Soft matter, self-assembled 3D photonic structures such as blue phase liquid crystals have of great interest to the displays industry and are highly desirable as spatial light modulators because of their polarisation independence and fast switching. However, these types of devices suffer from multistep fabrication conditions and require high threshold voltages. To overcome these limitations, two key points were considered: High flexoelectric liquid crystals are capable of uniform 3D self-assembly, with a wide temperature range but have high threshold voltages, whereas, other classes of high dielectric liquid crystals have fast electro-optic response times with low threshold voltages but show poor 3D self-assembly. In this work, new mixture formulations have been devised having both properties in moderation in order to achieve simple yet stable 3D self-assembled blue phases with fast response times at as low as possible applied fields. Dielectric materials were considered from a commercial source whereas, miscible flexoelectric soft materials were synthesised in-house. These synthesised materials were fully characterised. Then mixtures were formulated in commercial high dielectric hosts to study their miscibility, new mesogenic transitions and electro-optic responses in terms of flexoelectric and dielectric properties. The selected mixtures were further investigated for the rapid growth of blue phases and their compatibility with reactive mesogens to form stable blue phases at room temperature. This new formulation of materials has given rise to mixtures and devices which are inherently easy to fabricate allowing the robust and resilient growth of blue phases under an hour in standard laboratory conditions. Furthermore, polarisation independent electro-optic switching has been characterised at fields < 1V micron m-1. For phase modulation studies of these stabilised blue phase devices, phase shift was measured using a modified Young's slit interferometer. The observed results were very promising, with a full 2.5 pi phase shift observed at a field of 9.25 V micron m-1 when compared to earlier reported devices (which required complicated multistep fabrication processes) giving values of full 1.8 pi phase shifts at 20 V micron m-1.

Esta tese de doutorado apresenta os resultados do estudo sistemático das propriedades ópticas das interfaces que aparecem em dispositivos orgânicos atuais emissores de luz ou OLEDs. Estamos interessados no entendimento do papel de cada uma das interfaces metal/polímero e ITO/polímero sobre a emissão da camada orgânica ativa emissora de luz. Para tanto, se fez necessário o domínio de todas as etapas de preparação e caracterização de filmes finos orgânicos, desde a síntese química dos polímeros até a preparação de amostras adequadas que permitissem a realização dos objetivos propostos. Ênfase foi dada aos processos de excitação e de relaxação energética dos portadores de carga (elétrons e buracos) em filmes ultrafinos automontados próximos às interfaces, correlacionando-os direta ou indiretamente com os efeitos de interface. Através do desenvolvimento e domínio de uma nova metodologia de preparação de filmes orgânicos, verificamos que a intensidade da luminescência de um filme de prova ultrafino de poli(p-fenileno vinileno) (PPV) com espessura em torno de 1,5 nm sofre grandes variações em uma extensa região próxima às interfaces metálicas de Au, Al e de ITO (óxido de índio-estanho). Esta camada de prova foi gradualmente separada da interface variando-se de forma controlada a espessura de um filme polimérico espaçador opticamente inerte. O perfil de intensidade da fotoluminescência nas proximidades das interfaces foi determinado em função da distância entre as superfícies estudadas (vidro, quartzo, metálica ou ITO) e a camada de prova emissora de PPV. Duas regiões relacionadas a processos radiativos distintos foram bem estabelecidas para as interfaces metálicas: uma região de extinção, nas proximidades da interface (< 20 nm), onde a luminescência é fortemente suprimida e uma outra de aumento da luminescência entre 20 e 90 nm. A grande variação da intensidade da luminescência observada neste trabalho é explicada considerando efeitos de interferência em uma semicavidade óptica, além dos processos de transferência de energia tipo Förster entre estados do PPV e estados de plásmons superficiais no metal. Verificamos que a distribuição espacial da radiação emitida é profundamente alterada por processos não radiativos de transferência de energia e pelas condições impostas pelas interfaces em uma semicavidade óptica. Modificações da superfície de ITO foram realizadas pelo tratamento acídico com água-régia suave. Nós observamos que a refletividade do ITO é fortemente dependente do tempo do tratamento e da espessura do espaçador. Como nos filmes metálicos, a emissão de um filme de prova de PPV sofre alterações nas proximidades da interface contendo ITO. Aqui, os parâmetros materiais (índice de difração, reflectância e comprimento de onda da emissão), a estrutura de superfície do ITO e os fatores geométricos mostram um papel importante. Cálculos da intensidade da emissão nas proximidades das interfaces descrevem de modo satisfatório os resultados experimentais. Do perfil de intensidade calculado próximo das interfaces, concluímos que a espessura e a posição da camada ativa emissora de luz devem ser otimizadas de modo a coincidir com a região de aumento ou amplificação da luminescência. / This PhD thesis is an extensive study of the optical properties of the interfaces of organic light-emitting devices (OLED’s). In particular, we investigated the influence of interfaces metal/polymer and ITO/polymer on the emission of an active layer in such devices. Therefore, it was necessary to dominate all the processes of fabrication and characterization of the multilayered structures used in the present investigation. We have used a very thin PPV probe