O desenvolvimento de novos materiais para a aplicação em eletroanalítica, uma atividade extremamente atraente, visa produzir compostos com condutividade elétrica alta, estabilidade mecânica e química e grandes áreas superficiais. Assim, nesta tese foram desenvolvidos Carbonos Mesoporosos Ordenados, um tipo de material carbônico recentemente explorado para diversas aplicações devido às suas propriedades específicas e facilmente manipuláveis. A produção inicia-se com a síntese da sílica mesoporosa utilizada como template, seguida pela impregnação por molhamento incipiente utilizando moléculas que são concomitantemente, fontes de carbono e de um heteroátomo (S, N ou O). Após a polimerização e carbonização em atmosfera não-oxidante, removeu-se o template de sílica, obtendo-se um material altamente organizado de estrutura mesoporosa, caracterizado pelas análises de BET, MET e DRX em ângulos baixos. Os materiais sintetizados apresentaram área superficial grande e acessível, indicadas pelas as análises de BET, o que ofereceu uma alta eficiência de pré-concentração de analitos. A fim de garantir um carbono com características grafíticas e boa condutividade, partiu-se de fontes carbônicas aromáticas e utilizou-se o óxido de ferro como catalisador da polimerização. Com isso, obteve-se materiais com carácter grafítico, mostrado pelas análises de DRX e Raman, com excelentes propriedades elétricas e transferência eletrônica mais rápida, mostrado pelas análises eletroquímicas (VC e EIE) garantindo um material com excelente atividade eletrocatalítica. Os três diferentes tipos de dopagem geraram três materiais distintos, que diferem não apenas na composição química, mas também nas propriedades físicas, elétricas e em sua resposta eletroanalítica. Os materiais sintetizados foram aplicados na detecção do cloranfenicol, um antibiótico com propriedades antibacterianas e farmacocinéticas excelentes, porém proibido em produtos destinados ao consumo humano. A metodologia desenvolvida apresentou boa sensibilidade e limites de detecção e quantificação, além da capacidade de analisar diretamente leite em pó, sem a necessidade de etapas trabalhosas de preparo de amostra. / The development of new materials for electroanalitycal application aims to produce materials with high electric conductivity, mechanical and chemical stability, and high surface areas. So, in this thesis, it was developed Ordered Mesoporous Carbon, a carbonic material recently explored in several applications due its specific plasticity properties. The production starts with the mesoporous silica synthesis. It is used as template, followed by the incipient wetness impregnation using molecules that are both a carbon source and heteroatom precursor (S, N or O). After the polymerization and the non-oxidant atmosphere carbonization, the template was removed, what yielded a highy ordered mesoporous structure, demonstrated by BET, TEM and low-angle XRD analysis. The synthetized materials showed high and accessible surface area, demonstrated by BET, which allowed high pre-concentration efficiency with a fast diffusion process. In order to get a graphitic carbon with good conductivity, it was used aromatic carbon precursors and iron as polymerization catalyst. Consequently, a material with graphitic character was getting, as we can see at XRD and Raman, with excellent electric properties and faster electronic transference, showed by electrochemical analysis (CV and EIS), leading to a material with excellent electrocatalytic activity. The three different doping types leading to three distinct materials, which differ not only at chemical composition, but also at physical, electrics and electroanalytical properties. The materials was applied at chloramphenicol detection, an antibiotic with excellent antibacterial and pharmacokinetics properties. However, it is forbidden in edible products. The developed methodology has good sensibility, and limits of detection and quantification. In addition, was possible to analyze powder milk directly, without any other timing consuming procedure of sample preparing.

