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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
41

Amélioration du rendement matière lors de la cristallisation de lingots de silicium photovoltaïque multi-cristallin / lmproving the material yield in the crystallization of multi-crystalline photovoltaic silicon ingots

Laurent, Julien 02 December 2014 (has links)
Les lingots de Si-PV élaborés par solidification dirigée en creuset présentent des propriétés électriques dégradées dans les zones en contact avec le creuset (red zones). Dans ce contexte, le travail répond à une double problématique. Tout d’abord nous étudions l’influence de la pureté du creuset sur la qualité du silicium et l’étendue de la red zone, et apportons des éléments de compréhension sur les phénomènes physiques à l’origine de cette dernière. Pour cela, des lingots de taille laboratoire cristallisés dans des creusets de différentes puretés sont analysés électriquement et chimiquement. A partir de la compréhension des mécanismes mis en jeu, la deuxième problématique est de développer un creuset innovant permettant de réduire la pollution du lingot de silicium par le creuset et le revêtement, tout d’abord à l’échelle du laboratoire puis sur des lingots de taille semi-industrielle de 60 kg en vue d’un transfert de technologie à l’échelle industrielle. Des cellules photovoltaïques sont fabriquées à partir de lingots cristallisés dans des creusets en silice frittée utilisés dans l’industrie et des creusets innovants, afin de comparer leurs rendements de conversion et valider les effets bénéfiques du creuset innovant. / The majority of silicon used for PV applications is crystallized via directional solidification in silica crucibles with suitable coatings. The obtained ingots exhibit, however, poor electrical properties near the crucible walls (red zones). Until present, the physical mechanisms leading to this degradation are both unclear and unresolved. This thesis addresses exactly these two points. It analyses the root causes leading to the electrical degradation and it proposes an innovative crucible to limit it. An electrical and chemical quantitative study is performed to determine the influence of the purity of the crucible on the quality of the obtained silicon. Specifically, the extent of the red zone is analyzed in great detail in laboratory-scale ingots crystallized in crucibles of different purity. Once the role of impurities present in the crucible is determined, an innovative crucible is proposed and tested. Its scope is to minimize impurity diffusion from the crucible and its coating to the silicon. As proof of concept, laboratory scale (3 kg) and semi-industrial scale (60 kg) ingots are crystallized in this novel crucible and in a standard, reference crucible. The semi-industrial ingots are further used to fabricate solar cells. Characterization of the solar cells validates the beneficial effects of the innovative crucible with respect to the standard one.
42

