The aim of this thesis is to provide an in-depth investigation of zinc tin oxide, Zn1-xSnxOy or ZTO, grown by atomic layer deposition (ALD) as a buffer layer in Cu(In,Ga)Se2 (CIGS) solar cells. The thesis analyzes how changes in the ALD process influence the material properties of ZTO, and how these in turn affect the performance of CIGS solar cells. It is shown that ZTO grows uniformly and conformably on CIGS and that the interface between ZTO and CIGS is sharp with little or no interdiffusion between the layers. The band gap and conduction band energy level of ZTO are dependent both on the [Sn]/([Zn]+[Sn]) composition and on the deposition temperature. The influence by changes in composition is non-trivial, and the highest band gap and conduction band energy level are obtained at a [Sn]/([Zn]+[Sn]) composition of 0.2 at 120  °C. An increase in optical band gap is observed at decreasing deposition temperatures and is associated with quantum confinement effects caused by a decrease in crystallite size. The ability to change the conduction band energy level of ZTO enables the formation of suitable conduction band offsets between ZTO and CIGS with varying Ga-content. It is found that 15 nm thin ZTO buffer layers are sufficient to fabricate CIGS solar cells with conversion efficiencies up to 18.2 %. The JSC is in general 2 mA/cm2 higher, and the VOC 30 mV lower, for cells with the ZTO buffer layer as compared to cells with the traditional CdS buffer layer. In the end comparable efficiencies are obtained for the two different buffer layers. The gain in JSC for the ZTO buffer layer is associated with lower parasitic absorption in the UV-blue region of the solar spectrum and it is shown that the JSC can be increased further by making changes to the other layers in the traditional CdS/i-ZnO/ZnO:Al window layer structure. The ZTO is highly resistive, and it is found that the shunt preventing i-ZnO layer can be omitted, which further increases the JSC. Moreover, an additional increase in JSC is obtained by replacing the sputtered ZnO:Al front contact with In2O3 deposited by ALD. The large gain in JSC for the ZTO/In2O3 window layer stack compensates for the lower VOC related to the ZTO buffer layer, and it is demonstrated that the ZTO/In2O3 window layer structure yields 0.6 % (absolute) higher conversion efficiency than the CdS/i-ZnO/ZnO:Al window layer structure.

Amorphous oxide semiconductors are of potential interest in the display industry due to their high carrier mobility, transparency at visible wavelengths and excellent operational stability. In this dissertation, n-channel zinc-tin oxide thin-film transistors are fabricated based on a solution-based deposition approach, which allows low fabrication cost and high throughput. The effects of device configuration and process conditions on transistor performance are investigated, and circuit applications including inverters, amplifiers, and ring oscillators are demonstrated. Charge transport in the zinc-tin oxide field-effect transistors is also investigated. A transition from thermally-activated to band-like transport is observed with increasing carrier concentration in high mobility samples, which agrees well with the key predictions of the multiple trap and release model and also Mott’s mobility edge model. In addition, velocity distribution of charge carriers is studied with a time-resolved technique. This provides a more detailed picture of charge transport in field-effect transistors. P-channel organic semiconductor field-effect transistors are also investigated with a view to combine them with n-channel amorphous oxide transistors to create a hybrid organic-inorganic complementary technology. / text

Amorphous Oxide semiconductors have gained large interest in the display industry owing to their high carrier mobilities and low fabrication costs. In this thesis, n-channel solution based zinc-tin oxide (ZTO) thin-film transistors (TFTs) are studied from a circuit design perspective. The study includes an iterative process of circuit design, layout and test procedure of the fabricated devices in the lab. The device models used in circuit simulations are refined following the data fed back from each of these iterations which has enabled more accurate design of complex circuits using ZTO devices. The requirement and development of a physical compact model for performing accurate and predictive circuit simulations has been presented. The use of ZTO devices in low cost, transparent and flexible electronic applications has been investigated through the study of basic circuit blocks such as amplifiers, ring oscillators, inverters and a four stage Operational Amplifier. / text