O polímero de policaprolactona (PCL) dopado com [Eu (TTA) 3 (H2O) 2] no complexo 1, 2, 5, 10 e 15% de concentrações foram preparadas e as suas propriedades térmicas e de luminescência discutidas. As bandas de absorção de infravermelho no intervalo de 1800-1550 cm-1 correspondente ao ν sensível (C = O) foram seleccionados para a técnica de ajuste de curva de desconvolução e confirmou-se que os picos de componentes são deslocados gradualmente com o aumento da concentração de dopagem. O deslocamento do ν (C = O) banda para os β-dicetonato complexos para novas posições nos sistemas dopados (pCLE) proporcionam boa evidência de que o ião de metal está coordenado aos átomos de oxigénio dos grupos carbonilo PCL. Calorimetria exploratória diferencial (DSC) não mostraram alterações significativas na segunda temperatura de fusão (Tm2) para as amostras de cinema. No entanto, a cristalinidade é afectada pelo complexo dopante em materiais de polímero em maior concentração. A análise termogravimétrica (TGA) não mostra nenhuma perda de peso na gama de 50-200 ° C para os sistemas poliméricos dopados, corroborando a interacção da matriz de polímero com Eu3 + complexo n por substituição das moléculas de água no complexo precursor. A observação das bandas de emissão característicos resultantes das transições 5D0 → 7FJ (J = 0-4) dominadas pela hipersensibilidade transição 5D0 → 7F2 em torno de 614 nm, de íon Eu3 +, indicando que a incorporação de Eu3 + complexo no sistema de polímero. O valor da eficiência quântica de emissão de nível 5D0 para os materiais poliméricos dopados (η = 40-62%) são mais elevados do que para o complexo [Eu (TTA) 3 (H2O) 2] complexo (η = 29%), sugerindo que o matriz de polímero actua como co-sensibilizador do processo de luminescência. / The polycaprolactone (PCL) polymer doped with [Eu(tta)3(H2O)2] complex at 1, 2, 5, 10 and 15 % concentrations were prepared and their thermal and luminescence properties discussed. The IR absorption bands in the range of 18001550 cm1 corresponding to the sensitive ν(C=O) were selected for the deconvolution curve-fitting technique and was confirmed that the component peaks are gradually shifted with the increase of doping concentration. The displacement of the ν(C=O) band for the β-diketonate complex to new positions in doped systems (PCLE) provide good evidence that the metal ion is coordinated to the oxygen atoms from the PCL carbonyl groups. Differential scanning calorimetry (DSC) showed no significant changes in second melting temperature (Tm2) for the film samples. However, crystallinity is affected by the dopant complex in the polymer materials at higher concentration. Thermogravimetric analysis (TGA) shows no weight loss in the range of 50200 °C for the doped polymeric systems, corroborating the interaction of the polymer matrix with the Eu3+-complex by substitution of the water molecules in the complex precursor. The observation of the characteristic emission bands arising from the 5D0 → 7FJ transitions (J=0-4) dominated by the hypersensitive 5D0 → 7F2 transition at around 614 nm of Eu3+ ion, indicating the incorporation of the Eu3+ complex in the polymer system. The value of the emission quantum efficiency of 5D0 level for the doped polymer materials (η = 40 - 62 %) are higher than for the [Eu(TTA)3(H2O)2] complex (η = 29 %), suggesting that the polymer matrix acts as co-sensitizer of the luminescence process.

A solução sólida céria-samária é uma das principais candidatas para aplicação como eletrólito sólido em células a combustível de óxido sólido, devido sua alta condutividade iônica em temperaturas intermediárias (500-750 ºC) de operação. Um dos problemas ainda não solucionados com relação a este material é sua relativamente baixa sinterabilidade. Nesse trabalho foi utilizado o método de sinterização em duas etapas visando melhorar a densificação com reduzido tamanho médio de grãos. Soluções sólidas comercial e obtida por mistura de óxidos de composição Ce0,8Sm0,2O1,9 foram utilizadas. Para fins comparativos também foi utilizado o método denominado sinterização em duas etapas tradicional que visa a obtenção de amostras densas independentemente do tamanho médio de grãos. Resultados de densidade aparente e retração linear revelaram que ambos os tipos de amostras têm comportamento distinto. Para a solução sólida comercial, a retração total até 1400 ºC foi de ~18%. Só foram obtidos resultados de densidade significativos ao utilizar temperaturas elevadas (igual ou superior a 1300 ºC). Para o material obtido por mistura de óxidos não foi possível atingir densidades maiores que 90% da densidade teórica. A sinterização em duas etapas tradicional produziu amostras densas, da mesma forma, que a não-tradicional, mas com tamanhos de grãos consideravelmente maiores. Amostras sinterizadas por ambos os processos foram analisadas por espectroscopia de impedância para a determinação da condutividade elétrica em função da temperatura, e não apresentaram variação significativa nas condutividades intra e intergranular. A sinterização em duas etapas não resultou em melhorias na densificação e nem na condutividade elétrica das