Efficiency and stability studies for organic bulk heterojunction solar cells

Augustine, B. (Bobins) 29 November 2016 (has links)
Abstract The qualitative and quantitative characteristics of each component layer constituting the structure of organic bulk heterojunction solar cells (OSC-BHJ) contribute significantly towards its overall performance. One of the prevalent issues resulting in reduced device efficiency is due to the conformational inhomogeneities in the active and buffer layers. The mechanical stress, extended thermal exposure and presence of mutually reactive component layers etc., affects negatively on the device stability. Effective methods to address these issues will be extensively benefited by the industry since the current commercialisation of the technology is hindered owing to the lower efficiency and stability of these devices. This dissertation focuses on methods to coherently enhance the performance and longevity of the OSC-BHJ devices. The efficiency enhancements of the devices in this work were achieved through two main routes. The first route was through morphological improvement of the active layer. The second route was through boosting the electrical characteristics of hole transporting conducting polymer layer (HTL) by controlled annealing conditions. The introduction of a suitable additive in the active layer was found to reduce unfavourable phase segregation thus resulting in enhanced morphology. Further, the annealing conditions in different atmospheres (air, nitrogen and vacuum) were found to have a clear influence on the optimum functioning of the HTL in the device. Regarding the stability improvement study done in this work, a method of employing suitable interlayer was developed to effectively abate the internal degradation occurring in the device due to etching reaction on the indium tin oxide (ITO) anode by the HTL. Moreover, experimental investigations were carried out for drawing fundamental understanding of stability degenerating issues such as the influence of mechanical defects on transparent conducting metal oxide (ITO) anode on the performance of the device and heat induced degradations in the low band gap polymer-fullerene active layer. The highlight of this research is that the discovered methods are inexpensive, efficient, and easy to adopt. The results of the study could help the technology to overcome some of its limitations and accelerate its progress towards commercialisation. / Tiivistelmä Orgaanisten heteroliitosaurinkokennojen kerrosrakenteen ominaisuudet ja laatu vaikuttavat merkittävästi aurinkokennojen toiminnallisuuteen. Erityisesti rakenteelliset epähomogeenisuudet aktiivi- ja puskurikerroksissa heikentävät kennon hyötysuhdetta. Kennojen stabiilisuutta tarkasteltaessa myös mekaanisella rasituksella, pitkittyneellä lämpöaltistuksella ja materiaalien reagoinneilla keskenään kerrosten välillä, on selkeä negatiivinen vaikutus kennojen stabiilisuuteen. Orgaanisen aurinkokennoteknologian kaupallistamisen rajoitteina ovat kennojen heikko hyötysuhde ja stabiilisuus, joten menetelmät jotka tarjoavat ratkaisuja edellä mainittuihin ongelmiin, ovat erittäin tärkeitä teknologiaa kaupallistavalle teollisuudelle. Tämä väitöskirja keskittyy johdonmukaisesti selvittämään tapoja, joilla voidaan parantaa heteroliitosaurinkokennojen hyötysuhdetta ja elinikää. Hyötysuhteen tehostamiseksi valittiin kaksi eri lähestymistapaa, joista ensimmäisessä keskityttiin aktiivikerroksen morfologian parantamiseen ja toisessa aukkoja kuljettavan kerroksen sähköisten ominaisuuksien parantamiseen lämpökäsittelyprosessin avulla. Sopivan lisäaineen avulla aktiivikerroksen ei-toivottua kiteytymistä voidaan pienentää ja parantaa näin kerroksen morfologiaa. Lisäksi työssä todettiin, että lämpökäsittelyn aikaisella ympäristöolosuhteella (ilma, typpi, tyhjiö) on merkittävä vaikutus puskurikerroksen optimaaliseen toimintaan aurinkokennossa. Stabiilisuuden parantamiseksi kehitettiin välikerroksen hyödyntämiseen perustuva menetelmä, jolla voidaan tehokkaasti vähentää kennojen sisäisessä rakenteessa tapahtuvaa toiminnallisuuden heikkenemistä, joka aiheutuu aukkoja kuljettavan kerroksen syövyttävästä vaikutuksesta indiumtinaoksidi (ITO) pohjaiseen anodiin. Tämän lisäksi työssä tutkittiin kokeellisesti stabiilisuuteen heikentävästi vaikuttavia tekijöitä, kuten mekaanisen rasituksen aiheuttamia vaurioita metallioksidi (ITO) anodissa ja lämpöaltistuksesta aiheutuvia vikoja polymeeri-fullereeni rakenteeseen perustuvassa aktiivikerroksessa. Tutkimuksen keskeisin tulos on, että esitellyt keinot aurinkokennojen hyötysuhteen ja stabiilisuuden parantamiseen ovat edullisia, tehokkaita ja helppoja hyödyntää. Tulokset voivat merkittävästi edistää orgaanisten aurinkokennojen teknistä kehitystä ja kiihdyttää niiden tuloa kaupallisiksi tuotteiksi.
43

Consumo, eficiência alimentar e exigências nutricionais de vacas de corte na lactação e terminação / Intake, feed efficiency and nutritional requirements of lactating and fattening beef cows

