Dissertations / Theses on the topic 'Energy band gap'

With the increasing interest in wide-band gap devices, their potential benefits in power applications have been studied and explored with numerous studies conducted for both SiC and GaN devices. This thesis investigates the use of wide-band gap devices as the switching element in a semiconductor DC breaker. It involves the design of an efficient semiconductor DC breaker, its simulation in SPICE, construction of a hardware prototype and the comparative study of SiC and Si versions of the aforementioned breaker. The results obtained from the experiments conducted in the process of concluding this thesis show that the SiC version of the breaker is a superior option for a semiconductor DC breaker.

The focus of this doctoral thesis is the atomic level design of photocatalysts and gas sensing materials. The band gap narrowing in the metal oxides for the visible-light driven photocatalyst as well as the interaction of water and gas molecules on the reactive surfaces of metal oxides and the electronic structure of kaolinite has been studied by the state-of-art calculations. Present thesis is organized into three sections. The first section discusses the possibility of converting UV active photocatalysts (such as Sr2Nb2O7, NaTaO3, SrTiO3, BiTaO4 and BiNbO4) into a visible active photocatalysts by their band gap engineering. Foreign elements doping in wide band gap semiconductors is an important strategy to reduce their band gap. Therefore, we have investigated the importance of mono- and co-anionic/cationic doping on UV active photocatalysts. The semiconductor's band edge position is calculated with respect to the water oxidation/reduction potential for various doping. Moreover, the tuning of valence and conduction band edge position is discussed on the basis of dopant's p/d orbital energy. In the second section of thesis the energetic, electronic and optical properties of TiO2, NiO and β-Si3N4 have been discussed to describe the adsorption mechanism of gas molecules at the surfaces. The dissociation of water into H+ or OH- occurs on the O-vacancy site of the (001)-surface of rutile TiO2 nanowire, which is due to the charge transfer from Ti atom to water molecule. The dissociation of water into OH- and imino (NH) groups is also observed on the β-Si3N4 (0001)-surface due to the dangling bonds of the lower coordinated N and Si surface atoms. Fixation of the SO2 molecules on the anatase TiO2 surfaces with O-deficiency have been investigated by Density Functional Theory (DFT) simulation and Fourier Transform Infrared (FTIR) spectroscopy. DFT calculations have been employed to explore the gas-sensing mechanism of NiO (100)-surface on the basis of energetic and electronic properties. In the final section the focus is to describe the optical band gap of pristine kaolinite using the hybrid functional method and GW approach. Different possible intrinsic defects in the kaolinite (001) basal surface have been studied and their effect on the electronic structure has been explained. The detailed electronic structure of natural kaolinite has been determined by the combined efforts of first principles calculations and Near Edge X-ray Absorption Fine Structure (NEXAFS).

Second generation solar cells based on thin film semiconductors emerged as a result of the past ten years of intense research in the thin film preparation technology. Thin film solar cell technology can be cost effective as it uses comparatively cheap materials suitable for solar building integration. Chemical Vapour Deposition (CVD) is a well-known method for the deposition of high quality thin films. This thesis describes the synthesis of novel tin(II)dithiocarbamate [Sn(S2CNEt2)2] and bis(diphenylphosphinediselenoato) tin(II) [Sn(Ph2PSe2)2] and these complexes as single source precursor for the deposition of SnS and SnSe and by using the combination of [Sn(Ph2PSe2)2] with [Cu(acac)2], Cu2SnSe3 thin films were deposited by AACVD. By using suitable combinations of metal complexes ([nBu2Sn(S2CNEt2)2], [Cu(S2CNEt2)2] [Zn(S2CNEt2)2] [Zn(Se2CNEt2)2] [Zn(acac)2], [Sn(OAc)4], [Cu(PPh3){Ph2P(Se)NP(Se)Ph2}] thin films and nanocomposites of CZTS, CFTS, CZTSe, CFTSe, CZFTS, , CZFTSe, CZTSSE, CFTSSe and CZFTSSe were prepared. The effect of precursor concentration and deposition temperature on the structure, morphology and composition of the thin films were studied in detail using by powder X-ray diffraction (p-XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and elemental mapping. This thesis addressing the structural inhomogeneity, control of growth and material characterization is expected to yield closer performance parity between CZTS-Se and CIGS solar cells. A series of systematic experiments were carried out. Through AACVD and simple solvothermal methods CZFTS nanoparticles and thin films were prepared. The simple, potentially, low-cost nature of the CZTS nanoparticles and the enhancement of charge carrier mobility achieved suggest that these nanoparticles have potential in the improvement of OFETs and perhaps other organic electronic devices.

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This work studied tellurite glasses in a ternary system with the TeO2-Li2O-ZnO composition, divided in three groups with 10%, 15% and 20%mol Li2O fixed. For this study, was made the replacement of known TeO2 network former by ZnO. It used the Differential Scanning Calorimetry (DSC), optical absorption in ultraviolet-visible region (UV-VIS), Raman spectroscopy, Fourier transform infrared (FTIR), linear refractive index (n0) measurement and instrumented nanoindentation. The samples were prepared by melt quenching method in the bulk form. DSC results showed that the glass transition temperature (TG) virtually no change in the glass systems, while that there was an increase in the glass stability due to exchange of TeO2 by ZnO especially for 10 and 15% mol Li2O groups. By continuing, the UV-VIS results indicated a gradual increase in the band gap energy which was calculated by Urbach rule; this increased energy as TeO2 was replaced by ZnO, can also be seen as a blue shift. These same results were confirmed by a structural change seen by Raman spectroscopy: with the increased of ZnO, the vibrational modes located at 450 e 659 cm-1 which incorporate trigonal bipyramids of TeO4 are gradually replaced by vibrational modes at 735-760 cm-1 referred the creation of Zn2Te3O8 units. This behavior by Raman spectroscopy is also confirmed by the FTIR results with increased intensity of peaks related to vibrational modes of ZnO molecules. Therefore, it is verified that the addition of ZnO in the system has the property to decrease the amount of NBOs, which in turn decreases the polarizability of the oxide ion of the system and increases the band gap energy. Lastly, the increase in the band gap values and, Raman and DSC results showed that this glassy system acquires considerable glass stability, has good transmittance in the ultraviolet and visible regions, and thus appears as a promising candidate for host ions optically active.
Esta dissertação teve por objetivo estudar os vidros teluretos em um sistema ternário com composição TeO2-Li2O-ZnO, separados em três grupos com concentração fixa de 10%, 15% e 20% em mol de Li2O com a respectiva substituição do conhecido formador de rede TeO2 por ZnO. Tal estudo agregou as técnicas de Calorimetria Diferencial de Varredura (DSC), absorção óptica na região do ultravioleta-visível (UV-VIS), espectroscopia Raman, infravermelho por transformada de Fourier (FTIR), medidas de índice de refração linear (n0) e nanoindentação instrumentada. As amostras foram preparadas pelo método de melt quenching e obtidas na forma de bulk. Por meio dos resultados de DSC verificou-se que a temperatura de transição vítrea (TG) fica praticamente inalterada nesse sistema vítreo, enquanto que existe um aumento expressivo da estabilidade vítrea com a troca de TeO2 por ZnO, principalmente para os grupos com 10 e 15% em mol de Li2O. Já os resultados de UV-VIS mostraram um aumento gradual na energia de band gap, a qual foi calculada utilizando a Regra de Urbach. Esse aumento de energia, à medida que TeO2 era substituído por ZnO, também pode ser visto como um blue shift (deslocamento para o azul). Esse aumento de band gap foi confirmado por uma mudança estrutural vista por espectroscopia Raman: com o aumento na concentração de ZnO, os modos vibracionais localizados em 450 e 659 cm-1 que incorporam bipirâmides trigonais de TeO4 passam a ser gradualmente substituídos por modos vibracionais em 735-760 cm-1 que se referem a criação de unidades Zn2Te3O8. Esse comportamento por espectroscopia Raman também é confirmado através dos resultados de FTIR com aumento da intensidade dos picos relacionados a modos vibracionais de moléculas ZnO. É verificado assim que a adição de ZnO ao sistema tem a propriedade de diminuir a quantidade de NBOs, o que por sua vez, diminui a polarizabilidade do íon óxido do sistema e aumenta a energia de band gap. Com isto, o aumento nos valores de band gap e os resultados de DSC e Raman mostraram que esse sistema vítreo adquire considerável estabilidade vítrea, tem boa transmitância nas regiões do ultravioleta e visível e, assim, se mostra como um promissor candidato para hospedeiro de íons opticamente ativos.

Negli ultimi tempi sta assumendo grande importanza la ricerca sulla produzione di idrogeno dall’acqua tramite celle foto-elettrolitiche. In questa tesi vengono descritte le analisi condotte su un materiale che può essere coinvolto in questa applicazione: il TiO2 drogato con atomi di V. In particolare è stato valutato l’effetto del drogaggio sull’energy gap tramite misure di trasmittanza ottica effettuate in laboratorio su campioni con diverse concentrazioni di V e trattati termicamente a varie temperature. Nel primo capitolo vengono descritte le caratteristiche dei semiconduttori legate all’ottica, soffermandosi in particolare sul TiO2. Nel secondo capitolo sono illustrati l’apparato e il metodo sperimentale; viene inoltre fornita una descrizione dettagliata dei campioni analizzati. Nel terzo capitolo vengono esposti i risultati delle analisi dei dati.