amostras. Entretanto, a redução obtida no tamanho médio de grãos pode melhorar as propriedades mecânicas. / Samaria-doped ceria solid solution has been proposed to be used as solid electrolyte in Solid Oxide Fuel Cells due to its high ionic conductivity at intermediate temperatures (500-750 ºC). One of the main problems related to this solid solution is the relatively low sinterability. In this work, sintering of powder compacts was carried out by the two-step sintering method to improve the densification with simultaneous reduction of the mean grain size. Samaria-doped ceria, both commercial and prepared by solid state reactions, with composition Ce0.8Sm0.2O1.9 were investigated. For comparison purposes, the traditional two-step sintering method, by which dense specimens are produced, was also utilized. Apparent density and linear shrinkage results showed distinct features depending on the type of specimen. Total linear shrinkage for commercial solid solution up to ~ 1400 ºC was 18%, but high density values were obtained only for sintering experiments conducted at high temperatures ( 1300 ºC). Specimens prepared by solid state reactions did not attain density values higher than 90% of the theoretical one. The traditional method produced dense specimens as well as the two-step sintering, although the grain size was considerably higher in the former. Specimens sintered by the two methods were used for electrical conductivity measurements. No significant variation in both the grain and the grain boundary conductivities was obtained. The two-step sintering did not allow any improvement in the densification and in the electrical conductivity of samaria-doped ceria. However, the decrease in the mean grain size may contribute to improve the mechanical properties of this solid solution.

Doctor of Philosophy / Department of Chemistry / Emily McLaurin / Quantum dots are nanocrystalline semiconductors in which the size is so small that optoelectronic properties are size dependent. QDs have a lot of applications in displays, solar cells, lasers, light emitting diodes, etc. The optoelectronic properties of QDs depend on their size, composition, the shape of the particles and also the surface chemistry of the QDs. Phosphine based precursors have been mostly used in the synthesis of QDs. Due to the lack of tunable reactivity, this class of precursors, QDs with different shape are obtained by under different reaction conditions. With that, branched QDs are less likely to be obtained in one step reaction using phosphine based precursors. To synthesis QDs with a branched structure, in a single step synthesis, mixtures of precursors with different reactivity were used. Using dichalcogenides mixture, CdSe₁-xSx hyperbranched supra-quantum dots (HSQDs) where synthesized in a one-step microwave-assisted synthesis and shape evolution mechanism of formation of NCs studied. It is shown that the NCs formed in three steps of nucleation, aggregation, and growth. By controlling the reaction conditions, simple branched tetrapod NCs are prepared, but the obtained NCs have no emission due to unpassivated surface and defects which work as trap. To obtain luminescent NCs obtained through doping. Hyperbranched Mn²+:ZnSe₁-xSx NCs also prepared using a mixture of Ph₂Se₂ and Me₂S₂. The shape evolution mechanism of the formation of NCs was studied and it is shown that the NCs are formed via oriented attachment of initially formed nanoparticles. The NCs used for thiol sensing, and it observed that they have a better sensitivity and detection limit than spherical QDs. Although hyperbranched NCs have higher sensitivities over nonbranched NCs but, the spherical NCs have better detection limit and can dispersed in aqueous medium by ZnS shell growth followed by silica shell formation. To study the effect of ZnS shell thickness on sensing property of NCs, a set of spherical Mn:ZnSe@ZnS with different ZnS shell thickness were prepared and used for thiol sensing. It observed that in organic medium, thinner ZnS layer gives the highest sensitivity and QDs with thick ZnS shell layer have less sensitivity. For measurement in aqueous medium, QDs transferred to PBS buffer after formation of silica shell over QDs. It observed that NCs with a thin ZnS shell layer lose their emission and sensing completely. Thick ZnS shell protects NCs in the silica shell formation step but they show very low sensitivity to thiol compounds as well. ZnS shell with medium thickness gives the best sensitivity in an aqueous medium. The emission of Mn:ZnSe@ZnS QDs originated from d-d electron transition of Mn(II) ions and is independent to the size of QDs. To extend our study to QDs with band edge emission, preparation of luminescent InP QDs by post-synthetic modification is studied. InP NCs were synthesized using heat up method and successive injection of precursors. Narrow size distribution NCs obtained after size selection precipitation. Emissive NCs obtained after etching using InCl3 and fluoride containing salts. The study showed that more InCl3 case more etching and presence of fluoride-containing salt is necessary for band edge emission of the NCs.