Tiago Zanetti Albertini 19 January 2007 (has links)
O objetivo deste trabalho foi estimar as exigências e a eficiência energética de vacas de corte lactantes e não gestantes, bem como do par vaca/bezerro. Posteriormente foi correlacionada a eficiência do par vaca/bezerro durante a lactação com a eficiência das mesmas vacas durante a terminação. Na fase de lactação os pares vaca/bezerro foram avaliados desde após o nascimento (17±5, d DP) até a desmama (210 d). Após a desmama foi conduzido o ensaio de terminação (67 d) e abate somente das matrizes. Foram avaliadas 10 vacas adultas ½ Caracu x Nelore (CN) e 10 ½ Angus x Nelore (AN), acasaladas com touros Red Angus (RA) e Canchim (CC), respectivamente. Na lactação o oferecimento da dieta (2,30 Mcal EM/kg e 12,4% PB) variou individualmente ao longo do período com objetivo de manter constante o peso das matrizes ao longo da lactação. A mesma dieta foi oferecida a vontade para a progênie. Durante o ensaio de terminação em confinamento a dieta (2,37 Mcal EM/kg e 10,5% PB) foi fornecida à vontade. A ingestão de matéria seca das matrizes foi de 92,4 g MS/kg PM0,75 (CV=3,2%; P=0,458). Vacas AN apresentaram produção de leite corrigida para gordura 12% superior (P<0,05). A concentração energética do leite (Mcal/kg) das vacas CN foi 9,4% superior (P<0,05). A eficiência (Mcal leite/Mcal EM ingerida) não foi diferente. A exigência de energia metabolizável de lactação (EMl) foi maior (P<0,05) para vacas AN em relação as CN, 90,1 e 74,2 (EMl, kcal EMl/kg PM0,75), respectivamente. Bezerros ½CC¼AN¼NE apresentaram ingestão de energia metabolizável (IEM) proveniente do leite 11,3% (P<0,05) superior. Bezerros ½RA¼CR¼NE foram 10,7% mais eficientes (g GP210d/Mcal IEM leite+dieta sólida). Não houve diferença para eficiência dos pares vaca/bezerro, contudo houve considerável variação individual, onde a eficiência média foi 35,3 g GP210d/Mcal IEM par (CV=11,5%). A eficiência do par foi positivamente relacionada ao ganho do bezerro (r=0,79; P<0,01) e negativamente relacionada à IEM do par (r=-0,58; P<0,05). Vacas CN ao abate apresentaram EGS 29% menor, AOL 13% maior e maior proteína no corpo vazio (P<0,05). Vacas AN apresentaram 14,7% maior proporção de órgãos internos relativo ao peso vazio e maior peso dos intestinos (P<0,01). As correlações fenotípicas demonstraram associação entre as eficiência de secreção do leite das vacas nas fase de lactação e de ganho de peso na fase de terminação (r=0,43; P=0,09). A eficiência de secreção de leite das vacas na lactação apresentou correlação com a eficiência do par (r=0,68; P<0,01). O consumo alimentar residual (CAR) das vacas na terminação foi correlacionado com o CAR das vacas em lactação (r=0,53; P<0,05) e com o CAR dos pares (r=0.62; P<0.01). Isso indica que vacas de corte mais eficientes durante a terminação são também mais eficientes no período de cria. / This study estimated the requirements and feed efficiency of non-pregnant lactating beef cows, as well as cow calf pairs. It also correlated the efficiency of the cows and their progeny during lactation to efficiency determined for the same cows in a finishing trial after weaning. In the lactating phase cow calf pairs were evaluated from just after birth (17±5, d) to weaning at 210 d. The finishing trial for the mature cows started after weaning and lasted 67 d after wich cows were slaughtered. Twenty adult cows were evaluated, 10 ½ Caracu x Nelore (CN) and 10 Angus x Nelore, bred to Red Angus (RA) and Canchim (CC) bulls, respectively. During lactation the diet (2.30 Mcal ME/kg and 12.4% CP) was offered in variable amounts to maintain individual live weight and condition score constant. The same diet was offered ad libitum to the calves. During the finishing phase cows were fed ad libitum (2.37 Mcal ME/kg e 10.5% CP). The dry matter feed intake of cows was 92,4 and SD 2,9 g DM/kg BW0,75. AN cows had fat corrected milk 12% higher compared to CN cows (P<0.05). However, milk energy content (Mcal/kg) was 9.4% higher (P<0.05) for CN cows. Efficiency of milk production (Mcal milk/Mcal ME intake) was not different. Metabolizable energy for lactation (MEl) was higher (P<0.05) for AN cows in comparison to CN, respectively 90.1 and 74.2 (MEl, kcal MEl/kg BW0,75). ME milk intake was 11.3% (P<0.05) higher for ½CC¼AN¼NE calves. Rates of gain were not different between calves, but ½RA¼CR¼NE were 10.7% more efficient (g LWG210d/Mcal MEI milk+solid diet). There was no difference in cow calf pairs efficiency, but there was a great individual variability with a mean of 35,31 g and SD of 4,08 g LWG210d/Mcal EM for the pair. Cow/calf pair efficiency was positively related to calf weight gain (r=0.79; P<0.01) and negatively to the pair metabolizable energy intake (r=-0.58; P<0.05). At slaughter CN cows presented backfat thickness 29% lower, longissimus muscle area 13% higher and higher empty body weight protein (P<0,05). AN cows had 14.7% higher relative internal organ weight and higher total intestine weight (P<0.01). The phenotypical correlations between efficiency indexes indicate moderate association between cow efficiency measured during lactation and in a short finishing period after weaning (r=0.43; P=0.09). Exist correlations between cow efficiency lactation and efficiency of the pair (r=0.68; P<0.01). Residual Feed Intake (RFI) during the finishing phase was moderately correlated to the RFI calculated during the lactation period for the cow calf pairs RFI (r=0.62; P<0.01) and the cows (r=0.53; P<0.05) indicated that beef cows more efficient in feed conversion during the finishing phase are more efficient during the lactation period.
44