Amorphous Oxide Semiconductors (AOS) are widely being explored in the field of flexible and transparent electronics. In this thesis, solution processed zinc-tin oxide (ZTO) n-channel TFT based circuits are studied. Inverters, single stage amplifiers and ring oscillators are designed, fabricated and tested. 7-stage ring oscillators with output frequencies up to 106kHz and 5-stage ring oscillators with frequencies up to 75kHz are reported. A stable three stage op-amp with a buffered output is designed for a gain of 39.9dB with a unity gain frequency of 27.7kHz. A 7-stage ring oscillator with output frequency close to 1MHz is simulated and designed. The op-amp and the ring oscillator are ready to be fabricated and tested. An RPI model for a-Si, adapted to fit the ZTO device characteristics, is used for simulation. Development of a new model based on the physics behind charge transport in ZTO devices is explored. An expression for gate bias dependent mobility in ZTO devices is derived. / text

This dissertation focuses on characterizing the nanoscale and surface averaged electrical properties of transparent conducting oxide (TCO) electrodes such as indium tin oxide (ITO) and transparent metal-oxide (MO) electron selective interlayers (ESLs), such as zinc oxide (ZnO), the ability of these materials to rapidly extract photogenerated charges from organic semiconductors (OSCs) used in organic photovoltaic (OPV) cells, and evaluating their impact on the power conversion efficiency (PCE) of OPV devices. In Chapter 1, we will introduce the fundamental principles regarding the need for low cost power generation, the benefits of OPV technologies, as well as the key principles that govern the operation of OPV devices and the key innovations that have advanced this technology. In Chapter 2 of this dissertation, we demonstrate an innovative application of conductive probe atomic force microscopy (CAFM) to map the nanoscale electrical heterogeneity at the interface between an electrode, such as ITO, and an OSC such as the p-type OSC copper phthalocyanine (CuPc).(MacDonald et al. (2012) ACS Nano, 6, p. 9623) In this work we collected arrays of J-V curves, using a CAFM probe as the top contact of CuPc/ITO systems, to map the local J-V responses. By comparing J-V responses to known models for charge transport, we were able to determine if the local rate-limiting step for charge transport is through the OSC (ohmic) or the CuPc/ITO interface (nonohmic). These results strongly correlate with device PCE, as demonstrated through the controlled addition of insulating alkylphosphonic acid self-assembled monolayers (SAMs) at the ITO/CuPc interface. Subsequent chapters focus on the electrical property characterization of RF-magnetron sputtered ZnO (sp-ZnO) ESL films on ITO substrates. We have shown that the energetic alignment of ESLs and the organic semiconducting (OSC) active materials plays a critical role in determining the PCE of OPV devices and the appearance of, or lack thereof, UV light soaking sensitivity. For ZnO and fullerene interfaces, we have shown that either minimizing the oxygen partial pressure during ZnO deposition or exposure of ZnO to UV light minimizes the energetic offset at this interface and maximizes device PCE. We have used a combination of device testing, device modeling, and impedance spectroscopy to fully characterize the effects that energetic alignment has on the charge carrier transport and charge carrier distribution within the OPV device. This work can be found in Chapter 3 of this dissertation and is in preparation for publication. We have also shown that the local properties of sp-ZnO films varies as a function of the underlying ITO crystal face. We show that the local ITO crystal face determines the local nucleation and growth of the sp-ZnO films. We demonstrate that this effects the morphology, the chemical resistance to etching as well as the surface electrical properties of the sp-ZnO films. This is likely due to differences in the surface mobility of sputtered Zn and O atoms on these crystal faces during film nucleation. This affects the nanoscale distribution of electrical and chemical properties. As a result we demonstrate that the PCE, and UV sensitivity of the J-V response of OPVs using sp-ZnO ESLs are strongly impacted by the distribution of ITO crystal faces at the surface of the substrate. This work can be found in Chapter 4 of this dissertation and is in preparation for publication. These studies have contributed to a detailed understanding of the role that electrical heterogeneity, insulating barriers and energetic alignment at the MO/OSC interface play in OPV PCE.