Ce travail de thèse est issu d’une collaboration entre les laboratoires de recherche FEMTO-ST de l’université technologique de Belfort-Montbéliard et IRCELYON de l’université Claude Bernard à Villeurbanne. Les objectifs de cette étude portent sur la faisabilité d’élaborer par pulvérisation cathodique magnétron des films minces de cobaltite de lanthane nanostructurés. En effet, ces films présentent des propriétés catalytiques intéressantes pour l’oxydation des composés organiques volatiles comme le propène (C3H6) ou le monoxyde de carbone (CO) qui constituent la principale source de pollution de l’air. Il sera montré dans un premier temps que les cobaltites de lanthane de formule LaCoO3 ne sont pas efficaces pour ce type d’application. La composition chimique de ce matériau sera donc modifiée en y incorporant de l’argent de manière à faire varier les propriétés physico-chimiques des films et d’augmenter leurs performances catalytiques. La morphologie des films est directement impactée par l’introduction de Ag puisqu’elle évolue d’un système dense à un système « nanofilaire ». Une autre série de dépôts sera également élaborée et testée en catalyse constituée de cobaltites de lanthane dopées avec de l’argent mais aussi du cérium. On retiendra alors que les films de LaCoO3 + Ag sont plutôt efficaces et prometteurs puisqu’ils présentent des performances catalytiques se rapprochant de celles du platine (catalyseur de référence). Néanmoins, bien que les films aient toujours cette morphologie nanofilaire, les compositions chimiques des films élaborés à base de LaCoO3 + Ag + Ce doivent être optimisées afin d’augmenter leurs activités catalytiques. / This work was made in the frame of a scientific research relationships between the laboratory FEMTO-ST of the Technological University of Belfort-Montbéliard and the laboratory IRCELYON of the Claude Bernard University of Villeurbanne. This study aims at characterizing the feasibility of nanostructured lanthanum cobaltite thin films via magnetron sputtering. Indeed, it is well known these materials have interesting catalytic properties regarding the oxidation of volatile organic compounds such as propene (C3H6) or carbon monoxide (CO), the latter being the main source of air pollution. First, it has been shown that lanthanum cobaltites of formula LaCoO3 are not efficient for this type of application. The chemical composition of this material was then modified by incorporating silver so as to vary the physicochemical properties of the films and increase their catalytic performance. In consequence, the morphology of the films was directly impacted by the introduction of Ag since it evolved from a dense system to a "nanowire" system. Another series of deposits based on cobaltite modified by both silver and cerium additions have been also developed and tested during catalytic tests. It should be noted that the Ag containing thin films of LaCoO3 are rather efficient and then promising since they have catalytic performances close to those of platinum (the reference catalyst). Concerning the Ag and Ce containing perovskite films, although they still have this peculiar nanowired morphology, their chemical compositions have to be optimized in order to increase their catalytic activities.

A great deal of theoretical activity has resulted from blending the fields of computer science and quantum mechanics. Out of this work has come the concept of a quantum computer, which promises to solve problems currently intractable for classical computers. This promise has, in turn, generated a large amount of effort directed toward investigating quantum computing experimentally. ¶ Quantum computing is difficult because fragile quantum superposition states of the computer’s register must be protected from the environment. This is made more difficult by the need to manipulate and measure these states. ¶ This thesis describes work that was carried out both to investigate and to demonstrate the utility of rare earth ion dopants for quantum computation. Dopants in solids are seen by many as a potential means of achieving scalable quantum computing. Rare earth ion dopants are an obvious choice for investigating such quantum computation. Long coherence times for both optical and nuclear spin transitions have been observed as well as optical manipulation of the spin states. The advantage that the scheme developed here has over nearly all of its competitors is that no complex nanofabrication is required. The advantages of avoiding nano-fabrication are two fold. Firstly, coherence times are likely to be adversely effected by the “damage” to the crystal structure that this manufacture represents. Secondly, the nano-fabrication presents a very serious difficulty in itself. ¶ Because of these advantages it was possible to perform two-qubit operations between independent qubits. This is the first time that such operations have been performed and presents a milestone in quantum computation using dopants in solids. It is only the second time two-qubit operations have been demonstrated in a solid. ¶ The experiments performed in this thesis were in two main areas: The first was the characterisation of hyperfine interactions in rare earth ion dopants; the second, simple demonstrations directly related to quantum computation. ¶ The first experiments that were carried out were to characterise the hyperfine interactions in Pr[superscript 3]+:Y[subscript 2]SiO[subscript 5]. The characterisation was the first carried out for the dopants in a site of such low symmetry. The resulting information about oscillator strengths and transition frequencies should prove indispensable when using such a system for quantum computation. It has already enabled an increase in the coherence times of nuclear spin transitions by two orders of magnitudes. ¶ The experiments directly related to the demonstration of quantum computation were all carried out using ensembles. The presence of a significant distribution of resonant frequencies, or inhomogeneous broadening, meant that many different sub-ensembles could be addressed, based on their resonant frequencies. Furthermore, the properties of the sub-ensembles could be engineered by optically pumping unwanted members to different hyperfine states away from resonance with the laser. ¶ A previously demonstrated technique for realising ensembles that could be used as single qubits was investigated and improved. Also, experiments were carried out to demonstrate the resulting ensembles’ utility as qubits. Further to this, ions from one of the ensembles were selected out, based on their interaction with the ions of another. Elementary two qubit operations were then demonstrated using these ensembles.