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In this work were studied the tellurite glasses of the glass system (100-x-y)TeO2-yLi2O-xBaO obtained by melt quenching method and characterized by techniques X-Ray Diffraction (XRD), Differential Scanning Calorimetry (DSC), Raman Spectroscopy, Fourier Transform Infrared Spectroscopy (FTIR), UV-Vis Spectroscopy, linear refractive index and density measurements. The results of DRX measurements allowed classifying the samples with a standard characteristic diffraction amorphous structures. The DSC results show that the samples located close to the center of the glass-forming region have the highest values for the thermal stability, these being greater than 100 °C. Results of Raman spectroscopy show that there is a decrease in the connectivity of the network glass formed and of the TeO4 units with decreasing amount of tellurium. The units of TeO3+1 show an increase while for TeO3 units there is not a well defined behavior. The FTIR results show a decrease in TeO4 units and increase in TeO3 units with decreasing amount of tellurium. The Band Gap (Eg) energy values obtained are in agreement with those found in the literature for tellurite glasses. The results also indicate that electronic transitions that occur are of the type permitted indirect, still being observed an increase in Eg values as tellurium replaced. The structural changes create Non Bridging Oxygen (NBO), but the connection between the NBO and Te atoms is weak, which do not influence in Eg behavior. This influence starts to be strong above a certain value of BaO content (which depends on the Li2O content). While these values to the energy band gap increase, the values of the linear refractive index decreases, agreeing with what is presented in the literature. For polarizability ion oxide, only the samples with 5% Li2O shows behavior consistent with what is reported in the literature, inversely proportional to the Band Gap values and proportional to the refractive index.
Neste trabalho foram estudados os vidros teluretos do sistema vítreo (100-x-y)TeO2-yLi2O-xBaO obtidos pelo método de melt quenching e caracterizados pelas técnicas de Difração de Raios X (DRX), Calorimetria Diferencial de Varredura (DSC), Espectroscopia Raman, Espectroscopia no Infravermelho por Transformada de Fourier (FTIR), Espectroscopia UV-Vis, medidas de índice de refração linear e densidade. Os resultados das medidas de DRX permitiram classificar as amostras que apresentavam um padrão de difração característico de estruturas amorfas. Os resultados de DSC mostraram que as amostras localizadas próximas ao centro da região de formação vítrea apresentaram os maiores valores para a estabilidade térmica, sendo estes maiores que 100 °C. Os resultados de espectroscopia Raman mostraram que ocorre uma diminuição na conectividade da rede vítrea formada e das unidades de TeO4 com a diminuição da quantidade de telúrio. As unidades de TeO3+1 apresentaram um aumento, enquanto que para as unidades de TeO3 não há um comportamento bem definido. Os resultados de FTIR mostraram uma diminuição nas unidades de TeO4 e um aumento nas unidades de TeO3 com a diminuição da quantidade de telúrio. Os valores de energia de Band Gap (Eg) obtidos estão de acordo com os encontrados na literatura para vidros teluretos. Os resultados também indicam que as transições eletrônicas que ocorrem são do tipo permitida indireta, sendo observado ainda um aumento nos valores de Eg à medida que o telúrio é substituído. As modificações estruturais que ocorreram criam oxigênios não ligados (NBO – non-bridging-oxygen), mas os mesmos são fracamente conectados aos átomos de Te, não influenciando tanto nos valores de Eg até certa quantidade de BaO (que depende da quantidade de Li2O). Enquanto estes valores para a energia de Band Gap aumentam, os valores para o índice de refração linear diminuem, concordando com o que é apresentado pela literatura. Para a polarizabilidade do íon óxido, apenas as amostras com 5% de Li2O apresentaram comportamento coerente com o que é reportado na literatura, sendo inversamente proporcional ao Band Gap e proporcional ao índice de refração.

Magister Scientiae - MSc
In this research, novel hybrid perovskite materials were synthesized, characterized and applied in photovoltaic cells (PVCs) to enhance the performance of PVCs. Mixed-organic-cations tin halide perovskites (MOCTPs) were successfully synthesized using sol-gel method. These MOCTPs include guanidinium dimethylammonium tin iodide ([GA][(CH3)2NH2]SnI3) and guanidinium ethylmmonium tin iodide ([GA][CH3CH2NH3]SnI3). The MOCTPs were studied in comparison to their single-organic-cation tin perovskites (SOCTPs), which include guanidinium tin iodide (GASnI3), ethylammonium tin iodide ([CH3CH2NH3]SnI3) and dimethylammonium tin iodide [(CH3)2NH2]SnI3. High Resolution Scanning Electron Microscopy (HR SEM) of the five perovskite materials showed good crystallinity and tetragonal and hexagonal cubic shapes, characteristic of perovskites. These shapes were also confirmed from High Resolution Transmission Electron Microscopy (HR TEM), and the internal structure of the perovskites gave similar zone axes (ZAs) with those obtained from X-ray Diffraction (XRD). XRD showed tetragonal lattice shape for these perovskite materials. Fourier Transform Infrared (FTIR) demonstrated similar functional groups for both the SOCTPs and MOCTPs. FTIR bands that were observed are; N-H, C-H sp3, C-H aldehyde, N-H bend, C-N sp3 and N-H wag. From the 13C Nuclear Magnetic Resonance (NMR) results, the carbon atom of guanidinium iodide precursor shifts from downfield to upfield position, e.g. from 110.57 ppm to 38.49 ppm in GASnI3 SOCTP. This confirms a shift upfield of the carbon atom in guanidinium iodide precursor as it bonded to Sn metal in the perovskite chemical structure. Similar behavior was also observed for the NMR spectra of [GA][CH3CH2NH3]SnI3 MOCTP, where C-2 and C-3 atoms of ethylammonium iodide precursor shifted upfield from 37.03 ppm to 15.69 ppm and 16.06 ppm to 14.39 ppm respectively.

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In this work, the correlation between the structural morphology with thermal, optical and mechanical properties of (1 – x – y)TeO2-xLi2O-yMoO3 glasses was studied. The analysis was divided into three sets of samples, varying according to the composition for technique. The results reveal different behaviors for each set vitreous stabilities. The Raman spectroscopy and FTIR results showed a similar structural change between each set with decrease NBOs and new peaks position. The Raman and FTIR spectra results showed that with increasing content x and y, concomitantly, occur the conversion of TeO4 to TeO3+1 units, then, in addition to TeO3 units. Furthermore occurs change coordination in the structural units Mo atoms 4 to 6 and these structural changes. Li addition causes these structural changes. This fact confirmed by the Band Gap energy values, which increase with the increase of x and y, it decreases the optical basicity and refractive index values. By optical absorption measurements determined the Band Gap energy values of all samples. It was concluded that occur direct transitions allowed in all sets. The behavior of increasing Band Gap values and decreasing Optical basicity confirmed the decreasing in the NBO content leading to an indication of a more polymerized network for a variation of x mol%. Finally the behaviors elastic modulus and hardness, which shows decreased stiffness of the material with the incorporation of Li2O and MoO3 concomitantly, is presented. x
Este trabalho apresenta as correlações entre a morfologia estrutural e as propriedades térmicas, ópticas e mecânicas nos vidros (1 – x – y)TeO2 – xLi2O – yMoO3. Dividiram-se as análises em três conjuntos de amostras, de acordo com variação da composição, para cada técnica utilizada. Os resultados revelam diferentes comportamentos de estabilidades vítreas para cada conjunto. As medidas por espectroscopia de Raman e FTIR mostram mudanças estruturais similares entre cada conjunto com diminuição dos NBOs e novas posições de picos. Os resultados de Raman e FTIR mostram que com o aumento em conteúdo x e y ocorre a transformação de unidades TeO4 para TeO3 + 1 e, em seguida, para TeO3 além disso ocorre a mudança de coordenação do átomo de Mo de 4 para 6 e estas alterações estruturais têm sido relacionados com a adição de átomos de Li. Este fato é confirmado pelos valores de energia de Band Gap, que aumentam com o incremento de x e y, e diminuição dos valores de basicidade óptica e índice de refração. As energias de Band Gap, para todas as amostras, foram determinadas por medidas de absorção óptica na região do Ultravioleta. Foi concluído que ocorrem transições diretas permitidas em todos os conjuntos. E por fim apresenta-se os comportamentos de dureza e Módulo elástico, o que revela diminuição da rigidez do material com a incorporação de Li2O e MoO3 concomitantemente.

Philosophiae Doctor - PhD
The main aim of this study was to prepare band gap-engineered graphene quantum dot (GQD) structures which match the different energies of the visible region in the solar spectrum. These band gap-engineered graphene quantum dot structures were used as donor materials in rainbow Schottky junction solar cells, targeting all the energies in the visible region of the solar spectrum for improved solar-to-electricity power conversion efficiency. Structural characterisation of the prepared nanomaterials under solid-state nuclear magnetic resonance spectroscopy (SS-NMR) showed appearance of bands at 40 ppm due to the presence of sp3 hybridised carbon atoms from the peripheral region of the GQD structures. Other bands were observed at 130 ppm due to the presence of polycyclic aromatic carbon atoms from the benzene rings of the GQD backbone, and around 180 ppm due to the presence of carboxylic acid carbons from oxidation due to moisture. Fourier-transform infrared resonance (FTIR) spectroscopy further confirmed the presence of aromatic carbon atoms and oxidised carbons due to the presence of C=O, C=C and -OH functional groups, concurrent with SS-NMR results.
2023-12-01

A systematic study of trends in band gap and lattice energies for bare zinc oxide nanoparticles were performed by means of quantum chemical density functional theory (DFT) calculations and density of states (DOS) calculations. The geometry of the optimized structures and the appearance of their frontier orbitals were also studied. The particles studied varied in sizes from (ZnO)₆ up to (ZnO)₁₉₂.The functionalization of bare and hydroxylated ZnO surfaces with MPTMS was studied with emphasis on the adsorption energies for adsorption to different surfaces and the effects on the band gap for such adsorptions.

Nesta dissertação realizamos a síntese eletroquímica e a caracterização eletroquímica e óptica de polímeros conjugados eletroluminescentes no azul, como o poli(p-fenileno) (PPP) e alguns copolímeros. Filmes de PPP, poli(pirrol) (PPI), poli(3-metiltiofeno) (P3MET) e os copolímeros, copoli(p-fenileno-pirrol) (CPPI) e copoli(p-fenileno-3-metiltiofeno) (CP3MET), foram preparados por voltametria cíciica (VC) e cronoamperometria (CR) em eletrodos de óxido de estanho dopado com índio sobre vidro (ITO) em uma solução não-aquosa de acetonitrila e perclorato de tetrabutilamônio contendo os monômeros a diferentes concentrações. Durante a síntese eletroquímica dos filmes de PPP, PPI, P3MET, CPPI e CP3MET, foi usado CaC12 como agente secante em uma caixa-seca para reduzir a umidade do ar. Um tratamento de secagem permitiu um melhor controle sobre o crescimento dos filmes e a presença de umidade na síntese eletroquímica foi correlacionada as diferentes respostas eletroquímicas dos filmes. Os valores de potencial de ionização (PI) e de afinidade eletrônica (AE) foram calculados através da medida dos potenciais no início das curvas voltamétricas direta e inversa, quando foram obtidos os potenciais de oxidação e redução (Eoxd\' e Ered\'). Os valores de energia de gap eletrônico (EgapE) ara esses filmes foram também obtidos por medidas eletroquímicas. Através dos espectros de absorção no UVVIS, foi possível se calcular a energia de gap óptico (EgapO) para os diferentes filmes poliméricos.
In this work we describe the electrochemical and optical aspects of a series of electrochemically synthesized blue-electroluminescent conjugated polymers. The materials employed here comprised poly(p-phenylene) (PPP), poly(pyrro1e) (PPI), poly(3-methylthiophene) (P3MET), poly(p-pheny1ene-pyrrole) (CPPI) copolymer and poly(p-phenylene3methyIthiophene) (CP3MET) copolymer. The films were electrochemically synthesized and deposited onto indium-tin-oxide covered glass (ITO) electrodes. The latter was carried out using either cyclic voltammetry (VC) or cronoamperometry (CR) in a acetonitrile nonaqueous medium containing tetrabutilammonium perclorate and different concentration of the respective monomers. As a further film quality control, the synthesis was carried out within a glove box containing a CaCI2 salt, which acted as drying agent. The latter procedure allowed us to correlate the amount of moisture present within the glove box with the electrochemical properties of the films. The ionization potential (PI) and the electronic affinity (AE) were calculated using the oxidation and reduction on-set potentials of the films (Eoxd\' e Ered\'). The electronic gap (EgapE)d the optical gap energies were calculated using electrochemical and UV-VIS. spectroscopy respectively.