Pasivace aktivní vrstvy perovskitových solárních článků s invertovanou strukturou / Passivation of the active layer in perovskite solar cells with inverted architecture

Babincová, Kristina January 2021 (has links)
The topic of this work is the passivation of the active layer of perovskite solar cells with an inverted structure. The work is divided into theoretical and experimental part. The theoretical part describes in particular the passivation and modification of the perovskite layer as well as the characteristic properties of perovskite, including structure and stability. The experimental part deals with the preparation of photovoltaic cells with an inverted structure. For the characterization of photovoltaic cells, reference samples were prepared and their active layer was modified by plasma. The most used deposition technique for the preparation of layers was the spin coating method. From the performed experiments it can be concluded that the preparation of samples and their subsequent modification under laboratory conditions does not lead to the improvement of the final parameters of photovoltaic conversion. By transferring the sample preparation and passivation of the active layer to an inert atmosphere, it was possible to produce cells with higher efficiencies (compared to the reference sample), around 10 %. Another advantage of this plasma treatment of the active layer is that it also improves the stability of the prepared structures, which even after a few days in air show almost 80 % of the original efficiency.
45

Elektrické a dielektrické vlastnosti organických materiálů pro fotovoltaické aplikace / Electric and dielectric properties of organic materials for photovoltaic applications

Florián, Pavel January 2014 (has links)
Diploma thesis deals with the use of organic materials in photovoltaic applications and the study of their electric and dielectric properties. The theoretical part of thesis deals issue of the use of organic polymeric materials in photovoltaics and their advantages and disadvantages. Next are the results of various studies of organic solar cells by other authors. In the practical part of the work are shown experimental results (volt-ampere characteristics and impedance spectra) of samples of organic semiconductors and their evaluation.
46

Efektivnost provozu fotovoltaických generátorů / Operational efficiency of photovoltaic generators

Koval, Filip January 2008 (has links)
Objective of master’s thesis theoretical part is especially to illustrate influence of operation conditions, such as solar radiation, temperature or pollution of photovoltaic generator active area, on load and power characteristics of photovoltaic generator, or more precisely on photovoltaic conversion efficiency. Possible variants of increasing effectivity of using photovoltaic generator are explored, such as solar radiation concentration, photovoltaic generator active area cooling or aplication of optimalization circuit. Pivotal part of master‘s thesis is focused on experimental device practical realisation, concretely type MSQ36-10 photovoltaic generator with oriented concentrators of solar radiation. Practical realisation includes design of master‘s thesis experimental part construction with subsequent design of photovoltaic generator motion cycle necessary for adequate simulation of configuration variants solved using single testing photovoltaic generator. Description of own experimental device construction with list of measuring places used in task takes up. It is used automatic monitoring system working as independent measurement task for required values measuring and consecutive data collecting. It is done in two phases. First phase is measurement of all required values, in second phase measurement with attached optimalization circuit is made. Optimalization circuit sets best working point of photovoltaic generator according to actual working conditions. Master‘s thesis intention is experimental verification of solar radiation concentrators application convenience, orientation of photovoltaic generator or its mutual combination, namely using type MSQ36-10 photovoltaic generator. Objective is evaluation of reached energetic gain for all experimental device layouts in variable operating conditions.
47

Predicting Treatment Performance Using Ternary Plot : Macronutrients’ impact on biomass conversion efficiency

