Oxide Semiconductors For Organic Opto-electronic Devices

Development of transparent oxide semiconductors (TOS) from Earth-abundant materials is of great interest for cost-effective thin film device applications, such as solar cells, light emitting diodes (LEDs), touch-sensitive displays, electronic paper, and transparent thin film transistors. The need of inexpensive or high performance electrode might be even greater for organic photovoltaic (OPV), with the goal to harvest renewable energy with inexpensive, lightweight, and cost competitive materials. The natural abundance of zinc and the wide bandgap ($sim$3.3 eV) of its oxide make it an ideal candidate. In this dissertation, I have introduced various concepts on the modulations of various surface, interface and bulk opto-electronic properties of ZnO based semiconductor for charge transport, charge selectivity and optimal device performance. I have categorized transparent semiconductors into two sub groups depending upon their role in a device. Electrodes, usually 200 to 500 nm thick, optimized for good transparency and transporting the charges to the external circuit. Here, the electrical conductivity in parallel direction to thin film, i.e bulk conductivity is important. And contacts, usually 5 to 50 nm thick, are optimized in case of solar cells for providing charge selectivity and asymmetry to manipulate the built in field inside the device for charge separation and collection. Whereas in Organic LEDs (OLEDs), contacts provide optimum energy level alignment at organic oxide interface for improved charge injections. For an optimal solar cell performance, transparent electrodes are designed with maximum transparency in the region of interest to maximize the light to pass through to the absorber layer for photo-generation, plus they are designed for minimum sheet resistance for efficient charge collection and transport. As such there is need for material with high conductivity and transparency. Doping ZnO with some common elements such as B, Al, Ga, In, Ge, Si, and F result in n-type doping with increase in carriers resulting in high conductivity electrode, with better or comparable opto-electronic properties compared to current industry-standard indium tin oxide (ITO). Furthermore, improvement in mobility due to improvement on crystallographic structure also provide alternative path for high conductivity ZnO TCOs. Implementing these two aspects, various studies were done on gallium doped zinc oxide (GZO) transparent electrode, a very promising indium free electrode. The dynamics of the superimposed RF and DC power sputtering was utilized to improve the microstructure during the thin films growth, resulting in GZO electrode with conductivity greater than 4000 S/cm and transparency greater than 90 %. Similarly, various studies on research and development of Indium Zinc Tin Oxide and Indium Zinc Oxide thin films which can be applied to flexible substrates for next generation solar cells application is presented. In these new TCO systems, understanding the role of crystallographic structure ranging from poly-crystalline to amorphous phase and the influence on the charge transport and optical transparency as well as important surface passivation and surface charge transport properties. Implementation of these electrode based on ZnO on opto-electronics devices such as OLED and OPV is complicated due to chemical interaction over time with the organic layer or with ambient. The problem of inefficient charge collection/injection due to poor understanding of interface and/or bulk property of oxide electrode exists at several oxide-organic interfaces. The surface conductivity, the work function, the formation of dipoles and the band-bending at the interfacial sites can positively or negatively impact the device performance. Detailed characterization of the surface composition both before and after various chemicals treatment of various oxide electrode can therefore provide insight into optimization of device performance. Some of the work related to controlling the interfacial chemistry associated with charge transport of transparent electrodes are discussed. Thus, the role of various pre-treatment on poly-crystalline GZO electrode and amorphous indium zinc oxide (IZO) electrode is compared and contrasted. From the study, we have found that removal of defects and self passivating defects caused by accumulation of hydroxides in the surface of both poly-crystalline GZO and amorphous IZO, are critical for improving the surface conductivity and charge transport. Further insight on how these insulating and self-passivating defects cause charge accumulation and recombination in an device is discussed. With recent rapid development of bulk-heterojunction organic photovoltaics active materials, devices employing ZnO and ZnO based electrode provide air stable and cost-competitive alternatives to traditional inorganic photovoltaics. The organic light emitting diodes (OLEDs) have already been commercialized, thus to follow in the footsteps of this technology, OPV devices need further improvement in power conversion efficiency and stable materials resulting in long device lifetimes. Use of low work function metals such as Ca/Al in standard geometry do provide good electrode for electron collection, but serious problems using low work-function metal electrodes originates from the formation of non-conductive metal oxide due to oxidation resulting in rapid device failure. Hence, using low work-function, air stable, conductive metal oxides such as ZnO as electrons collecting electrode and high work-function, air stable metals such as silver for harvesting holes, has been on the rise. Devices with degenerately doped ZnO functioning as transparent conductive electrode, or as charge selective layer in a polymer/fullerene based heterojunction, present useful device structures for investigating the functional mechanisms within OPV devices and a possible pathway towards improved air-stable high efficiency devices. Furthermore, analysis of the physical properties of the ZnO layers with varying thickness, crystallographic structure, surface chemistry and grain size deposited via various techniques such as atomic layer deposition, sputtering and solution-processed ZnO with their respective OPV device performance is discussed. We find similarity and differences in electrode property for good charge injection in OLEDs and good charge collection in OPV devices very insightful in understanding physics behind device failures and successes. In general, self-passivating surface of amorphous TCOs IZO, ZTO and IZTO forms insulating layer that hinders the charge collection. Similarly, we find modulation of the carrier concentration and the mobility in electron transport layer, namely zinc oxide thin films, very important for optimizing device performance.