Solid Oxide Fuel Cells (SOFCs) are devices that directly convert chemical energy into electrical energy, without proceeding through a Carnot combustion cycle. These devices are based on the usage of solid oxide electrolytes operating at relatively elevated temperatures. Two major hurdles must be overcome in order to decrease the operating temperatures of practical SOFCs. The first relates to reducing ohmic losses within solid electrolytes. The second relates to the need for developing high performance electrodes since electrolyte reaction rates at both anode and cathode are affected detrimentally as operating temperatures fall. This PhD project has focussed on addressing the first hurdle in two innovative ways: 1. the implementation of solid electrolytes with higher ionic conductivity than zirconia, 2. the development of very thin film electrolytes as thick as 5ƒÝm. Several thin films with novel electrode-electrolyte structures were fabricated and evaluated in order to demonstrate the viability of low temperature SOFC operations. Development of such thin films was innovative and challenging to achieve. The approach taken in this work involved fabricating a dense and thin gadolinia doped ceria (10GDC - Gd 10wt%, Ce 90wt%) oxide electrolyte. 10GDC is an electrolyte exhibiting higher conductivities than conventional materials during low temperature operations. A research contribution of this PhD was the demonstration of the deposition of 10GDC thin films using RF magnetron sputtering for the first time. 10GDC thin film electrolytes with thickness in a range between 0.1 to 5ƒÝm were fabricated on 10 yttrium stabilised zirconium (10YSZ) substrates by using a RF magnetron sputterer. The primary parameters controlling 10GDC thin film deposition using this method were explored in order to identify optimal conditions. The fabricated films were subsequently analysed for their morphology, composition and stoichiometry using a variety of methods, including Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray Spectrometry (EDS), optical microscopy, X-ray Photoelectron Spectroscopy (XPS), and X-ray Diffraction (XRD). A preliminary test was conducted in order to examine the function of 10GDC thin film electrolytes together with the cathode and anode substrates at intermediate temperatures (700oC). A complete planar single cell was designed and assembled for this purpose. However, when fully assembled and tested, the cell failed to generate any voltage or current. Consequently, the remainder of the PhD work was focused on systematically exploring the factors contributing to the assembled fuel cell failure. As fabrication failure analysis is seldom reported in the scientific literature, this analysis represents a significant scientific contribution. This analysis proceeded in a series of steps that involved several different methods, including SEM, red dye analysis, surface morphology and cross section analysis of the cell. It was found that pinholes and cracks were present during the fuel cell operating test. Cathode delamination was also found to have occurred during the test operation. This was determined to be due to thermal expansion mismatch between the cathode substrate and the 10GDC electrolyte thin film. A series of suggestions for future research are presented in the conclusion of this work.