The recent application of semiconductor materials, such as GaN, to power electronics has led to the development of a new generation of devices, which promise lower losses, higher operating frequencies and reductions in equipment size. The aim of this research is to study the capabilities of emerging GaN power devices, to understand their advantages, drawbacks, the challenges of their implementation and their potential impact on the performance of power converters. The thesis starts by presenting the development of a simple model for the switching transients of a GaN cascode device under inductive load conditions. The model enables accurate predictions to be made of the switching losses and provides an understanding of the switching process and associated energy flows within the device. The model predictions are validated through experimental measurements. The model reveals the suitability of the cascode device to soft-switching converter topologies. Two GaN cascode transistors are characterised through experimental measurement of their switching parameters (switching speed and switching loss). The study confirms the limited effect of the driver voltage and gate resistance on the turn-off switching process of a cascode device. The performance of the GaN cascode devices is compared against state-of-the-art super junction Si transistors. The results confirm the feasibility of applying the GaN cascode devices in half and full-bridge circuits. Finally, GaN cascode transistors are used to implement a 270V - 28V, 1.5kW, 1 MHz phase-shifted full-bridge isolated converter demonstrating the use of the devices in soft-switching converters. Compared with a 100 kHz silicon counterpart, the magnetic component weight is reduced by 69% whilst achieving a similar efficiency of 91%.

Optical properties of Tl4In3GaSe8, Tl4InGa3Se8, Tl4In3GaS8, Tl2InGaS4 and Tl4InGa3S8 chain and layered crystals were studied by means of photoluminescence (PL) and transmission-reflection experiments. Several emission bands were observed in the PL spectra within the 475-800 nm wavelength region. The results of the temperature- and excitation intensity-dependent PL measurements in 15-300 K and 0.13×
10-3-110.34 W cm-2 ranges, respectively, suggested that the observed bands were originated from the recombination of electrons with the holes by realization of donor-acceptor or free-to-bound type transitions. Transmission-reflection measurements in the wavelength range of 400-1100 nm revealed the values of indirect and direct band gap energies of the crystals studied. By the temperature-dependent transmission measurements in 10-300 K range, the rates of change of the indirect band gap of the samples with temperature were found to be negative. The oscillator and dispersion energies, and zero-frequency refractive indices were determined by the analysis of the refractive index dispersion data using the Wemple&ndash
DiDomenico single-effective-oscillator model. Furthermore, the structural parameters of all crystals were defined by the analysis of X-ray powder diffraction data. The determination of the compositional parameters of the studied crystals was done by energy dispersive spectral analysis experiments.

Organic semiconductors are a new key technology for large-area and flexible thin-film electronics. They are deposited as thin films (sub-nanometer to micrometer) on large-area substrates. The technologically most advanced applications are organic light emitting diodes (OLEDs) and organic photovoltaics (OPV). For the improvement of performance and efficiency, correct modeling of the electronic processes in the devices is essential. Reliable characterization and validation of the electronic properties of the materials is simultaneously required for the successful optimization of devices. Furthermore, understanding the relations between material structures and their key characteristics opens the path for innovative material and device design. In this thesis, two material characterization methods are developed, respectively refined and applied: a novel technique for measuring the charge carrier mobility μ and a way to determine the ionization energy IE or the electron affinity EA of an organic semiconductor. For the mobility measurements, a new evaluation approach for space-charge limited current (SCLC) measurements in single carrier devices is developed. It is based on a layer thickness variation of the material under investigation. In the \"potential mapping\" (POEM) approach, the voltage as a function of the device thickness V(d) at a given current density is shown to coincide with the spatial distribution of the electric potential V(x) in the thickest device. On this basis, the mobility is directly obtained as function of the electric field F and the charge carrier density n. The evaluation is model-free, i.e. a model for μ(F, n) to fit the measurement data is not required, and the measurement is independent of a possible injection barrier or potential drop at non-optimal contacts. The obtained μ(F, n) function describes the effective average mobility of free and trapped charge carriers. This approach realistically describes charge transport in energetically disordered materials, where a clear differentiation between trapped and free charges is impossible or arbitrary. The measurement of IE and EA is performed by characterizing solar cells at varying temperature T. In suitably designed devices based on a bulk heterojunction (BHJ), the open-circuit voltage Voc is a linear function of T with negative slope in the whole measured range down to 180K. The extrapolation to temperature zero V0 = Voc(T → 0K) is confirmed to equal the effective gap Egeff, i.e. the difference between the EA of the acceptor and the IE of the donor. The successive variation of different components of the devices and testing their influence on V0 verifies the relation V0 = Egeff. On this basis, the IE or EA of a material can be determined in a BHJ with a material where the complementary value is known. The measurement is applied to a number of material combinations, confirming, refining, and complementing previously reported values from ultraviolet photo electron spectroscopy (UPS) and inverse photo electron spectroscopy (IPES). These measurements are applied to small molecule organic semiconductors, including mixed layers. In blends of zinc-phthalocyanine (ZnPc) and C60, the hole mobility is found to be thermally and field activated, as well as increasing with charge density. Varying the mixing ratio, the hole mobility is found to increase with increasing ZnPc content, while the effective gap stays unchanged. A number of further materials and material blends are characterized with respect to hole and electron mobility and the effective gap, including highly diluted donor blends, which have been little investigated before. In all materials, a pronounced field activation of the mobility is observed. The results enable an improved detailed description of the working principle of organic solar cells and support the future design of highly efficient and optimized devices
Organische Halbleiter sind eine neue Schlüsseltechnologie für großflächige und flexible Dünnschichtelektronik. Sie werden als dünne Materialschichten (Sub-Nanometer bis Mikrometer) auf großflächige Substrate aufgebracht. Die technologisch am weitesten fortgeschrittenen Anwendungen sind organische Leuchtdioden (OLEDs) und organische Photovoltaik (OPV). Zur weiteren Steigerung von Leistungsfähigkeit und Effizienz ist die genaue Modellierung elektronischer Prozesse in den Bauteilen von grundlegender Bedeutung. Für die erfolgreiche Optimierung von Bauteilen ist eine zuverlässige Charakterisierung und Validierung der elektronischen Materialeigenschaften gleichermaßen erforderlich. Außerdem eröffnet das Verständnis der Zusammenhänge zwischen Materialstruktur und -eigenschaften einen Weg für innovative Material- und Bauteilentwicklung. Im Rahmen dieser Dissertation werden zwei Methoden für die Materialcharakterisierung entwickelt, verfeinert und angewandt: eine neuartige Methode zur Messung der Ladungsträgerbeweglichkeit μ und eine Möglichkeit zur Bestimmung der Ionisierungsenergie IE oder der Elektronenaffinität EA eines organischen Halbleiters. Für die Beweglichkeitsmessungen wird eine neue Auswertungsmethode für raumladungsbegrenzte Ströme (SCLC) in unipolaren Bauteilen entwickelt. Sie basiert auf einer Schichtdickenvariation des zu charakterisierenden Materials. In einem Ansatz zur räumlichen Abbildung des elektrischen Potentials (\"potential mapping\", POEM) wird gezeigt, dass das elektrische Potential als Funktion der Schichtdicke V(d) bei einer gegebenen Stromdichte dem räumlichen Verlauf des elektrischen Potentials V(x) im dicksten Bauteil entspricht. Daraus kann die Beweglichkeit als Funktion des elektrischen Felds F und der Ladungsträgerdichte n berechnet werden. Die Auswertung ist modellfrei, d.h. ein Modell zum Angleichen der Messdaten ist für die Berechnung von μ(F, n) nicht erforderlich. Die Messung ist außerdem unabhängig von einer möglichen Injektionsbarriere oder einer Potentialstufe an nicht-idealen Kontakten. Die gemessene Funktion μ(F, n) beschreibt die effektive durchschnittliche Beweglichkeit aller freien und in Fallenzuständen gefangenen Ladungsträger. Dieser Zugang beschreibt den Ladungstransport in energetisch ungeordneten Materialien realistisch, wo eine klare Unterscheidung zwischen freien und Fallenzuständen nicht möglich oder willkürlich ist. Die Messung von IE und EA wird mithilfe temperaturabhängiger Messungen an Solarzellen durchgeführt. In geeigneten Bauteilen mit einem Mischschicht-Heteroübergang (\"bulk heterojunction\" BHJ) ist die Leerlaufspannung Voc im gesamten Messbereich oberhalb 180K eine linear fallende Funktion der Temperatur T. Es kann bestätigt werden, dass die Extrapolation zum Temperaturnullpunkt V0 = Voc(T → 0K) mit der effektiven Energielücke Egeff , d.h. der Differenz zwischen EA des Akzeptor-Materials und IE des Donator-Materials, übereinstimmt. Die systematische schrittweise Variation einzelner Bestandteile der Solarzellen und die Überprüfung des Einflusses auf V0 bestätigen die Beziehung V0 = Egeff. Damit kann die IE oder EA eines Materials bestimmt werden, indem man es in einem BHJ mit einem Material kombiniert, dessen komplementärer Wert bekannt ist. Messungen per Ultraviolett-Photoelektronenspektroskopie (UPS) und inverser Photoelektronenspektroskopie (IPES) werden damit bestätigt, präzisiert und ergänzt. Die beiden entwickelten Messmethoden werden auf organische Halbleiter aus kleinen Molekülen einschließlich Mischschichten angewandt. In Mischschichten aus Zink-Phthalocyanin (ZnPc) und C60 wird eine Löcherbeweglichkeit gemessen, die sowohl thermisch als auch feld- und ladungsträgerdichteaktiviert ist. Wenn das Mischverhältnis variiert wird, steigt die Löcherbeweglichkeit mit zunehmendem ZnPc-Anteil, während die effektive Energielücke unverändert bleibt. Verschiedene weitere Materialien und Materialmischungen werden hinsichtlich Löcher- und Elektronenbeweglichkeit sowie ihrer Energielücke charakterisiert, einschließlich bisher wenig untersuchter hochverdünnter Donator-Systeme. In allen Materialien wird eine deutliche Feldaktivierung der Beweglichkeit beobachtet. Die Ergebnisse ermöglichen eine verbesserte Beschreibung der detaillierten Funktionsweise organischer Solarzellen und unterstützen die künftige Entwicklung hocheffizienter und optimierter Bauteile