Gobl, Madeleine January 2022 (has links)
Black soldier fly larvae (BSFL) waste treatment is becoming a more sought-after organic waste treatment since it produces larvae for animal feed as well as fertilizer, the need for prediction and optimization of treatment performance increases. This study aims to predict biomass conversion efficiency (BCE) for waste going into treatment, using only the nutritional data from other studies as it could give a good performance estimation while using available data. First, macronutrient fractions, based on a normalized total weight of volatile solids (VS), were calculated from nutritional data of other studies and of this present study.  Using the results, coordinates of these samples were calculated and put on the ternary plot, revealing trends for different macronutrient compositions. To validate these trends, selected nutrient compositions were created as waste mixtures containing fish, bread and vegetable waste and then treated by BSFL. After treatment, BCE and waste reduction in both VS and wet weight basis were noted.  The results showed that a composition high in carbohydrate and low in fat content is favorable for a high BCE value while protein content remained similar across all treatments and only seemed to slightly increase BCE. Treatment A5 held the highest BCE%VS (32.6 ± 3.5) with a composition of 73%VS carbohydrates, 19%VS protein and 8%VS fat and control treatment (A0) with no fish waste held the highest BCE%WW  (21.2 ± 1.8).   When comparing with the results of the other studies used to make the trends in the ternary plot, predictions of BCE were more accurate for a composition  of  70%VS carbohydrates, 20-25%VS protein and &lt; 8%VS fat and also for compositions with similar waste substrates, as their percental changes were similar. This suggests that it is possible to predict high BCE  values from nutritional data in a ternary plot and could be of use when optimizing larval production. / Fluglarvskompostering med den amerikanska vapensflugan (Hermetia illucens) är en avfallsbehandling för organiskt avfall som producerar larver och gödselmedel som kan används som djurfoder respektive gödselmedel.  Många studier har undersökt hur makronäringsämnen påverkar larvproduktion eller behandlingseffektiviteten och kommit till olika resultat. I dagens läge skulle det underlätta om man kunde uppskatta den högsta möjliga effektiviteten baserat på data om avfallet som redan finns utan att behöva gå igenom en längre studie först. Den här studien har som syfte att undersöka om det är möjligt att förutspå biomassomvandlings-effektivitet (BCE) från makronäringsdata tagen från andra studier i ett triangulärt diagram. I denna studie användes studierna av Lopes et al., (2020) och Isibika et al., (2021) som basdata i triangulär diagrammet.  För att validera det trender som sågs i det triangulära diagrammet utfördes tester på valda kompositioner beståendes av ansjovis, bröd och grönsaksavfall med fluglarvkompostering. För att kunna applicera makronäringsämnernas data till triangulär diagrammet, beräknades mängden protein, kolhydrater och fett som en andel av den totala mängden glödförlust (VS).  Efter behandling beräknades BCE på våtvikt (WW) och VS basis.  Resultaten tyder på att en avfallskomposition med hög halt kolhydrater och låg halt fett (70%VS kolhydrater, 20–25%VS protein and &lt;8%VS fett) bidrog till ett högt BCE värde, där proteinhalten var snarlik i alla behandlingar och verkade ha ett litet bidrag till ett högt BCE värde. Behandlingen A5 hade det högsta BCE%VS värdet (32.6 ± 3.5) med en komposition av 73%VS kolhydrater, 19%VS protein och 8%VS fett och kontroll behandlingen A0 (utan ansjovis avfall) hade högst BCE%WW värde (21.2 ± 1.8).   Vid jämförelse mellan de andra studierna och resultaten, var uppskattningar av BCE mer precisa för en komposition med ca 70%VS kolhydrater, 20–25%VS protein and &lt;8%VS fett och för uppskattningar baserad på data från rapporter med liknande avfallssubstrat, då deras procentuella förändringar var liknande varandra. Detta stärker hypotesen att det är möjligt att kunna förutspå högt BCE värde med hjälp av näringsdata från avfallet och skulle kunna användas för att optimera av larvproduktion.
48

Solid-State NMR Characterization of the Structure and Morphology of Bulk Heterojunction Solar Cells

Baughman, Jessi Alan 20 August 2012 (has links)
No description available.
49

Beyond "More than Moore": Novel applications of BiFeO3 (BFO)-based nonvolatile resistive switches / Neuartige Anwendungen des BiFeO3 (BFO)-basierten nichtflüchtigen Widerstandsschaltern