layer (1.5 nm) to map the optical properties very near the metal/organic and the Indium-Tin Oxide (ITO)/organic interfaces. A new Spin-Layer-by-Layer method was employed which allowed a control of deposition of layers at the monolayer level. Precise variation of the metal/PPV or ITO/PPV separation over the entire substrate surface was achieved by the deposition of an organic inert spacer layer. The ITO surface modifications were carried out by soft acidic aquaregia treatment. A strong modulation of the probe layer emission was observed near the metal and ITO interfaces. These results are explained by calculations which include competing short range radiationless energy transfer and intensity modulation due effects produced by the optical cavity formed by metal/polymer films/air. At small distances (<20 nm) from interface, collective excitations in the metal act as energy acceptors, which open up an efficient nonradiative channel. Here, material parameters (diffraction index, reflectance and emission wavelength, for example), surface treatment and structure as well as geometrical factors may play an important role.

Esta tese de doutorado apresenta os resultados do estudo sistemático das propriedades ópticas das interfaces que aparecem em dispositivos orgânicos atuais emissores de luz ou OLEDs. Estamos interessados no entendimento do papel de cada uma das interfaces metal/polímero e ITO/polímero sobre a emissão da camada orgânica ativa emissora de luz. Para tanto, se fez necessário o domínio de todas as etapas de preparação e caracterização de filmes finos orgânicos, desde a síntese química dos polímeros até a preparação de amostras adequadas que permitissem a realização dos objetivos propostos. Ênfase foi dada aos processos de excitação e de relaxação energética dos portadores de carga (elétrons e buracos) em filmes ultrafinos automontados próximos às interfaces, correlacionando-os direta ou indiretamente com os efeitos de interface. Através do desenvolvimento e domínio de uma nova metodologia de preparação de filmes orgânicos, verificamos que a intensidade da luminescência de um filme de prova ultrafino de poli(p-fenileno vinileno) (PPV) com espessura em torno de 1,5 nm sofre grandes variações em uma extensa região próxima às interfaces metálicas de Au, Al e de ITO (óxido de índio-estanho). Esta camada de prova foi gradualmente separada da interface variando-se de forma controlada a espessura de um filme polimérico espaçador opticamente inerte. O perfil de intensidade da fotoluminescência nas proximidades das interfaces foi determinado em função da distância entre as superfícies estudadas (vidro, quartzo, metálica ou ITO) e a camada de prova emissora de PPV. Duas regiões relacionadas a processos radiativos distintos foram bem estabelecidas para as interfaces metálicas: uma região de extinção, nas proximidades da interface (< 20 nm), onde a luminescência é fortemente suprimida e uma outra de aumento da luminescência entre 20 e 90 nm. A grande variação da intensidade da luminescência observada neste trabalho é explicada considerando efeitos de interferência em uma semicavidade óptica, além dos processos de transferência de energia tipo Förster entre estados do PPV e estados de plásmons superficiais no metal. Verificamos que a distribuição espacial da radiação emitida é profundamente alterada por processos não radiativos de transferência de energia e pelas condições impostas pelas interfaces em uma semicavidade óptica. Modificações da superfície de ITO foram realizadas pelo tratamento acídico com água-régia suave. Nós observamos que a refletividade do ITO é fortemente dependente do tempo do tratamento e da espessura do espaçador. Como nos filmes metálicos, a emissão de um filme de prova de PPV sofre alterações nas proximidades da interface contendo ITO. Aqui, os parâmetros materiais (índice de difração, reflectância e comprimento de onda da emissão), a estrutura de superfície do ITO e os fatores geométricos mostram um papel importante. Cálculos da intensidade da emissão nas proximidades das interfaces descrevem de modo satisfatório os resultados experimentais. Do perfil de intensidade calculado próximo das interfaces, concluímos que a espessura e a posição da camada ativa emissora de luz devem ser otimizadas de modo a coincidir com a região de aumento ou amplificação da luminescência. / This PhD thesis is an extensive study of the optical properties of the interfaces of organic light-emitting devices (OLED’s). In particular, we investigated the influence of interfaces metal/polymer and ITO/polymer on the emission of an active layer in such devices. Therefore, it was necessary to dominate all the processes of fabrication and characterization of the multilayered structures used in the present investigation. We have used a very thin PPV probe layer (1.5 nm) to map the optical properties very near the metal/organic and the Indium-Tin Oxide (ITO)/organic interfaces. A new Spin-Layer-by-Layer method was employed which allowed a control of deposition of layers at the monolayer level. Precise variation of the metal/PPV or ITO/PPV separation over the entire substrate surface was achieved by the deposition of an organic inert spacer layer. The ITO surface modifications were carried out by soft acidic aquaregia treatment. A strong modulation of the probe layer emission was observed near the metal and ITO interfaces. These results are explained by calculations which include competing short range radiationless energy transfer and intensity modulation due effects produced by the optical cavity formed by metal/polymer films/air. At small distances (<20 nm) from interface, collective excitations in the metal act as energy acceptors, which open up an efficient nonradiative channel. Here, material parameters (diffraction index, reflectance and emission wavelength, for example), surface treatment and structure as well as geometrical factors may play an important role.