Orientador: Prof. Dr. Jeverson Teodoro Arantes Junior
Tese (doutorado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, Santo André, 2018.
Investigamos, sistematicamente, as propriedades estruturais e eletrônicas do óxido de zinco nanoporoso sob tração e compressão biaxial utilizando cálculos de primeiros princípios baseados na Teoria do Funcional da Densidade. O sistema apresenta uma alta concentração de nanoporos lineares orientados nas direções cristalográcas [0001] e [01-10], bem como um lme no nanoporoso. Para compressões maiores do que 4% com relação ao parâmetro de rede, foi observada uma distorção estrutural nas regiões menos densas do material poroso, mostrando uma tendência à mudança de fase localizada. O coe- ciente de Poisson calculado dos nanoporos orientados na direção [0001] foi negativo. Isto signica que quando o material poroso foi tracionado, expandiu-se transversalmente. Já quando comprimido, o material contraiuse na direção transversal. Os materiais que possuem esta característica são conhecidos como materiais auxéticos. Nossos resultados mostram que o valor do gap de energia foi modulado pelas deformações biaxiais com uma tendência oposta ao bulk. A densidade dos estados eletrônicos conrmou nossas observações. A tendência estrutural inversa da superfície dos nanoporos é o principal mecanismo para o comportamento inverso do gap sob compressão e tração. Dentro do nosso conhecimento, este é o primeiro reporte de um comportamento inverso do gap de energia de estruturas de ZnO sob compressão e tração biaxial. Nossos resultados sugerem que a nanoporosidade, conjuntamente com tra- ção e compressão biaxial, podem ser empregadas como um método dentro da engenharia de gap para customizar materiais funcionais que requerem controle da atividade eletrônica.
This work investigated, systematically, the structural and electronic properties of nanoporous zinc oxide, under biaxial strain, through rst-principles methods, based on total energy ab initio calculations using Density Functional Theory. The system was in a massive nanopore concentration regime. We studied linear pores in [0001] and [01-10] direction and a porous thin lm. Using a biaxial tension above 4% of the ZnO bulk lattice parameter, we observed a distortion resulting in a local phase change region in the material's structure. The calculated Poisson's coecient was negative for the [0001] pore. When stretched, they become thicker in the perpendicular direction to the applied force. These materials are known as auxetic. Our results show that the energy band gap value is tuned by the strain with an uncommon opposite trend related to the bulk. The density of electronic states conrmed the energy gap modulation. The structural inverse trend of nanopores surface is the principal mechanism for gap inverse behavior under compressive and tensile strain. From the best of our knowledge, this is the rst report about opposite Egap trend in strained nanopores. Our results suggest that nanoporosity and biaxial strain could be employed as a method within the band gap engineering for tailored functional matexi rials that require control of the electronic activity.

Dans cette thèse, nous nous sommes intéressés aux propriétés semi-conductrices des oxydes formés sur les alliages base nickel en milieu primaire des REP. L'objectif étant de mettre en évidence les effets de la pression partielle en hydrogène, de la nature de l'alliage et de l'état de surface sur les types de semi-conductions et les énergies de bandes interdites. La technique photoélectrochimique a été employée pour caractériser ces propriétés semi-conductrices. D'autres techniques de caractérisation complémentaires ont été également utilisées telles que le MEB-FEG, la diffraction des rayons X, la spectroscopie Raman et l'XPS. Les essais de corrosion ont été effectués en milieu primaire simulé (autoclave en titane, température 325°C, durée 500 heures). Des échantillons d'alliages 600 et 690 de polissage 1 µm diamant, ont été oxydés aux P(H2) < 0,01 ; 0,3 et 6,5 bar. L'état de surface ne concernait que l'alliage 600 oxydé à P(H2) = 0,3 bar. Nous avons utilisé une nouvelle méthode d'ajustement numérique pour la détermination des gaps. Les résultats obtenus montrent que seule la pression d'hydrogène affecte le type de semi-conduction des oxydes présentés par les hautes énergies, il passe du type-n (P(H2) < 0,01) en type proche de l'isolant (P(H2) = 0,3 et 6,5 bar). Un comportement du type-n a été enregistré à basse énergie quels que soit les paramètres d'étude. Les énergies de bande interdites des oxydes NiO, Cr2O3 et NiFe2O4 ont été révélées.

Les proprietes des composes rnisb sont etudiees sous plusieurs aspects : magnetisme, transport, structure electronique. Les composes hexagonaux avec une terre rare legere sont metalliques, les phases cubiques du type semi-heusler avec les terres rares lourdes sont des semiconducteurs a faible gap. Des phenomenes de magnetoresistance geante sont observes a basse temperature, d'autant plus importants que la densite de porteurs est plus faible. Ils sont expliques par la polarisation par le moment de la couche 4f des niveaux d'impuretes situes dans le gap du semiconducteur. Le champ cristallin, ainsi que l'ordre magnetique a basse temperature, ont ete etudies par diffusion (diffraction) de neutrons. Certaines proprietes magnetiques (absence d'ordre magnetique avec le pr, structures af dans le second groupe, orientation des moments) ont pu etre expliquees au moins qualitativement. Cenisb est un compose de type kondo avec une temperature de kondo de l'ordre de 8k. Des mesures de photoemission ont permis de preciser la structure des bandes de valence de ces composes, en accord avec des calculs de structure electronique. Par photoemission resonante dans tbnisb et gdcu, differents canaux de resonance ont ete resolus en fonction de l'energie, qui dependent de la structure des multiples et de la configuration des niveaux excites.

Mestrado em Física Aplicada
O estudo dos nitretos, de elementos do grupo III, semicondutores transparentes no visível, tem registado nos últimos anos um enorme avanço, dado o crescente interesse pelos mesmos, quer na forma de slmes finos, quer em monocristais. Estes materiais apresentam-se como fortes candidatos para servirem de base a componentes de semicondutores a operarem na zona da radiação electromagnética do azul e ultra-violeta, zonas estas não abrangidas pelos semicondutores convencio&is. Assim espera-se um enorme impacto destes materiais na electrónica e optoelectrónica, em aplicações gráficas e de memórias de alta densidade. As suas fortes ligações atómicas torna- -os também candidatos para aplicações em equipamentos de elevada potência e elevada temperatura, sendo também resistentes à corrosão. Neste trabalho efectuou-se o estudo das emissões observadas sensivelmente a meio da banda de emissões proibidas (adiante designado como "gap") em epicamadas de GaN crescido sobre carboneto de silício e safira. A caracterização das amostras foi realizada utilizando como técnicas experimentais a espectroscopia em estado estacionário e resolvido no tempo, e catodoluminescência. A dependência com a temperatura da intensidade e os tempos de vida das emissões em estudo, permitiram estabelecer modelos de recombinação dos diferentes centros ópticos.

Currently, in the United States, on-road vehicles are primarily powered by petroleum fuels (gasoline and diesel). These vehicles have caused serious climate change effects from emissions of greenhouse gas (GHG) and health and environmental impacts from criteria air pollutant (CAP). The recent success of shale gas development has brought industry interest in using natural gas to power on-road vehicles. In addition to low costs and wide availability of this national fuel source, natural gas is a common feedstock to produce alternative fuels. The question arises of whether using natural gas for transportation could help or hinder the environment. In this dissertation, I study the economic and environmental effects of a wide range of natural gas fuel pathways for a selection of light duty (LDV) and medium and heavy duty (MHDV) vehicle types. I choose to focus on two environmental metrics: GHGs and CAPs emitted over the life cycle of each potential pathway for natural gas use. First in Chapters 2 and 3, I use life-cycle analysis to understand the emissions of GHGs from different natural gas pathway for LDVs and MHDVs. Then in Chapter 4 I focus on the CAP emissions from these vehicles. Overall, I find that none of the natural gas pathways eliminate life cycle air emissions. In fact, only a few pathways reduce life cycle GHG emissions and/or life cycle air pollution damages compared to baseline petroleum fuels (gasoline for light-duty vehicles (LDVs) and diesel for heavy-duty vehicles (HDVs)). For the cases of light duty vehicles (LDVs) and transit buses, battery electric vehicles (BEVs) powered by natural gas-based electricity provide significant reduction in life cycle GHG emissions and life cycle air pollution damages (for almost all counties) compared to the baseline petroleum fuels. However, the actual electricity that charges BEVs may not be natural gas-based electricity in most parts of the U.S. When powered by U.S. grid electricity (using average emission factors for 2010 and 2014), BEVs reduce life cycle GHG emissions to a lesser extent but increase life cycle air pollution damages significantly. Compressed natural gas (CNG), while reducing GHG emissions and CAP emissions (except CO) at tailpipe, are more likely to increase life cycle GHG emissions and increase life cycle air pollution damages in the majority of U.S. counties. For heavy-duty trucks, CNG sparking-ignition (SI) trucks and liquefied natural gas (LNG) high-pressure direct ignition (HPDI) trucks have mixed environmental impacts. While they are unlikely to reduce life cycle GHG emissions compared to diesel, they reduce life cycle air pollution damages in 76-99% of U.S. counties for local-haul tractor-trailers and in 32-71% of U.S. counties for long-haul tractor-trailers. In Chapters 5 and 6, I examine the economic impacts of natural gas fuel pathways for two vehicle types, tractor-trailers and transit buses. I study the economic feasibility of a national natural gas refueling infrastructure for long-haul trucks in U.S., which is a prerequisite for natural gas tractor-trailers. I find that a transition to natural gas fuels in long-haul trucks is more expensive when the shares of natural gas trucks are below 5% because of low refueling demands and over-capacity of the refueling infrastructure to ensure network coverage. At higher shares of natural gas trucks, both the total refueling capacity and the net economic benefits of the national refueling infrastructure increase almost linearly as adoption increases. Finally, in Chapter 6, I provide an economic-technology assessment for transit buses by considering both life cycle ownership costs and life cycle social costs due to GHG emissions and CAP emissions. Transit buses are early adopters of alternative fuel technologies because of funding supports and operation characteristics (such as high fuel consumption and private refueling infrastructure). I find that the availability of external funding is crucial for transit agencies to adopt any alternative fuel option. Without external funding, only rapid-charging battery electric buses (BEBs) have lower ownership & social costs than conventional diesel buses. When external funding is available to reduce bus purchase costs by 80%, BEBs become much more cost-effective. In this case, life cycle ownership and social costs of BEBs are 37-43% lower than conventional diesel buses. Including life cycle social costs does not change the ranking of alternative fuel options. The findings in this dissertation suggest different strategies of using natural gas for different vehicle markets. Natural gas is best used in electric power generation than to produce gaseous or liquid fuels for powering on-road LDVs. The use of CNG and LNG for heavy-duty trucks may continue as there are less alternative fuel options but issues such as methane leakage should be addressed to avoid important climate change effect. Finally, natural gas-based transportation fuels can at best partially mitigate climate change or air pollution damages, so other mitigation strategies in the transportation sector are ultimately needed to achieve sustainable transportation.