Calibration of the length of a chain of single gold atoms

Using a scanning tunnelling microscope or mechanically controllable break junction it has been shown that it is possible to control the formation of a wire made of single gold atoms. In these experiments an interatomic distance between atoms in the chain of ∼3.6 Å was reported which is not consistent with recent theoretical calculations. Here, using precise calibration procedures for both techniques, we measure the length of the atomic chains. Based on the distance between the peaks observed in the chain length histogram we find the mean value of the interatomic distance before chain rupture to be 2.5±0.2 Å. This value agrees with the theoretical calculations for the bond length. The discrepancy with the previous experimental measurements was due to the presence of He gas, that was used to promote the thermal contact, and which affects the value of the work function that is commonly used to calibrate distances in scanning tunnelling microscopy and mechanically controllable break junctions at low temperatures.

Characterization of the interfaces between Au(hkl) single crystal basal plane electrodes and [Emmim][Tf2N] ionic liquid

The interface between Au(hkl) basal planes and the ionic liquid 1-Ethyl-2,3-dimethyl imidazolium bis(trifluoromethyl)sulfonil imide was investigated by using both cyclic voltammetry and laser-induced temperature jump. Cyclic voltammetry showed characteristic features, revealing surface sensitive processes at the interfaces Au(hkl)/[Emmim][Tf2N]. From laser-induced heating the potential of maximum entropy (pme) is determined. Pme is close to the potential of zero charge (pzc) and, therefore, the technique provides relevant interfacial information. The following order for the pme values has been found: Au(111) > Au(100) > Au(110). This order correlates well with work function data and values of pzc in aqueous solutions.

APLICAÇÃO DA TEORIA DOS JOGOS NA GESTÃO DE PESSOAS: UMA ANÁLISE DA VARIÁVEL SALÁRIO

Esta dissertação apresenta os principais aspectos da Teoria dos Jogos, mostrando sua aplicação como instrumento analítico na Gestão de Pessoas no que diz respeito à variável salário. Considera a organização e o trabalhador como conceitos gerais, sem identificar o setor de atuação, ramo de atividade, classificação jurídica em função do seu faturamento, total de empregados ou participação de mercado dessa organização. Da mesma forma o conceito trabalhador não recebe qualquer identificação em relação ao setor de atividade onde trabalha, função, salário ou formação profissional. A organização é toda estrutura que gera bens e serviços para a sociedade e o trabalhador é todo elemento que emprega sua força de trabalho na produção de bens e serviços. Os objetivos estabelecidos para este estudo são: identificar as possibilidades de aplicação da Teoria dos Jogos na Gestão de Pessoas considerando a variável salário como elemento de conflito entre a organização e o trabalhador; mostrar se a forma de representação extensiva é mais apropriada ou não para analisar o cenário de embate na decisão de contratar ou não o trabalhador ou pagar mais ou menos salário e a existência do Equilíbrio de Nash. A metodologia qualitativa com apoio bibliográfico e documental caracteriza esta pesquisa qualitativa quanto a metodologia de pesquisa. Os métodos qualitativos contribuem para interpretar fenômenos do cotidiano, podendo ser composto por dados simbólicos situados em determinado contexto. A pesquisa documental é uma contribuição importante ao estudo do tema proposto, já que a pesquisa qualitativa não é uma proposta rigidamente estruturada e isto permite que o pesquisador use a imaginação e criatividade para atingir o objetivo. Os resultados obtidos pela pesquisa dão conta de que é possível a aplicação da Teoria dos Jogos na Gestão de Pessoas considerando o embate entre os jogadores (o trabalhador e a organização) em torno do salário, discutido no capítulo 4 nas representações da matriz de payoff de um jogo estratégico e nas figuras 9,10,11,e 16. A representação na forma extensiva, outro objetivo, indicando os payoffs entre duas decisões centrais representadas por X = flexibilização com renúncia dos direitos pelos trabalhadores e Y = flexibilização/adaptação/negociação, conforme figura 16. O gestor de pessoas percebe as estratégias existentes para a organização e trabalhador para a tomada de decisão, ao mesmo tempo em que pode avaliar a situação que esteja vivendo e fazer simulações em busca de novas propostas. Por fim, o Equilíbrio de Nash para a aplicação na Gestão de Pessoas é discutido no item 4.1.3, sendo possível verificar que tanto o trabalhador como a organização podem chegar a uma decisão favorável para ambos e manter seus objetivos pretendidos inicialmente. Na figura 17, esse equilíbrio é apresentado depois da tomada de decisão do trabalhador pela proposta feita pela organização na sequência O2 e o trabalhador ficou com o ramo de sequência T2 com o valor de 20 moedas. A potencialidade da Teoria dos Jogos na Gestão de Pessoas está no fato de que quem atua em uma organização compartilha resultados bons ou ruins obtidos pelas escolhas alheias, individuais e construídas coletivamente.