Photovoltaics manufactured using organic materials as a substitute for inorganic materials may provide for cheaper production of solar cells if their efficiencies can be made comparable to existing technologies. Photovoltaic devices are comprised of layered structures where the electrical, chemical, and physical properties at the multiple interfaces play a significant role in the operation of the completed device. This thesis attempts to establish a relationship between interfacial properties and overall device performance by investigation of both the organic/organic heterojunction interface, as well as the interface between the inorganic substrate and the first organic layer with useful insights towards enhancing the efficiency of organic solar cells.It has been proposed that residual chemical species may act as barriers to charge transfer at the interface between the transparent conductor (TCO) and the first organic layer, possibly causing a large contact resistance and leading to reduced device performance. Previous work has investigated the surface of the TCO but no baseline characterization of carbon-free surfaces has previously been given. In this work clean surfaces are investigated to develop a fundamental understanding of the intrinsic spectra such that further analyses of contaminated surfaces can be presented systematically and reproducibly to develop a chemical model of the TCO surface.The energy level offset at the organic/organic heterojunction has been proposed to relate to the maximum potential achievable for a solar cell under illumination, however, few experimental observations have been made where both the interface characterization and device performance are presented. Photovoltaic properties are examined in this work with titanyl phthalocyanine used as a novel donor material for enhancement of spectral absorption and optimization of the open-circuit potential. Characterization of the interface between TiOPc and C60 coupled with characterization of the interface between copper phthalocyanine and C60 shows that the higher ionization potential of TiOPc does correlate to greater open circuit potentials.Examination of photovoltaic behavior using equivalent circuit modeling relates the importance of series resistance and recombination to the homogeneity of the solar cell structure.

The research presented in this dissertation explores the possibility of using colloidal indium tin oxide (ITO) nanoparticle solutions to direct write transparent conducting coatings (TCCs), as an alternative route for TCC fabrication. ITO nanoparticles with narrow size distribution of 5-7 nm were synthesized using a non-aqueous synthesis technique, and fabricated into films using spin coating on substrates made from glass and fused quartz. The as-coated films were very transparent (>95% transmittance), but highly resistive, with sheet resistances around 10¹³ Ω/sq . Pre-annealing plasma treatments were investigated in order to improve the electrical properties while avoiding high temperature treatments. Composite RIE treatment recipes consisting of alternating RIE treatments in O₂ plasma and in Ar plasma were able to reduce the sheet resistance of as spin coated ITO films by 4-5 orders of magnitude, from about 10¹³ Ω/sq in as-coated films to about 3 x 10⁸ Ω/sq without any annealing. Plasma treatment, in combination with annealing treatments were able to decrease the sheet resistance by 8-9 orders of magnitude down to almost 10 kΩ/sq , equivalent to bulk resistivity of ~0.67 Ω.cm. Investigation into effectiveness of various RIE parameters in removing residual organics and in reducing the sheet resistance of colloidal ITO films suggested that while reactive ion annealing (RIE) pressure is an important parameter; parameters like plasma power, number of alternating O₂-Ar RIE cycles were also effective in reducing the residual organic content. Impedance spectroscopy analysis of the colloidal ITO films indicated the dominance of the various interfaces, such as grain boundaries, insulating secondary phases, charge traps, and others in determining the observed electrical properties.