Questa tesi ha come obiettivo quello di misurare la dipendenza spettrale di alcune proprietà ottiche, come trasmittanza e riflettanza, al fine di ricavare l’energy gap di film sottili costituiti da nanocrystalline silicon oxynitride (nc-SiOxNy) per applicazioni in celle solari HIT (Heterojunction Intrinsic Thin layer). Questi campioni sono stati depositati presso l’Università di Konstanz (Germania) tramite tecnica PECVD (Plasma-Enhanced Chemical Vapor Deposition). Questo materiale risulta ancora poco conosciuto per quanto riguarda le proprietà optoelettroniche e potrebbe presentare una valida alternativa a silicio amorfo (a-Si) e ossido di silicio idrogenato amorfo (a-SiOx:H) che sono attualmente utilizzati in questo campo. Le misure sono state effettuate presso i laboratori del Dipartimento di Fisica e Astronomia, settore di Fisica della Materia, dell’Università di Bologna. I risultati ottenuti mostrano che i campioni che non hanno subito alcun trattamento termico (annealing) presentano un energy gap che cresce linearmente rispetto alla diluizione di protossido di azoto in percentuale. Nei campioni analizzati sottoposto ad annealing a 800°C si è osservato un aumento dell’Eg dopo il trattamento. Un risultato ottimale consiste in un gap energetico maggiore di quello del silicio amorfo (a-Si) e del silicio amorfo idrogenato (a-Si:H), attualmente utilizzati in questa tipologia di celle, per evitare che questo layer assorba la luce solare che deve invece essere trasmessa al silicio sottostante. Per questo motivo i valori ottenuti risultano molto promettenti per future applicazioni fotovoltaiche.

Nous etudions la transition superfluide du modele boson-fermion ou les bosons sont des paires d'electrons initialement localises et les fermions des electrons itinerants. Lorsque l'on s'approche de la transition, les bosons deviennent quasi-libres alors qu'il apparait un pseudo-gap dans la densite d'etats fermionique

Ce travail de these est consacre a l'elaboration et l'etude des proprietes electroniques de la phase quasicristalline alpdre. La recherche d'une procedure d'elaboration nous a permis d'obtenir des echantillons de phase icosaedrique pure de tres grande qualite structurale. L'alliage quasicristallin alpdre presente des proprietes de transport exceptionnelles pour un alliage constitue uniquement de metaux. En particulier, nous avons confirme que la valeur de resistivite de certains echantillons de i-alpdre peut atteindre #4#37 1 cm, ce qui est 10#6 fois superieure a celle des metaux standards, et 10#3 fois superieure a celles des amorphes metalliques. Les valeurs de resistivite de ces echantillons et leur dependance en temperature semblent s'approcher de celles des systemes ayant franchi la transition metal-isolant. Toutefois, il existe de fortes variations des proprietes de transport entre differents echantillons de la phase i-alpdre. D'autres echantillons ont montre des proprietes electroniques semblables a celles des phases icosaedriques bien connues i-alpdmn et i-alcufe qui se trouvent du cote metallique d'une transition metal-isolant. Nous avons etabli que ces disparites de proprietes de transport sont liees a des variations de composition et de qualite structurale. A l'inverse des metaux, meilleure est la qualite structurale plus la resistivite des echantillons est elevee ce qui exclu la possibilite d'une transition metal-isolant par le desordre (anderson) dans cette phase. D'autre part, nos mesures de densite d'etats electroniques permettent d'etablir la presence d'un pseudogap au niveau de fermi mais pas de gap reel comme dans les semi-conducteurs. On a donc affaire a un type de transport nouveau qui n'obeit pas aux lois connues dans les materiaux classiques (amorphes, semi-conducteurs, metaux). Un modele de transport par sauts entre etats critiques pourrait expliquer une transition metal-isolant dans ces structures ordonnees sans gap. Nous avons entrepris, par ailleurs, des mesures d'energie de surface de couches minces quasicristallines en collaboration avec l'industrie de revetements aps. Ces mesures, nous ont permis d'etablir que les couches minces quasicristallines ont une faible mouillabilite

Ce memoire presente une etude experimentale d'un compose organique isolant ayant des proprietes magnetiques unidimensionnelles (1d): cu#2(c#5h#1#2n#2)#2cl#4. C'est un systeme antiferromagnetique de heisenberg s=1/2 en echelle de spins. Les interactions d'echanges entre les electrons non apparies des ions cu#2#+ forment une structure magnetique en echelle que l'on peut decrire par deux parametres d'echanges, j entre les barreaux et j le long des deux chaines. Comme toutes les echelles de spin-1/2 ayant un nombre pair de chaines couplees, ce systeme a un gap d'energie dans le spectre des excitations. Les proprietes de l'etat fondamental et, dans une certaine limite des etats excites, sont alors similaires a celles des chaines de haldane (s=1). A contrario les echelles comportant un nombre impair de chaines sont critiques (sans gap) et appartiennent a la meme classe d'universalite que les chaines de spin-1/2 dont la solution est donnee par l'ansatz de bethe. Cette these presente une etude assez complete des proprietes thermodynamiques et dynamiques de ce compose. Les mesures thermodynamiques ou statiques reposent sur l'utilisation de magnetometres squid ou, pour les champs magnetiques intenses, d'oscillateurs torsionnels a haute resolution. Les techniques de resonance electronique de spin (rpe) dans la gamme micro-ondes et de resonance magnetique nucleaire sur le proton ont ete utilisees pour etudier les proprietes dynamiques liees aux fonctions de correlations telle que la largeur de raie rpe ou le temps de relaxation nucleaire spin-reseau t#1. Nous avons determine l'ensemble des parametres essentiels lies au magnetisme de ce compose: cu#2(c#5h#1#2n#2)#2cl#4 est decrit par un hamiltonien de heisenberg dont les interactions d'echanges forment une echelle de spins dans la limite de couplage fort: j 13. 2k et j 2. 5k. Le gap d'energie entre l'etat fondamental non-magnetique s=0 et les etats excites triplets (s=1) est 10. 5k

Les niveaux des defauts dans la bande interdite du semiconducteur sont etudies ainsi que les phenomenes de transport et les proprietes optiques. On note des effets remarquables de passivation et de modification des defauts par hydrogenation

L'etude des echantillons massifs de cuin::(1-x)ga::(x)se::(2) de type p permet de mettre au point la solution electrolytique acide en presence du couple redix v**(2+/3+). Etude des positions energetiques des bandes par mesures capacitives. Etude de la variation de la bande interdite en fonction de x et mesure des longueurs de diffusion par l'evolution du photocourant en fonction du potentiel. Etude des proprietes optiques et electroniques des couches minces cugase::(2) de type p en fonction des ecarts a la stoechiometrie

La technique de diffusion inelastique des neutrons a ete utilisee pour caracteriser le spectre des excitations magnetiques de basse energie dans les composes a electrons fortement correles cenisn, ce#1#-#xla#xru#2si#2 et ceru#2ge#2. Cenisn est un compose kondo semimetallique dont le spectre des excitations magnetiques est compose de deux modes d'energie 2 et 4 mev et respectivement piques au centre et bord de zone de brillouin. L'application d'un champ magnetique met en evidence la nature differente de ces modes : le premier se deplace vers les plus hautes energies et la reponse du second s'elargit. Les modeles de gap d'hybridation particularises pour ce compose permettent de relier le mode a 4 mev aux proprietes macroscopiques observees. La dynamique des moments magnetiques pres d'une instabilite magnetique a ete etudiee dans le compose ce#1##xla#xru#2si#2 avec x = 0. 075. De facon surprenante, un ordre magnetique non conventionnel a ete mis en evidence (m = 0. 02 #b et t#n = 1. 8 k). La dynamique de spin par rapport au compose pur a ete reliee, grace a la theorie des fluctuations de spin de moriya, aux mesures macroscopiques. L'application d'un champ magnetique sur le compose ceru#2si#2 met en evidence le changement de la reponse dynamique du systeme de part et d'autre de la transition pseudometamagnetique. La reponse quasielastique et a courte portee a bas champ est remplacee par un ordre statique a longue distance en champ fort (h = 12 t). Dans ce contexte, la phase antiferromagnetique du compose ferromagnetique ceru#2ge#2 a ete caracterisee. Il existe alors une analogie entre ce compose sous sa temperature de curie et ceru#2si#2 au dessus du champ metamagnetique.