APLICAÇÃO DA TEORIA DOS JOGOS NA GESTÃO DE PESSOAS: UMA ANÁLISE DA VARIÁVEL SALÁRIO

Esta dissertação apresenta os principais aspectos da Teoria dos Jogos, mostrando sua aplicação como instrumento analítico na Gestão de Pessoas no que diz respeito à variável salário. Considera a organização e o trabalhador como conceitos gerais, sem identificar o setor de atuação, ramo de atividade, classificação jurídica em função do seu faturamento, total de empregados ou participação de mercado dessa organização. Da mesma forma o conceito trabalhador não recebe qualquer identificação em relação ao setor de atividade onde trabalha, função, salário ou formação profissional. A organização é toda estrutura que gera bens e serviços para a sociedade e o trabalhador é todo elemento que emprega sua força de trabalho na produção de bens e serviços. Os objetivos estabelecidos para este estudo são: identificar as possibilidades de aplicação da Teoria dos Jogos na Gestão de Pessoas considerando a variável salário como elemento de conflito entre a organização e o trabalhador; mostrar se a forma de representação extensiva é mais apropriada ou não para analisar o cenário de embate na decisão de contratar ou não o trabalhador ou pagar mais ou menos salário e a existência do Equilíbrio de Nash. A metodologia qualitativa com apoio bibliográfico e documental caracteriza esta pesquisa qualitativa quanto a metodologia de pesquisa. Os métodos qualitativos contribuem para interpretar fenômenos do cotidiano, podendo ser composto por dados simbólicos situados em determinado contexto. A pesquisa documental é uma contribuição importante ao estudo do tema proposto, já que a pesquisa qualitativa não é uma proposta rigidamente estruturada e isto permite que o pesquisador use a imaginação e criatividade para atingir o objetivo. Os resultados obtidos pela pesquisa dão conta de que é possível a aplicação da Teoria dos Jogos na Gestão de Pessoas considerando o embate entre os jogadores (o trabalhador e a organização) em torno do salário, conforme pode ser visto no capítulo 4 nas representações da matriz de payoff de um jogo estratégico e nas figuras 9,10,11,e 16. A representação na forma extensiva, constitui outro objetivo, indicando os payoffs entre duas decisões centrais representadas por X = flexibilização com renúncia dos direitos pelos trabalhadores e Y = flexibilização/adaptação/negociação, conforme figura 16. Ao analisar a figura, o gestor de pessoas percebe as estratégias existentes para a organização e trabalhador para a tomada de decisão, ao mesmo tempo em que pode avaliar a situação que esteja vivendo e fazer simulações em busca de novas propostas. Por fim, o Equilíbrio de Nash para a aplicação na Gestão de Pessoas é discutido no item 4.1.3, sendo possível verificar que tanto o trabalhador como a organização podem chegar a uma decisão favorável para ambos e manter seus objetivos pretendidos inicialmente. Na figura 17, esse equilíbrio é apresentado depois da tomada de decisão do trabalhador pela proposta feita pela organização na sequência O2 e o trabalhador ficou com o ramo de sequência T2 com o valor de 20 moedas. A potencialidade da Teoria dos Jogos na Gestão de Pessoas surge do fato de que quem atua em uma organização compartilha resultados bons ou ruins obtidos pelas escolhas alheias, escolhas individuais e pelas escolhas construídas coletivamente. Quando o trabalhador resolve produzir menos, a empresa sofre com a perda do lucro gerado pelo ritmo mais lento de trabalho. Para mudar esse quadro, a empresa toma a decisão de aumentar o salário e o trabalhador por sua vez desenvolve a tarefa com maior velocidade e em maior quantidade e ela pode retomar o seu lucro. Nesses jogos há cobranças de desempenho, exigência para atingir metas, pressões, conflitos com clientes e lideranças. Logo, a Teoria dos Jogos pode ser aplicada como instrumento para o gestor de Pessoas avaliar a situação vivida para a tomada de decisão que resolva a situação de embate.