Submitted by Mateus Gallucci Masteghin (mgmasteghin@gmail.com) on 2018-06-26T11:25:57Z No. of bitstreams: 1 masteghin_mg_me_araiq_int.pdf: 9325879 bytes, checksum: ad179c16b4a7ebea4933249a05a03ba1 (MD5) / Approved for entry into archive by Ana Carolina Gonçalves Bet null (abet@iq.unesp.br) on 2018-06-28T17:19:59Z (GMT) No. of bitstreams: 1 masteghin_mg_me_araiq_int.pdf: 9325879 bytes, checksum: ad179c16b4a7ebea4933249a05a03ba1 (MD5) / Made available in DSpace on 2018-06-28T17:19:59Z (GMT). No. of bitstreams: 1 masteghin_mg_me_araiq_int.pdf: 9325879 bytes, checksum: ad179c16b4a7ebea4933249a05a03ba1 (MD5) Previous issue date: 2018-06-06 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Nesse trabalho, realizou-se um estudo a fim de compreender os mecanismos de transporte e as interações gás-sólido que ocorrem na superfície de nanoestruturas de SnO, Sn3O4 e SnO2, preparadas em diferentes dispositivos. Com o objetivo de se obter uma melhor compreensão dos fenômenos envolvidos, optou-se por estudar, individualmente e coletivamente (única e mútiplas), as nanofitas de cada uma das três composições, sendo que o primeiro método permite descartar interferências extrínsecas, analisando-se apenas os mecanismos intrínsecos de condução nas nanoestruturas, sem a presença de barreiras de potencias geradas pelo contato semicondutor/semicondutor e, na maioria dos casos, sem o possível contato não-ôhmico metal/semicondutor. Para isso, os materiais foram sintetizados pelo método de redução carbotérmica e, posteriormente, foram caracterizados por DRX, Raman, UV-Vis e MEV-FEG para confirmar a eficácia da síntese, parte fundamental para a obtenção de resultados confiáveis. Os materiais também foram caracterizados em relação à sua resposta como sensor de gás na presença de gases oxidantes e redutores (por exemplo, NO2 e CO) em baixas concentrações (na escala de ppm) e em temperaturas de trabalho entre 100 °C e 350°C, sendo que para atingir tais temperaturas utilizou-se o método convencional de aquecimento e o método de self-heating, sendo o último promissor por não necessitar de fonte externa para realizar o aquecimento, gerando economia de energia e possibilitando maior mobilidade na detecção de vazamentos. As principais novidades deste trabalho são a caracterização individual de nanofitas de Sn3O4 e des micro-discos de SnO como sensor de gás, o estudo da resposta sensora de nanofitas de mesma composição química com diferentes diâmetros (em nano escala), permitindo o cálculo da camada de depleção (comprimento de Debye) para cada estequiometria, e na escolha do método self-heating de aquecimento para o estudo sensor das estruturas de SnO e Sn3O4. Para realizar esses estudos, fabricou-se dispositivos individuais utilizando trilhas interdigitais e eletrodos específicos em um equipamento de feixe duplo (Focused Ion Beam - FIB) equipado para realizar litografia eletrônica. Deste modo, a principal contribuição do trabalho para a literatura será o estudo das interações sólido-gás em materiais termodinamicamente instáveis (SnO e Sn3O4), no estudo de como o gás analito influencia na espessura da camada de depressão (indiretamente, nas propriedades sensoras) e na utilização de um novo método de sensoriamento de gás (self-heating) para estes materiais. Ao final, espera-se que todo este estudo permita o desenvolvimento de materiais sensores com elevada sensibilidade, seletividade, rápido tempo de resposta e capacidade de miniaturização, sendo essa última característica muito importante quando almeja-se futuras aplicações práticas desse material em dispositivos eletrônicos portáteis. / In the following work, it was carried out a study in order to understand the transport mechanisms and the gas-solid interactions that occur on the surface of SnO, Sn3O4, and SnO2 nanostructures, made-up over different devices. As the main goal of a better understanding regarding involved interaction phenomena, it was chosen to study the nanostructures individually (single-element devices) and as multiple structures (carpet mode devices), in which the former allows to discard extrinsic interferences, such as potential Schottky-type barriers as a result of the semiconductor/semiconductor contact, and in the most