Mise en évidence par mesures de conductivité électrique des transformations structurelles à caractère relaxationnel induites par traitement thermique. Etude des variations de la bande interdite optique. Etude du rôle privilégié de certains centres dans les phénomènes de transport

Nous presentons les premiers resultats obtenus avec un dispositif experimental permettant de changer la contrainte uniaxiale continument a tres basse temperature. Le principe de l'appareil consiste a controler la pression d'helium appliquee sur un soufflet metallique connecte thermiquement a la boite de melange d'un refrigerateur a dilution. Nous etudions l'effet de la contrainte uniaxiale, appliquee selon l'axe c du compose tetragonal uru#2si#2. Nous trouvons que la temperature de transition supraconductrice t#c varie de facon parabolique en fonction de la contrainte #c avec une pente de 76 mk/kbar a #c = 0 kbar et une pente nulle a 6. 5 kbar. La temperature de transition antiferromagnetique t#n varie lineairement en fonction de la contrainte avec une pente egale a 32 mk/kbar. Nous rapportons les premieres mesures de l'evolution du gap des excitations de la phase antiferromagnetique en fonction de la contrainte uniaxiale selon l'axe c. Il decroit lineairement avec une pente de 0. 63 k/kbar. Grace aux mesures de champ critique, nous donnons la premiere estimation de la croissance de la masse effective avec la contrainte selon l'axe c, m*(6. 5 kbar) = 1. 07 m*(0 kbar). Pour le compose hexagonal upt#3, nous confirmons que la temperature de transition supraconductrice t#+#c decroit, d'abord avec une pente de 14. 71. 5 mk/kbar, pour une contrainte appliquee suivant l'axe c inferieure a 2 kbar puis decroit, avec une pente de 5. 20. 7 mk/kbar, pour des contraintes superieures. En variant de 0 a 8. 4 kbar la contrainte #a appliquee selon l'axe a, nous trouvons que la temperature t#+#c decroit regulierement avec une pente de 2. 00. 7 mk/kbar. A partir de l'evaluation du coefficient a de la loi = #0+at#2 et de la pente du second champ critique a bas champ, nous trouvons que la masse effective augmente avec la contrainte suivant l'axe c et diminue avec la contrainte suivant l'axe a:m*(#c = 6. 5 kbar) = 1. 26 m*(#c = 0 kbar) ; m*(#a = 6. 5 kbar) = 0. 86 m*(#a = 0 kbar).

Les transistors a effet champ a contact metal-semiconducteur, non passives, realises sur arseniure de gallium sont sujet a une degradation progressive de leurs performances statiques et dynamiques aux hyperfrequences. Ce defaut de fonctionnement est en parti attribue aux surfaces d'arseniure de gallium situees de part et d'autres de la grille. La stabilisation des composants requiert donc de la passivation de ces zones grace a des materiaux de haute qualite dielectrique realisant une interface stable avec gaas. Dans cette optique, les proprietes physico-chimiques et electriques de films de silice et de nitrure de silicium deposes en phase vapeur assiste par plasma sont etudiees en fonction du rapport des debits des gaz employe, de la temperature du substrat, de la puissance et de la frequence de l'excitation du plasma. . . Cette approche systematique permet de determiner des parametres de depot qui donnent des films ayant tres bonnes proprietes electriques: une resistivite de 10**(14) a 10**(16) ohm. Cm et un champ de claquage superieur a 10**(6) v/cm sont ainsi obtenus apres un recuit dont on soulignera l'importance. Apres mise au point d'une preparation de surface avant depot, la densite d'etats sur la bande interdite du semiconducteur a l'interface gaas/si::(3)n::(4) presente un minimum de 7. 10**(11) ev**(-2). Les depots ainsi optimalises sont utilises pour la passivation des transistors mesfet gaas. Le recouvrement d'un composant par une couche mince introduit une modification de ses caracteristiques statiques; celle-ci est expliquee conjointement par un effet piezo-electrique et par un effet de surface inherent au mode de depot. Suivant les resultats obtenus en tests de fiabilite, le nitrure de silicium s'avere etre le meilleur choix pour reussir la passivation du composant. De plus, des pretraitements par plasma et une meilleure adaptation du procede de fabrication au mode de passivation sont proposes pour ameliorer encore la stabilite a long terme des caracteristiques des transistors

Etude de monocristaux de eumo::(6)s::(8) et d'echantillons frittes de yb::(1,2-x)eu::(x)mo::(6)s::(8) basee sur des mesures de transport sous pression et sous champ magnetique, des mesures de la susceptibilite magnetique et des mesures rpe; mise au point d'un dispositif automatise de mesures de transport. Correlations entre la temperature de transition structurale, la remontee de la resistivite a basse temperature et la transition supraconductrice sous pression; effets de la composition des echantillons frittes. Mise en evidence d'une valeur tres elevee du coefficient de chaleur massique electronique. Discussion des proprietes anormales dans le cadre d'un modele de melange de phases triclinique et rhomboedrique et d'un modele de supraconductivite propre

碩士
中原大學
應用物理學系
82
A detail fitting method of the metastable semiconductors alloys presented.Alloy composition and temperature are simul- taneously considered together by combined empirical formula of composition and modified temperature terms. This fitting method is based on the least-square technique scheme,and therefore, necessitates known values of the experi- mental data for the related binaries at two ends (for composi- tion;X=0 and X=1) of ternary alloy,which taken as the input data during performing iteration processes.One can decide quantitily that the resultant value of the bowing parameter for band gap is temperature dependence also. If one hopes to study temperature influences on the fermi leevel,it is necessary to calculate the ratio of effective mass of hole and electron at the band edges. In conclusion,it found that temperature influence on the half of the energy band gap and the fermi level for undoped semiconductors are similar to each other.

碩士
國立臺灣大學
材料科學與工程學研究所
100
In this thesis, six donor-acceptor low band gap conjugated copolymers containing thienopyrazine derivative as acceptor unit were designed and synthesized via Suzuki coupling and Stille coupling. Various donors, based on fluorene and thiophene derivatives, with different chemical structures were employed to investigate the effects of coplanarity, bridging atom and strong electron withdrawing group on the optical absorptions, the electronic band structures and the stability of the copolymers. All the copolymers synthesized showed bimodal absorption spectra with small band gap (< 2 eV). Comparing to the counterparts containing fluorene derivatives, the copolymers with thiophene based donors exhibited relative reddish optical absorptions, smaller band gaps and better photochemical stability. Considering the thiophene based copolymers, the better coplanarity led to stronger optical absorption at long wavelengths corresponding to enhanced intra-charge transfer as well as better stability. The introduction of cyclopentadithiophene with fused ring structures would further lower the band gap. The lowest unoccupied molecular orbital (LUMO) was similar for all the copolymers, which should be determined by the thienopyrazine unit. The highest occupied molecular orbital (HOMO) would be significantly elevated by improving the coplanarity. The introduction of strong electron withdrawing cyano group on thiophene could significantly lower the HOMO while retaining low optical band gap.

The focus of this dissertation is on the dynamics of electromagnetic systems for energy harvesting and filtering applications. The inclusion of magnets into systems generates nonlinearity due to the nature of electromagnetic interactions. In this work, magnetic nonlinearity manifests in tip interactions for cantilever beams, coupling effects for electromagnetic transduction, and bistable potential wells for a two beam system. These electromagnetic interactions are used to add non-contact coupling effects for the creation of bistable oscillators or arrays of coupled beams for energy filtering.

Nonlinearity at the tip of cantilever beams acts to change the dynamic and static behavior of the system. In this dissertation, these interactions are analyzed both with and without the nonlinear tip interactions. A linear analysis of the system without the tip interaction first provides insight into the shifting frequencies of the first four natural oscillation modes when considering a rigid body tip mass with rotational inertia and a center of mass that is offset from the tip of the beam. Then, the characterization of the nonlinearities in the beam stiffness and magnetic interaction provide insight into the static and dynamic behavior of the beam. The analytical and numerical investigations, using Rayleigh-Ritz methods and an assumed static deflection, are shown to be consistent with experimental tests. These methods provide a framework for theoretically establishing nonlinear static modes and small-amplitude linear modes that are consistent with physical behavior.

In electromagnetic coupling, the role of nonlinearity can have a detrimental or beneficial effect on energy harvesting. This work includes an investigation of the response of an energy harvester that uses electromagnetic induction to convert ambient vibration into electrical energy. The system's response behavior with linear coupling or a physically motivated form of nonlinear coupling is compared with single and multi-frequency base excitation. This analysis is performed with combined theoretical and numerical studies.

The ability of magnets to add nonlinearity to a system allows for the expansion of the phenomenological behavior of said system and potential advantages and disadvantages for energy harvesting. This work studies a two beam system made up of carbon fiber cantilever beams and attached magnetic tip masses with a focus on energy harvesting potential. Numerical and experimental investigations reveal an array of phenomena from static bifurcations, chaotic oscillations, and sub-harmonic orbits. These features are used to highlight the harvesting prospects for a similarly coupled system.

Beyond nonlinearity, the non-contacting coupling effects of magnets allow for the hypothetical creation of energy filtering systems. In this work, the band structure of a two dimensional lattice of oscillating beams with magnetic tip masses is explored. The focus of the wave propagation analysis is primarily on regions in the band structure where propagation does not occur for the infinite construction of the system. These band gaps are created in this system of 2 x 2 repeating unit cells by periodically varying the mass properties and, for certain configurations, the frequency band gaps manifest in different size and band location. Uncertainty in these regions is analyzed using potential variations associated with specific physical parameters in order to elucidate their influence on the band gap regions. Boundary effects and damping are also investigated for a finite-dimensional array, revealing an erosion of band gaps that could limit the expected functionality.

Dissertation

This work presents a spectroscopic and theoretical study of several energy materials using synchrotron-based techniques. Two classes of materials are studied: solids that have reported photocatalytic properties, and lithium compounds that are thought to form during the cycling of modern battery electrodes. An overview of synchrotron soft X-ray spectroscopic techniques is presented, along with the theory and procedures associated with performing such measurements. These measurements are compared to density functional theory (DFT) calculations, as implemented by the WIEN2k package, along with a description of the DFT method. Calculated electronic structure is shown to be a useful aid in interpreting the results of X-ray emission and X-ray near-edge absorption measurements (XES and XANES), allowing conclusions about the physical structure and properties of the materials to be reached. Two photocatalytic systems are outlined, the first of which is a solid solution of GaN and ZnO (GaN:ZnO) that exhibits an unexpected reduction in band gap. By carefully comparing common hybridized features from O, N and Zn core emission lines, a binding energy picture of the valence and conduction bands of GaN:ZnO is constructed, allowing its band gap reduction to be described as a consequence of heterojunctions between predominantly GaN and ZnO regions within the solid solution. This description attempts to resolve controversy in the literature regarding the origin of the band gap reduction, as well as to rule out a hypothesized oxynitride superlattice structure as the explanation. The second photocatalytic system studied is a carbon nitride derivative, poly(triazine imide) (PTI) that displays high crystallinity and that could be very inexpensive to produce due to its elemental abundance. Through resonant excitation, two inequivalent N sites in PTI can be probed by X-ray emission spectroscopy, indicating the material is not a conjugated polymer like other reported carbon nitrides. The band gap of the system is observed to decrease in response to disordered Li loading, an e ect that is con rmed by DFT calculation. Several potential disorder models of the Li loading of PTI are investigated with DFT force minimization in order to choose a structural candidate capable of producing calculated X-ray spectra that agree with our measurements. The presented lithium study attempts to use a modern soft X-ray absorption facility to characterize the Li surface by-products inherent to the charge-discharge cycling of a battery electrode. A survey of potential Li compounds was performed using Li K-edge XANES will be compared to DFT calculations and X-ray Raman Scattering measurements performed by collaborators in the future. Correlating measurements of the survey compounds with charge-cycled electrode measurements will be an area for future work.