Synthesis and characterisation of interfacial layers in organic solar cells

The quest for renewable energy sources has led to growing attention in the research of organic photovoltaics (OPVs), as a promising alternative to fossil fuels, since these devices have low manufacturing costs and attractive end-user qualities, such as ease of installation and maintenance. Wide application of OPVs is majorly limited by the devices lifetime. With the development of new encapsulation materials, some degradation factors, such as water and oxygen ingress, can almost be excluded, whereas the thermal degradation of the devices remains a major issue. Two aspects have to be addressed to solve the problem of thermal instability: bulk effects in the photoactive layer and interfacial effects at the photoactive layer/charge-transporting layers. In this work, the interface between photoactive layer and electron-transporting zinc oxide (ZnO) in devices with inverted architecture was engineered by introducing polymeric interlayers, based on zinc-binding ligands, such as 3,4-dihydroxybenzene and 8-hydroxyquinoline. Also, a cross-linkable layer of poly(3,4-dimethoxystyrene) and its fullerene derivative were studied. At first, controlled reversible addition-fragmentation chain transfer (RAFT) polymerisation was employed to achieve well-defined polymers in a range of molar masses, all bearing a chain-end functionality for further modifications. Resulting polymers have been fully characterised, including their thermal and optical properties, and introduced as interlayers to study their effect on the initial device performance and thermal stability. Poly(3,4-dihydroxystyrene) and its fullerene derivative were found unsuitable for application in devices as they increased the work function of ZnO and created a barrier for electron extraction. On the other hand, their parental polymer, poly(3,4-dimethoxystyrene), and its fullerene derivative, upon cross-linking, resulted in enhanced efficiency and stability of devices, if compared to control. Polymers based on 8-hydroxyquinoline ligand had a negative effect on the initial stability of the devices, but increased the lifetime of the cells under accelerated thermal stress. Comprehensive studies of the key mechanisms, determining efficiency, such as charge generation and extraction, were performed by using time-resolved electrical and spectroscopic techniques, in order to understand in detail the effect of the interlayers on the device performance. Obtained results allow deeper insight into mechanisms of degradation that limit the lifetime of devices and prompt the design of better materials for the interface stabilisation.

Graphene-MoS2 Hybrid Technology for Large-Scale Two-Dimensional Electronics

Two-dimensional (2D) materials have generated great interest in the last few years as a new toolbox for electronics. This family of materials includes, among others, metallic graphene, semiconducting transition metal dichalcogenides (such as MoS2) and insulating Boron Nitride. These materials and their heterostructures offer excellent mechanical flexibility, optical transparency and favorable transport properties for realizing electronic, sensing and optical systems on arbitrary surfaces. In this work, we develop several etch stop layer technologies that allow the fabrication of complex 2D devices and present for the first time the large scale integration of graphene with molybdenum disulfide (MoS2) , both grown using the fully scalable CVD technique. Transistor devices and logic circuits with MoS2 channel and graphene as contacts and interconnects are constructed and show high performances. In addition, the graphene/MoS2 heterojunction contact has been systematically compared with MoS2-metal junctions experimentally and studied using density functional theory. The tunability of the graphene work function significantly improves the ohmic contact to MoS2. These high-performance large-scale devices and circuits based on 2D heterostructure pave the way for practical flexible transparent electronics in the future. The authors acknowledge financial support from the Office of Naval Research (ONR) Young Investigator Program, the ONR GATE MURI program, and the Army Research Laboratory. This research has made use of the MI.

Adsorption Calorimetry for Energy Conversion Technologies: Applications in Organic Photovoltaics, Catalysis, and Atomic Layer Deposition

Thesis (Ph.D.)--University of Washington, 2016-07

Acompanhamento da construção do edifício "Castilho 15"

Relatório de Estágio para obtenção do grau de Mestre em Engenharia Civil

Influence of alkylphosphonic acid grafting on the electronic and magnetic properties of La2/3Sr1/3MnO3 surfaces

Self-assembled monolayers (SAMs) are highly promising materials for molecular engineering of electronic and spintronics devices thanks to their surface functionalization properties. In this direction, alkylphosphonic acids have been used to functionalize the most common ferromagnetic electrode in organic spintronics: La2/3Sr1/3MnO3 (LSMO). However, a study on the influence of SAMs grafting on LSMO electronic and magnetic properties is still missing. In this letter, we probe the influence of alkylphosphonic acids-based SAMs on the electronic and magnetic properties of the LSMO surface using different spectroscopies. We observe by X-ray photoemission and X-ray absorption that the grafting of the molecules on the LSMO surface induces a reduction of the Mn oxidation state. Ultraviolet photoelectron spectroscopy measurements also show that the LSMO work function can be modified by surface dipoles opening the door to both tune the charge and spin injection efficiencies in organic devices such as organic light-emitting diodes.