of the cases when dealing with single-element devices, without the possible metal/semiconductor non-ohmic contact. Thus, the materials were synthesized by the carbothermal reduction method and characterized by XRD, Raman Spectroscopy, UV-Vis light measurements, and SEM-FEG. The materials were investigated as gas sensors, using oxidizing and reducing gases (such as NO2 and CO) in low concentration levels (ppm), and with working temperatures ranging from 100 °C to 300 °C. These working temperatures were reached using the conventional heating and the self-heating methods, the latter being advantageous for not requiring an external source to the heating, resulting in low dissipated power and allowing higher mobility when seeking for in-situ leakage detections. The highlighted contributions from this work are the Sn3O4 nanobelts and SnO micro-disks characterization as single-element gas sensor devices and the study of different diameters of the same material (nanobelts with same oxidation state), that allowed to calculate the depletion layer length (Debye length) for each stoichiometry; besides the use of the self-heating method in the gas sensor study of SnO and Sn3O4. In the end, the author wishes that all the study performed allows the development of gas sensor devices with high sensitivity, selectivity, fast response and recovery times, and the miniaturization capability. / FAPESP: 2015/21033-0 & BEPE-FAPESP: 2017/12870-0

Il y a un intérêt croissant concernant la découverte de nouvelles méthodes commercialement viables pour réaliser des analyses spectro-électrochimiques — combinant des techniques électrochimiques et spectrales. Pour ce faire, nous avons préparé un matériau d'électrode transparent et conducteur, l’oxyde d’indium dopé à l’étain. Nous avons utilisé la technique d’électrofilage conduisant à la formation de fibres très fines avec une surface spécifique élevée. Ces électrodes ont ensuite été recouvertes d'une couche supplémentaire de silice poreuse et fonctionnalisée pour maximiser la surface spécifique et introduire des propriétés de détection supplémentaires. Le dispositif a été utilisé dans la détection du bleu de méthylène qui est un colorant industriel mais également un polluant environnemental. il a été mis en évidence qu’avec l'utilisation d'une telle électrode, il était possible de détecter des concentrations inférieures aux niveaux environnementaux nocifs. Enfin, les électrodes fonctionnalisées ont également été utilisées avec succès pour générer une luminescence plus intense et plus stable, ce qui ouvre de nouvelles perspectives pour la conception de capteurs spectroélectrochimiques / There is a growing interest in finding new and commercially viable methods of performing a spectroelectrochemical analysis which combines electrochemical and spectral techniques. For this purpose, an electrode material that is transparent and conductive needs to be prepared. In this work, such electrode was prepared by electrospinning which is a technique capable of forming very thin fibers with high surface area. Those electrodes were also covered with additional layer of porous and functionalized silica to maximize the surface area and introduced additional sensing properties. This material was used in the detection of methylene blue which is an industrial dye and an environmental pollutant. It was found that using such electrode it was possible to detect concentrations that are smaller than the harmful environmental levels. Finally, the layers were also used with success to generate luminescence which is opening new prospects for the design of spectroelectrochemical sensors