Magister Scientiae - MSc
Solar energy generation arises as a result of direct conversion of sunlight into electricity a by solar cell; which is mainly made up of a semiconducting material incorporated into a system. It is emerging as one of the most reliable and cost efficient renewable energy sources. Within the solar field, organic bulk heterojunction photovoltaic cells have proved of being able to have a great impact in the future years; mainly due to the easy processability of the active layer and substrate, their cost effectiveness and above all, a good power conversion efficiency associated to the close 3-dimensional interpenetrating network that is generated from blending donor and acceptor semiconducting materials together in a bulk heterojunction active layer. In this research work, we therefore report on the study of a newly developed organic bulk heterojunction active layer based on a blend of a star-copolymer generation 1 poly(propylenethiophenoimine)-co-poly(ethylenedioxythiophene) (G1PPT-co-PEDOT) as donor material with N,N-diisopropylnaphthalene diimide (NDI) as acceptor material. Both materials were chemically synthesized. The synthesis of G1PPT-co-PEDOT started first by the functionalization of generation 1 poly(propyleneimine) tetramine, G1PPI into G1PPT by condensation reaction in the presence of 2-thiophene carboxaldehyde under Nitrogen gas followed by the copolymerization of G1PPT with ethylene dioxythiophene (EDOT) monomer in the presence of ammonium persulfate, (NH4)2S2O8 as oxidant. On the other hand, NDI was also synthesized via condensation reaction of 1,4,5,8-naphthalene tetracarboxylic dianhydride in the presence of two (2) equivalences of N,N-diisopropylamine at 110 oC overnight in DMF. Both materials were characterized using FT-IR, UV-Vis spectroscopy, Fluorescence spectroscopy, Voltammetry, HRSEM microscopy and XRD. Based on the cyclic voltammetry and UV-Vis results, we were able to calculate the HOMO, LUMO and band gap energy (Eg) values of both the donor and acceptor to be -4.03 eV, -6.287 eV and 2.25 eV for iii the donor G1PPT-co-PEDOT respectively and -4.302 eV, -7.572 eV and 3.27 eV for the acceptor respectively. From these results, the energy diagram for both donor and acceptor was drawn and it comes out that the separation between the HOMO of the donor and the LUMO of the acceptor ΔEg = 1.985 eV, the ideal value for a good donor-acceptor combination. Also the offset energy that is, the energy difference between the LUMO of the donor and the LUMO of the acceptor is 0.302 eV.