Isolating the photovoltaic junction: atomic layer deposited TiO2-RuO2 alloy Schottky contacts for silicon photoanodes

We synthesized nanoscale TiO2-RuO2 alloys by atomic layer deposition (ALD) that possess a high work function and are highly conductive. As such, they function as good Schottky contacts to extract photogenerated holes from n-type silicon while simultaneously interfacing with water oxidation catalysts. The ratio of TiO2 to RuO2 can be precisely controlled by the number of ALD cycles for each precursor. Increasing the composition above 16% Ru sets the electronic conductivity and the metal work function. No significant Ohmic loss for hole transport is measured as film thickness increases from 3 to 45 nm for alloy compositions >= 16% Ru. Silicon photoanodes with a 2 nm SiO2 layer that are coated by these alloy Schottky contacts having compositions in the range of 13-46% Ru exhibit average photovoltages of 525 mV, with a maximum photovoltage of 570 mV achieved. Depositing TiO2-RuO2 alloys on nSi sets a high effective work function for the Schottky junction with the semiconductor substrate, thus generating a large photovoltage that is isolated from the properties of an overlying oxygen evolution catalyst or protection layer.

Study of heterostructures of Cu3BiS3–buffer layer measured by Kelvin probe force microscopy measurements (KPFM)

The interface formed between Cu3BiS3 thin films and the buffer layer is a potentially limiting factor to the performance of solar cells based on Al/Cu3BiS3/buffer heterojunctions. The buffer layers of ZnS and In2S3 were grown by coevaporation, and tested as an alternative to the traditional CdS deposited by chemical bath deposition. From the Kelvin probe force microscopy measurements, we found the values of the work function of ZnS, In2S3, and CdS, layers deposited into Cu3BiS3. Additionally, different electronic activity was found for different grain boundaries (GBs), from studies under illumination, we also found the net doping concentration and the density of charged GB states for Cu3BiS3 and Cu3BiS3/CdS.

When will a flame describing function approach to thermoacoustics work well?

In any thermoacoustic analysis, it is important not only to predict linear frequencies and growth rates, but also the amplitude and frequencies of any limit cycles. The Flame Describing Function (FDF) approach is a quasi-linear analysis which allows the prediction of both the linear and nonlinear behaviour of a thermoacoustic system. This means that one can predict linear growth rates and frequencies, and also the amplitudes and frequencies of any limit cycles. The FDF achieves this by assuming that the acoustics are linear and that the flame, which is the only nonlinear element in the thermoacoustic system, can be adequately described by considering only its response at the frequency at which it is forced. Therefore any harmonics generated by the flame's nonlinear response are not considered. This implies that these nonlinear harmonics are small or that they are sufficiently filtered out by the linear dynamics of the system (the low-pass filter assumption). In this paper, a flame model with a simple saturation nonlinearity is coupled to simple duct acoustics, and the success of the FDF in predicting limit cycles is studied over a range of flame positions and acoustic damping parameters. Although these two parameters affect only the linear acoustics and not the nonlinear flame dynamics, they determine the validity of the low-pass filter assumption made in applying the flame describing function approach. Their importance is highlighted by studying the level of success of an FDF-based analysis as they are varied. This is achieved by comparing the FDF's prediction of limit-cycle amplitudes to the amplitudes seen in time domain simulations.

Measuring the Characteristic Function of the Work Distribution

We propose an interferometric setting for the ancilla-assisted measurement of the characteristic function of the work distribution following a time-dependent process experienced by a quantum system. We identify how the configuration of the effective interferometer is linked to the symmetries enjoyed by the Hamiltonian ruling the process and provide the explicit form of the operations to implement in order to accomplish our task. We finally discuss two physical settings, based on hybrid optomechanical-electromechanical devices, where the theoretical proposals discussed in our work could find an experimental demonstration.

Traffic controls for construction and maintenance work zones. Volume I - office function.

Federal Highway Administration, Washington, D.C.