<p>The purpose of this thesis work was to find a way to measure basic light emission properties of nitrogen-and-boron-doped 6H-SiC, which are fabricated with a growth method developed at Linköping University. The research is in its initial phase and the light properties as well as optical measurement techniques are important. The aim is that the results of the measurements will provide feedback to the growth process what quality and doping levels that are required to get the maximum amount of light. The measurements were performed at the Laboratory of Lighting Technology, Technical University of Darmstadt, Germany.</p><p>Two measuring methods with different excitation sources were tested: a double monochromator and a setup using near UV-filters. While the double monochromator was able to project wavelengths in steps down to 0.5 nm with a high accuracy, the filters were only available in steps of 10 nm where the accuracy of the wavelength values varied. The double monochromator was chosen for the continuing measurements.</p><p>When using excitation light between 375-390 nm the emitted light was in the visible wavelength region. The light properties measured were the irradiance (measured in W/m²) and the peak wavelength were maximum luminescence occurred.</p><p>The result showed that sample 2-4 had a peak wavelength at approximately 580‑582 nm for the excitation wavelength 375 nm. For sample 5 the peak wavelength occurred at 582 nm at the excitation wavelength 390 nm. Sample 1, the unintentionally doped, did not show any measurable results as expected.</p><p>When irradiance of the excitation light was approx. 8 W/m² the irradiance at the peak of luminescence for the samples varied between 15.03-29.35 mW/m². The low values are believed to be the result of the emitted light scattering in all directions whereas the measurements are done in one direction and only from a small area of the sample.</p><p>The measurements has shown that it is possible to measure the light properties of the grown material even though the samples were not finalized (capsulated) LED’s. The results from the measurements are of interest for the continuing development of the material.</p>

Thesis (Ph. D.)--Ohio State University, 2006. / Title from first page of PDF file. Includes bibliographical references (p. 232-237).

The electronic structure of some transition metal compounds, specifically, Ca-doped LaMnO3, fundamental Mn oxides (MnO, Mn2O3, Mn3O4, and MnO2), and Fe-doped ZnO is studied using a combination of soft X-ray spectroscopy and atomic multiplet calculations. X-ray absorption spectroscopy (XAS) and X-ray emission spectroscopy (XES) are used as experimental tools to probe the unoccupied and occupied partial density of electronic states,respectively.<p> Ca-doped LaMnO3 perovskites have attracted great attention due to their colossal magnetoresistance and a wide range of magnetic and structural transitions. The magnetic and charge transport properties of these perovskites are directly related with Mn 3d-occupancy or Mn-valency and therefore, an investigation of the Mn-valence at Ca-doped LaMnO3 system is important. In this system, the Mn-valency is generally considered as a mixture of Mn3+ and Mn4+. But my research suggests the presence of Mn2+ at the surface of Ca-doped LaMnO3 samples. It is observed that increasing Ca-doping decreases Mn2+ concentration, and conversely, increases Mn3+ concentration. High temperature annealing at 1000 °C in air leads to the full reduction of surface Mn2+. Mechanisms for these observations are proposed in this study.<p> Mn oxides (MnO, Mn2O3, Mn3O4, and MnO2) are often used as reference standards for determining the Mn-valency in Mn-related complex systems and therefore a detailed understanding of their electronic structure is necessary. The Mn L2,3 XAS and O K XAS are measured for the four Mn oxides consisting of three common Mn oxidation states (Mn2+ in MnO, Mn3+ in Mn2O3, mixture of Mn2+ and Mn3+ in Mn3O4, and Mn4+ in MnO2). A significant energy shift with a systematic trend is observed in measured Mn L2,3 and O K absorption edges. These energy shifts are identified as a characteristic shift for different Mn oxidation states. Mn L2,3 Resonant Inelastic X-ray Scattering (RIXS) spectroscopy is demonstrated as a powerful tool in describing low energy excitations, e.g. d-d excitations and charge-transfer excited states in Mn oxides. For the first time, a RIXS study of Mn2O3,Mn3O4, and MnO2 is accomplished. Atomic multiplet calculations are used to successfully reproduce the energy positions and intensity variations of d-d excitation peaks observed in the experiment, and thus to describe the experimental RIXS spectra.<p> Finally, the local electronic structure of Fe implanted ZnO samples, a useful diluted magnetic semiconductor for spintronics, is investigated to shed light on the existing debate about the origin of ferromagnetism in these materials. Fe L2,3 XAS reveals that doped Fe ions are present in both Fe2+ and Fe3+ valence states. A combined theoretical and experimental study shows that doped ions are incorporated into Zn-sites of ZnO in tetrahedral symmetry. Fe L3- RIXS measurements demonstrate that a high Fe-ion dose of 8 × 107 cm-2 causes formation of FeO clusters, while low dose samples exhibit more free carriers.