Organic semiconductors are a new key technology for large-area and flexible thin-film electronics. They are deposited as thin films (sub-nanometer to micrometer) on large-area substrates. The technologically most advanced applications are organic light emitting diodes (OLEDs) and organic photovoltaics (OPV). For the improvement of performance and efficiency, correct modeling of the electronic processes in the devices is essential. Reliable characterization and validation of the electronic properties of the materials is simultaneously required for the successful optimization of devices. Furthermore, understanding the relations between material structures and their key characteristics opens the path for innovative material and device design. In this thesis, two material characterization methods are developed, respectively refined and applied: a novel technique for measuring the charge carrier mobility μ and a way to determine the ionization energy IE or the electron affinity EA of an organic semiconductor. For the mobility measurements, a new evaluation approach for space-charge limited current (SCLC) measurements in single carrier devices is developed. It is based on a layer thickness variation of the material under investigation. In the \"potential mapping\" (POEM) approach, the voltage as a function of the device thickness V(d) at a given current density is shown to coincide with the spatial distribution of the electric potential V(x) in the thickest device. On this basis, the mobility is directly obtained as function of the electric field F and the charge carrier density n. The evaluation is model-free, i.e. a model for μ(F, n) to fit the measurement data is not required, and the measurement is independent of a possible injection barrier or potential drop at non-optimal contacts. The obtained μ(F, n) function describes the effective average mobility of free and trapped charge carriers. This approach realistically describes charge transport in energetically disordered materials, where a clear differentiation between trapped and free charges is impossible or arbitrary. The measurement of IE and EA is performed by characterizing solar cells at varying temperature T. In suitably designed devices based on a bulk heterojunction (BHJ), the open-circuit voltage Voc is a linear function of T with negative slope in the whole measured range down to 180K. The extrapolation to temperature zero V0 = Voc(T → 0K) is confirmed to equal the effective gap Egeff, i.e. the difference between the EA of the acceptor and the IE of the donor. The successive variation of different components of the devices and testing their influence on V0 verifies the relation V0 = Egeff. On this basis, the IE or EA of a material can be determined in a BHJ with a material where the complementary value is known. The measurement is applied to a number of material combinations, confirming, refining, and complementing previously reported values from ultraviolet photo electron spectroscopy (UPS) and inverse photo electron spectroscopy (IPES). These measurements are applied to small molecule organic semiconductors, including mixed layers. In blends of zinc-phthalocyanine (ZnPc) and C60, the hole mobility is found to be thermally and field activated, as well as increasing with charge density. Varying the mixing ratio, the hole mobility is found to increase with increasing ZnPc content, while the effective gap stays unchanged. A number of further materials and material blends are characterized with respect to hole and electron mobility and the effective gap, including highly diluted donor blends, which have been little investigated before. In all materials, a pronounced field activation of the mobility is observed. The results enable an improved detailed description of the working principle of organic solar cells and support the future design of highly efficient and optimized devices.:1. Introduction 2. Organic semiconductors and devices 2.1. Organic semiconductors 2.1.1. Conjugated π system 2.1.2. Small molecules and polymers 2.1.3. Disorder in amorphous materials 2.1.4. Polarons 2.1.5. Polaron hopping 2.1.6. Fermi-Dirac distribution and Fermi level 2.1.7. Quasi-Fermi levels 2.1.8. Trap states 2.1.9. Doping 2.1.10. Excitons 2.2. Interfaces and blend layers 2.2.1. Interface dipoles 2.2.2. Energy level bending 2.2.3. Injection from metal into semiconductor, and extraction 2.2.4. Excitons at interfaces 2.3. Charge transport and recombination in organic semiconductors 2.3.1. Drift transport 2.3.2. Charge carrier mobility 2.3.3. Thermally activated transport 2.3.4. Diffusion transport 2.3.5. Drift-diffusion transport 2.3.6. Space-charge limited current 2.3.7. Recombination 2.4. Mobility measurement 2.4.1. SCLC and TCLC 2.4.2. Time of flight 2.4.3. Organic field effect transistors 2.4.4. CELIV 2.5. Organic solar cells 2.5.1. Exciton diffusion towards the interface 2.5.2. Dissociation of CT states 2.5.3. CT recombination 2.5.4. Flat and bulk heterojunction 2.5.5. Transport layers 2.5.6. Thin film optics 2.5.7. Current-voltage characteristics and equivalent circuit 2.5.8. Solar cell efficiency 2.5.9. Limits of efficiency 2.5.10. Correct solar cell characterization 2.5.11. The \"O-Factor\" 3. Materials and experimental methods 3.1. Materials 3.2. Device fabrication and layout 3.2.1. Layer deposition 3.2.2. Encapsulation 3.2.3. Homogeneity of layer thickness on a wafer 3.2.4. Device layout 3.3. Characterization 3.3.1. Electrical characterization 3.3.2. Sample illumination 3.3.3. Temperature dependent characterization 3.3.4. UPS 4. Simulations 5.1. Design of single carrier devices 5.1.1. General design requirements 5.1.2. Single carrier devices for space-charge limited current 5.1.3. Ohmic regime 5.1.4. Design of injection and extraction layers 5.2. Advanced evaluation of SCLC – potential mapping 5.2.1. Potential mapping by thickness variation 5.2.2. Further evaluation of the transport profile 5.2.3. Injection into and extraction from single carrier devices 5.2.4. Majority carrier approximation 5.3. Proof of principle: POEM on simulated data 5.3.1. Constant mobility 5.3.2. Field dependent mobility 5.3.3. Field and charge density activated mobility 5.3.4. Conclusion 5.4. Application: Transport characterization in organic semiconductors 5.4.1. Hole transport in ZnPc:C60 5.4.2. Hole transport in ZnPc:C60 – temperature variation 5.4.3. Hole transport in ZnPc:C60 – blend ratio variation 5.4.4. Hole transport in ZnPc:C70 5.4.5. Hole transport in neat ZnPc 5.4.6. Hole transport in F4-ZnPc:C60 5.4.7. Hole transport in DCV-5T-Me33:C60 5.4.8. Electron transport in ZnPc:C60 5.4.9. Electron transport in neat Bis-HFl-NTCDI 5.5. Summary and discussion of the results 5.5.1. Phthalocyanine:C60 blends 5.5.2. DCV-5T-Me33:C60 5.5.3. Conclusion 6. Organic solar cell characteristics: the influence of temperature 6.1. ZnPc:C60 solar cells 6.1.1. Temperature variation 6.1.2. Illumination intensity variation 6.2. Voc in flat and bulk heterojunction organic solar cells 6.2.1. Qualitative difference in Voc(I, T) 6.2.2. Interpretation of Voc(I, T) 6.3. BHJ stoichiometry variation 6.3.1. Voc upon variation of stoichiometry and contact layer 6.3.2. V0 upon stoichiometry variation 6.3.3. Low donor content stoichiometry 6.3.4. Conclusion from stoichiometry variation 6.4. Transport material variation 6.4.1. HTM variation 6.4.2. ETM variation 6.5. Donor:acceptor material variation 6.5.1. Donor variation 6.5.2. Acceptor variation 6.6. Conclusion 7. Summary and outlook 7.1. Summary 7.2. Outlook A. Appendix A.1. Energy pay-back of this thesis A.2. Tables and registers
Organische Halbleiter sind eine neue Schlüsseltechnologie für großflächige und flexible Dünnschichtelektronik. Sie werden als dünne Materialschichten (Sub-Nanometer bis Mikrometer) auf großflächige Substrate aufgebracht. Die technologisch am weitesten fortgeschrittenen Anwendungen sind organische Leuchtdioden (OLEDs) und organische Photovoltaik (OPV). Zur weiteren Steigerung von Leistungsfähigkeit und Effizienz ist die genaue Modellierung elektronischer Prozesse in den Bauteilen von grundlegender Bedeutung. Für die erfolgreiche Optimierung von Bauteilen ist eine zuverlässige Charakterisierung und Validierung der elektronischen Materialeigenschaften gleichermaßen erforderlich. Außerdem eröffnet das Verständnis der Zusammenhänge zwischen Materialstruktur und -eigenschaften einen Weg für innovative Material- und Bauteilentwicklung. Im Rahmen dieser Dissertation werden zwei Methoden für die Materialcharakterisierung entwickelt, verfeinert und angewandt: eine neuartige Methode zur Messung der Ladungsträgerbeweglichkeit μ und eine Möglichkeit zur Bestimmung der Ionisierungsenergie IE oder der Elektronenaffinität EA eines organischen Halbleiters. Für die Beweglichkeitsmessungen wird eine neue Auswertungsmethode für raumladungsbegrenzte Ströme (SCLC) in unipolaren Bauteilen entwickelt. Sie basiert auf einer Schichtdickenvariation des zu charakterisierenden Materials. In einem Ansatz zur räumlichen Abbildung des elektrischen Potentials (\"potential mapping\", POEM) wird gezeigt, dass das elektrische Potential als Funktion der Schichtdicke V(d) bei einer gegebenen Stromdichte dem räumlichen Verlauf des elektrischen Potentials V(x) im dicksten Bauteil entspricht. Daraus kann die Beweglichkeit als Funktion des elektrischen Felds F und der Ladungsträgerdichte n berechnet werden. Die Auswertung ist modellfrei, d.h. ein Modell zum Angleichen der Messdaten ist für die Berechnung von μ(F, n) nicht erforderlich. Die Messung ist außerdem unabhängig von einer möglichen Injektionsbarriere oder einer Potentialstufe an nicht-idealen Kontakten. Die gemessene Funktion μ(F, n) beschreibt die effektive durchschnittliche Beweglichkeit aller freien und in Fallenzuständen gefangenen Ladungsträger. Dieser Zugang beschreibt den Ladungstransport in energetisch ungeordneten Materialien realistisch, wo eine klare Unterscheidung zwischen freien und Fallenzuständen nicht möglich oder willkürlich ist. Die Messung von IE und EA wird mithilfe temperaturabhängiger Messungen an Solarzellen durchgeführt. In geeigneten Bauteilen mit einem Mischschicht-Heteroübergang (\"bulk heterojunction\" BHJ) ist die Leerlaufspannung Voc im gesamten Messbereich oberhalb 180K eine linear fallende Funktion der Temperatur T. Es kann bestätigt werden, dass die Extrapolation zum Temperaturnullpunkt V0 = Voc(T → 0K) mit der effektiven Energielücke Egeff , d.h. der Differenz zwischen EA des Akzeptor-Materials und IE des Donator-Materials, übereinstimmt. Die systematische schrittweise Variation einzelner Bestandteile der Solarzellen und die Überprüfung des Einflusses auf V0 bestätigen die Beziehung V0 = Egeff. Damit kann die IE oder EA eines Materials bestimmt werden, indem man es in einem BHJ mit einem Material kombiniert, dessen komplementärer Wert bekannt ist. Messungen per Ultraviolett-Photoelektronenspektroskopie (UPS) und inverser Photoelektronenspektroskopie (IPES) werden damit bestätigt, präzisiert und ergänzt. Die beiden entwickelten Messmethoden werden auf organische Halbleiter aus kleinen Molekülen einschließlich Mischschichten angewandt. In Mischschichten aus Zink-Phthalocyanin (ZnPc) und C60 wird eine Löcherbeweglichkeit gemessen, die sowohl thermisch als auch feld- und ladungsträgerdichteaktiviert ist. Wenn das Mischverhältnis variiert wird, steigt die Löcherbeweglichkeit mit zunehmendem ZnPc-Anteil, während die effektive Energielücke unverändert bleibt. Verschiedene weitere Materialien und Materialmischungen werden hinsichtlich Löcher- und Elektronenbeweglichkeit sowie ihrer Energielücke charakterisiert, einschließlich bisher wenig untersuchter hochverdünnter Donator-Systeme. In allen Materialien wird eine deutliche Feldaktivierung der Beweglichkeit beobachtet. Die Ergebnisse ermöglichen eine verbesserte Beschreibung der detaillierten Funktionsweise organischer Solarzellen und unterstützen die künftige Entwicklung hocheffizienter und optimierter Bauteile.:1. Introduction 2. Organic semiconductors and devices 2.1. Organic semiconductors 2.1.1. Conjugated π system 2.1.2. Small molecules and polymers 2.1.3. Disorder in amorphous materials 2.1.4. Polarons 2.1.5. Polaron hopping 2.1.6. Fermi-Dirac distribution and Fermi level 2.1.7. Quasi-Fermi levels 2.1.8. Trap states 2.1.9. Doping 2.1.10. Excitons 2.2. Interfaces and blend layers 2.2.1. Interface dipoles 2.2.2. Energy level bending 2.2.3. Injection from metal into semiconductor, and extraction 2.2.4. Excitons at interfaces 2.3. Charge transport and recombination in organic semiconductors 2.3.1. Drift transport 2.3.2. Charge carrier mobility 2.3.3. Thermally activated transport 2.3.4. Diffusion transport 2.3.5. Drift-diffusion transport 2.3.6. Space-charge limited current 2.3.7. Recombination 2.4. Mobility measurement 2.4.1. SCLC and TCLC 2.4.2. Time of flight 2.4.3. Organic field effect transistors 2.4.4. CELIV 2.5. Organic solar cells 2.5.1. Exciton diffusion towards the interface 2.5.2. Dissociation of CT states 2.5.3. CT recombination 2.5.4. Flat and bulk heterojunction 2.5.5. Transport layers 2.5.6. Thin film optics 2.5.7. Current-voltage characteristics and equivalent circuit 2.5.8. Solar cell efficiency 2.5.9. Limits of efficiency 2.5.10. Correct solar cell characterization 2.5.11. The \"O-Factor\" 3. Materials and experimental methods 3.1. Materials 3.2. Device fabrication and layout 3.2.1. Layer deposition 3.2.2. Encapsulation 3.2.3. Homogeneity of layer thickness on a wafer 3.2.4. Device layout 3.3. Characterization 3.3.1. Electrical characterization 3.3.2. Sample illumination 3.3.3. Temperature dependent characterization 3.3.4. UPS 4. Simulations 5.1. Design of single carrier devices 5.1.1. General design requirements 5.1.2. Single carrier devices for space-charge limited current 5.1.3. Ohmic regime 5.1.4. Design of injection and extraction layers 5.2. Advanced evaluation of SCLC – potential mapping 5.2.1. Potential mapping by thickness variation 5.2.2. Further evaluation of the transport profile 5.2.3. Injection into and extraction from single carrier devices 5.2.4. Majority carrier approximation 5.3. Proof of principle: POEM on simulated data 5.3.1. Constant mobility 5.3.2. Field dependent mobility 5.3.3. Field and charge density activated mobility 5.3.4. Conclusion 5.4. Application: Transport characterization in organic semiconductors 5.4.1. Hole transport in ZnPc:C60 5.4.2. Hole transport in ZnPc:C60 – temperature variation 5.4.3. Hole transport in ZnPc:C60 – blend ratio variation 5.4.4. Hole transport in ZnPc:C70 5.4.5. Hole transport in neat ZnPc 5.4.6. Hole transport in F4-ZnPc:C60 5.4.7. Hole transport in DCV-5T-Me33:C60 5.4.8. Electron transport in ZnPc:C60 5.4.9. Electron transport in neat Bis-HFl-NTCDI 5.5. Summary and discussion of the results 5.5.1. Phthalocyanine:C60 blends 5.5.2. DCV-5T-Me33:C60 5.5.3. Conclusion 6. Organic solar cell characteristics: the influence of temperature 6.1. ZnPc:C60 solar cells 6.1.1. Temperature variation 6.1.2. Illumination intensity variation 6.2. Voc in flat and bulk heterojunction organic solar cells 6.2.1. Qualitative difference in Voc(I, T) 6.2.2. Interpretation of Voc(I, T) 6.3. BHJ stoichiometry variation 6.3.1. Voc upon variation of stoichiometry and contact layer 6.3.2. V0 upon stoichiometry variation 6.3.3. Low donor content stoichiometry 6.3.4. Conclusion from stoichiometry variation 6.4. Transport material variation 6.4.1. HTM variation 6.4.2. ETM variation 6.5. Donor:acceptor material variation 6.5.1. Donor variation 6.5.2. Acceptor variation 6.6. Conclusion 7. Summary and outlook 7.1. Summary 7.2. Outlook A. Appendix A.1. Energy pay-back of this thesis A.2. Tables and registers

The properties of RNiSb compounds were studied from various points of view: Magnetism, transport, electronic structure. The compounds with a light rare earth are metallic, while the cubic phases with a heavy rare earth element have the semi-Heusler structure and are narrow gap semiconductors. A giant magnetoresistance effect was found at low temperatures, the larger as the density of charge carriers is weak. It was explained by the polarisation of the impurity levels situated within the band gap of the semiconductor under the field of the magnetic moment of the 4f shell. The crystal field, as well as the magnetic order at low temperatures, were studied by neutron scattering and diffraction. Particular magnetic properties (absence of magnetic order in the Pr compound, antiferromagnetic structure in the second group, orientation of the moments) have been explained, at least qualitatively. CeNiSb is a Kondo-type compound with a Kondo temperature of about 8 K. Photoemission measurements have allowed to analyse the electronic structure in the valence band of these compounds, in agreement with band structure calculations. By resonant photoemission of TbNiSb and GdCu, different resonance channels have been resolved, which depend on the spin configuration of the excited states.