Du, Nan 27 May 2016 (has links) (PDF)
The size reduction of transistors has been the main reason for a successful development of semiconductor integrated circuits over the last decades. Because of the physically limited downscaling of transistors, alternative technologies namely the information processing and nonvolatile resistive switches (also termed memristors) have come into focus. Memristors reveal a fast switching speed, long retention time, and stable endurance. Nonvolatile analog bipolar resistive switching with a considerable large On/Off ratio is reported in BiFeO3 (BFO)-based resistive switches. So far resistive switches are mainly applied in memory applications or logic operations. Given the excellent properties of BFO based memristors, the further exploration of functionalities for memristive devices is required. A new approach for hardware based cryptographic system was developed within the framework of this dissertation. By studying the power conversion efficiencies on BFO memristor at various harmonics, it has been shown that two sets of clearly distinguishable power ratios are achievable when the BFO memristor is set into high or into low resistance state. Thus, a BFO-based binary encoding system can be established. As an example the unrecoverable seizure information from encoded medical data suggests the proper functioning of the proposed encryption system. Aside from cryptographic functionality, the single pairing spike timing dependent plasticity (STDP) in BFO-based artificial synapses is demonstrated, which can be considered as the cornerstone for energy-efficient and fast hardware-based neuromorphic networks. In comparison to the biological driven realistic way, only single one pairing of pre- and postsynaptic spikes is applied to the BFO-based artificial synapse instead of 60-80 pairings. Thus, the learning time constant of STDP function can be reduced from 25 ms to 125 us. / In den letzten Jahrzehnten war die Größenreduktion von Transistoren einer der Hauptgründe für die Leistungssteigerung von integrierten Halbleiterschaltungen. Aufgrund des physikalisch beschränkten Skalierungspotentials, werden alternative Technologien für Halbleiterschaltungen entwickelt. Dazu zählen neuartige Widerstandsschalter, sogenannte Memristoren, welche wegen ihrer schnellen Schaltgeschwindigkeit, langen Speicherzeit und stabilen Haltbarkeit in den Fokus der Forschung gerückt sind. Das nichtflüchtige analoge bipolare Schalten des Widerstandwertes mit einem On/Off Verhältnis größer als 100 wurde in BiFeO 3 (BFO)-basierten Widerstands-schaltern beobachtet. Bisher wurden Widerstandsschalter hauptsächlich als Speicher oder in rekonfigurierbaren Logikschaltungen verwendet. Aufgrund der ausgezeichneten Eigenschaften von BFO-basierten Memristoren, ist die Untersuchung weiterer neuer Funktionalitäten vielversprechend. Als neuer Ansatz für ein Hardware-basiertes Kryptosystem wird in der vorliegenden Arbeit die Ausnutzung des Leistungsübertragungskoeffizienten in BFO Memristoren vorgeschlagen. Mit Hilfe der unterschiedlichen Oberschwingungen, welche von einem BFO Memristor im ON und OFF Zustand generiert werden, wurde ein Kryptosystem zum Kodieren binärer Daten entwickelt. Ein Test des Hardware-basierten Kryptosystems an Biodaten ergab, dass die kodierten Biodaten keine vorhersagbare Korrelation mehr enthielten. In der vorliegenden Arbeit wurden darüberhinaus BFO-basierte künstliche Synapsen mit einer Aktionspotentials-Intervall abhängigen Plastizität (STDP) für Einzelpulse entwickelt. Diese Einzelpuls-STDP legt den Grundstein für energieffiziente und schnelle neuromorphe Netzwerke mit künstlichen Synapsen. Im Vergleich zu biologischen Synapsen mit einer 60-80-Puls-STDP und einem Lernfenster auf der ms-Zeitskale, konnte das Lernfenster von BFO-basierten künstlichen Synapsen von 25 ms auf 125 μs reduziert werden. Solch ein schnelles Lernen ermöglicht auch die extreme Reduzierung des Leistungsverbrauchs in neuromorphen Netzwerken.
50

Síntese e caracterização de filmes de óxidos metálicos nanoparticulados para aplicação em células solares sensibilizadas por corante (DSCs)