Made available in DSpace on 2016-06-02T20:36:45Z (GMT). No. of bitstreams: 1 5302.pdf: 3050627 bytes, checksum: d14aad95482698e7d39d217f3b9d0922 (MD5) Previous issue date: 2011-11-22 / Universidade Federal de Sao Carlos / In this study, in the first step, Indium tin oxide nanoparticles were synthesized via a non-aqueous route involving the solvothermal treatment of indium (III) acetylacetonate and tin (IV) chloride in polyethylene glycol Mw=1000. The use of microwave heating reduced the reaction time considerably when compared to traditional heating methods. An analysis by transmission electron microscopy (TEM) revealed particles of relatively uniform sizes and shapes. The high crystallinity of the material was observed by high resolution transmission electron microscopy (HRTEM). The nanocristal size founded by count was 5,1nm. A powder X-ray diffraction analysis indicated that all the materials were crystalline. Infrared spectra confirmed the presence of organic material on the nanoparticle surface. By thermogravimetric analysis (TGA) determined that 11.3% of the total mass corresponds to the polymer. Resistivity values below 10-1 Ω.cm were obtained in thin films and pellets, and semiconductor behavior. In the second step, a model to control the covered area of graphene oxide (GO) sheets by ITO nanoparticles was proposed. The method used was add graphene oxide at the synthetic route to obtain pure ITO. The composites were characterized by XRD, FT-IR, TGA and TEM. XRD results for the synthesized materials confirmed the diffraction patterns of ITO in the different composites synthesized. Through the analysis of FT-IR was possible confirm the presence of the polymer formed on the surface of the oxide nanoparticle and functional groups of graphene oxide sheets. The polymer attached on the oxide surface is responsible for the strong interaction between the ITO and graphen oxide sheets. TEM images for the samples with different cover percentage showed the controller achieved with the synthesis proposed. The composite with 100 or 10% of metal oxides covering the sheets surface did not show the presence of nanocrystals out sheets. The percent value of the covered area obtained of 15% founded by image J analisys is near to the calculated value. From this value we can say that the model works well to control the covered area of GO by nanocristals. The electrical resistivity values found are comparable to the pure ITO, however, with a smaller amount of ITO. / Neste estudo, na primeira etapa, nanopartículas de óxido de índio dopado com estanho foram sintetizadas por uma rota não aquosa envolvendo o tratamento solvotermal de acetilacetonato de índio (III) e cloreto de estanho (IV) em polietilenoglicol de massa molecular 1000. O uso de aquecimento auxiliado por microondas reduziu o tempo de reação quando comparado aos métodos tradicionais de aquecimento. A análise por microscopia eletrônica de transmissão (TEM) mostrou partículas com tamanho e forma relativamente uniformes. A alta cristalinidade do material foi observada por microscopia eletrônica de alta resolução (HRTEM). O tamanho dos nanocristais obtidos por contagem foi de 5,1 nm. A análise de difração de Raios-X (DRX) indicou a cristalinidade do material. O espectro de infravermelho (FT-IR) confirmou a presença do material orgânico na superfície das nanopartículas. Pela análise termogravimétrica (TGA) determinou que 11,3% da massa total corresponde ao polímero. Resistividade abaixo de 10-1 Ω.cm foi obtido no filme e na pastilha, com comportamento semicondutor do óxido. Na segunda etapa, um modelo de controlar a área das folhas de óxido de grafeno (OG) coberta por nanocristais foi proposto. O método usado foi adicionar óxido de grafeno à rota de síntese do ITO puro. Os compósitos foram caracterizados por DRX, FT-IR, TGA e TEM. Os resultados de difração de Raios-X confirmaram o padrão de difração do ITO nos diferentes compósitos. Pela análise de FT-IR foi possível confirmar a presença do polímero na superfície das nanoparticulas e os grupos funcionais das folhas de óxido de grafeno. O polímero ligado na superfície do óxido e responsável pela forte interação entre o ITO e as folhas de óxido de grafeno. As imagens de TEM para as amostras com porcentagens de cobertura diferente mostraram o controle alcançado com o método de síntese proposto. Os compósitos com 100% e 10% de óxido metálico cobrindo a superfície das folhas mostraram que não ocorreu a formação de nanopartículas fora das folhas. O valor de 15 % de porcentagem de área coberta obtido é próximo ao valor calculado. A partir deste valor, pode-se dizer que o modelo funciona bem para controlar a área de OG coberta por nanocristais. Os valores de resistividade elétrica encontrados são comparáveis ao ITO puro, no entanto, com uma quantidade menor de ITO.