient absorption spectroscopy and microscopy) used to examine exciton behavior. Next, the effects of disorder and dephasing pathways on the ability of perovskite QDs to coherently couple is investigated through the lens of superradiance in Chapter 3. After this, the temperature-dependent exciton transport within perovskite QD superlattices is imaged with high spatial and temporal resolutions in Chapter 4. The experimental transport data on these superlattices provides evidence for environment-assisted quantum transport, which, until this study, had yet to be realized in solid-state systems. In Chapter 5, attention is switched to verifying the existence and deepening the understanding of the behavior of several spatially separated interlayer excitons in a tungsten disulfide/tetracene heterostructure. Finally, Chapter 6 summarizes the preliminary results obtained through transient absorption spectroscopy on other TMDC/polyacene heterostructures where separation of the triplet pair state is attempted. </p><p dir="ltr">It is this author’s hope that this dissertation will not only summarize their graduate work but will also serve as inspiration for others to continue learning and contribute to the advancement of the energy research field.</p>