Paula, Leonardo Ferreira de 29 April 2014 (has links)
In this work, thin and compact films of TiO2, Nb2O5 and WO3 nanoparticles were prepared to be used as contact/blocking layer in dye sensitized solar cells (DSCs). The films were produced by deposition of 30 bilayers of TiO2(ac)/TiO2(bas), TiO2(ac)/Nb2O5(bas) and TiO2(ac)/WO3(bas) using the layer-by-layer technique (LbL) from nanoparticle sols of TiO2 (pH = 2 and 10), Nb2O5 (pH = 10) and WO3 (pH 10) prepared by sol-gel method. The TiO2/TiO2 and TiO2/Nb2O5 underlayers resulted in an increase of 25% and 87% respectively, in the efficiency of DSCs when compared to those without the contact/blocking layers. The application of TiO2/WO3 films did not result in any improvement of DSC efficiency. Factors such as thickness, nanoparticles homogeneity, oxides concentration on the films and roughness directly influence on the efficiency of such films as contact/blocking layer. Field Emission Scanning Electron Microscopy (FESEM) and Atomic Force Microscopy (AFM) images, confirmed that all films are constituted by spherical nanoparticles with homogeneous diameters smaller than 20 nm, resulting on compact and low porous surfaces. This morphology ensures a physical barrier between the electrolyte and the conductive glass used as electrode in DSCs. The TiO2/TiO2 and TiO2/Nb2O5 films also exhibited higher roughness than the surface of the conductive glass without the bilayers, which increases the interaction with the mesoporous TiO2 film. The molar ratios of the species present on the films are controlled by the pH employed during deposition, and were determined by X- ray photoelectron spectroscopy (XPS). The Ti4+/Nb5+ and Ti4+/W6+ ratios were 1.6 and 19 respectively, which evidences a higher concentration of TiO2 nanoparticles on the films. For a better understanding of the role of the bilayers on the charge transfer processes, the substrates were analyzed by Electrochemical Impedance Spectroscopy (EIS). The electronic properties of the oxides also influence the efficiency of the LbL films as contact/blocking layers. Due to its higher band gap, Nb2O5 nanoparticles impose an electronic barrier to the electrons transfer from the conductive substrate to the electrolyte, additionally to the physical barrier. / Neste trabalho foram preparados filmes finos e compactos de óxidos nanoparticulados de TiO2, Nb2O5 e WO3 para a aplicação como camada de contato/bloqueio em células solares sensibilizadas por corante (DSCs). Os filmes foram produzidos pela deposição de 30 bicamadas de TiO2(ác)/TiO2(bás), TiO2(ác/Nb2O5(bás) e TiO2(ác)/WO3(bás) utilizando a técnica de automontagem (Layer-by-Layer ou LbL), a partir dos sóis nanoparticulados de TiO2 (pH = 2 e 10), Nb2O5 (pH = 10) e WO3 (pH = 10) sintetizados pelo método sol-gel. A presença das bicamadas de TiO2/TiO2, TiO2/Nb2O5 gerou aumentos relativos na eficiência das DSCs de 25% e 87% respectivamente, quando comparadas às DSCs sem as bicamadas. Já o filme de TiO2/WO3 não gerou nenhuma melhoria na eficiência das DSCs. Fatores como a espessura, homogeneidade das nanopartículas, concentração dos óxidos nos filmes e a rugosidade influenciam diretamente na eficiência dos filmes como camada de contato/bloqueio. Imagens de Microscopia Eletrônica de Varredura com Emissão de Campo (MEV-FEG) e Microscopia de Força Atômica (MFA) confirmaram que todos os filmes apresentaram nanopartículas esféricas com diâmetros homogêneos e menores que 20 nm, o que acarreta na formação de superfícies compactas e pouco porosas. Esta morfologia garante uma barreira física entre o eletrólito e a superfície do vidro condutor utilizado como eletrodo nas DSCs. Os filmes de TiO2/TiO2 e TiO2/Nb2O5 apresentaram também rugosidades maiores que a da superfície do vidro condutor sem as bicamadas, o que aumenta a interação entre com o filme de TiO2 mesoporoso. As razões molares das espécies presentes nos filmes são controladas pelo pH empregado durante as deposições, e foram determinadas por Espectroscopia de Fotoelétrons Excitados por raios-X (XPS). As razões Ti4+/Nb5+ e Ti4+/W6+ foram de 1,6 e 19 respectivamente, o que evidencia uma maior quantidade de nanopartículas de TiO2 nos filmes. Para melhor entender o papel das bicamadas nos processos de transferência de cargas, os substratos foram analisados por Espectroscopia de Impedância Eletroquímica (EIE). As propriedades eletrônicas dos óxidos também influenciam na eficiência dos filmes automontados como camada de contato/bloqueio. Devido ao seu maior valor de band gap, as nanopartículas de Nb2O5 impõem, além de uma barreira física, uma barreira eletrônica para a transferência dos elétrons do substrato condutor para o eletrólito. / Mestre em Química

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