Transparent glass-ceramics have been of industrial interest because of their multifarious applications. These are becoming increasingly important because of the flexibility that is associated with this route of fabricating intricate sizes and shapes as per the requirement. A number of glass-ceramics, based on well known ferroelectric crystalline phases (LiNbO3, LaBGeO5, SrBi2Nb2O9, Bi2WO6 etc.) were fabricated and their polar and electro-optic properties were reported. Keeping the potential applications of transparent glass-nano/microcrystal composites in view, attempts were made to fabricate SrBi2B2O7 and CaBi2B2O7 glasses and glass-nano/microcrystal composites. An attempt has been made to employ strontium bismuth borate SrBi2B2O7 (SBBO) as a reactive host glass matrix for growing the nanocrystals of ferroelectric oxides belonging to the Aurivillius family. The in situ nucleation and growth of SrBi2Nb2O9 (SBN) nanocrystals in a reactive SrBi2B2O7-Nb2O5 system and its influence on various physical (dielectric, pyroelectric and optical) properties were investigated. The strategy has been to visualize the formation of nanocrystalline SrBi2Nb2O9 as a result of the simple chemical reaction between glassy SrBi2B2O7 and Nb2O5. Indeed at lower concentrations of Nb2O5 transparent glasses were obtained which upon heat-treatment at appropriate temperatures yielded nanocrystalline SrBi2Nb2O9 phase in a transparent glass matrix. Textured SrBi2Nb2O9 ceramics were obtained by quenching the melts of SrBi2B2O7-Nb2O5 in equimolar ratio and their physical properties were studied. A strong anisotropy in physical properties (which are akin to single crystals) were demonstrated in the textured ceramics.

<p>I papperstillverkning ställs det krav inte bara på kvalité och kvantitet utan också att stickprov från produktion utförs och tas hand om på ett korrekt sätt. Från det att ett stickprov tas ut och undersöks på brukets laboratorium kan en del källor till förändringar på provresultatet uppstå. Sådana förändringar kan uppstå för det första vid hanteringen av stickprov från pappersmaskin och provens transportering till laboratoriet och för det andra vid laboratoriets hantering och uppföljning av kvalitén. En annan faktor som kan påverka stickproven är klimatet. Årstiderna vår och höst är de tider som proverna kan påverkas mest. Prover undersöks med jämna mellanrum från färdigt papper och används till kalibrering av on-line mätning på pappersmaskin. Vissa av provresultaten skickas direkt till kunden i form av ett analyscertifikat.</p><p>I detta examensarbete var syftet att analysera vissa felkällor i provhanteringen och vad klimatet hade för påverkan på provresultatet. Det undersöktes hur varierande klimatförhållanden på pappersmaskin kunde påverka provresultaten för prov som undersöktes direkt på laboratoriet. Resultat från de proven har sen jämförts med prov som konditionerades en tid på laboratoriet i ett fast klimat (23°C, 50 % RH). Prov konditionerades både efter att provet tagits ut direkt och efter att provet hade legat uppe i maskinhallen under en längre tid. I arbetet ingick det att årstider skulle simuleras och det utfördes på Stora Enso Research Center i Falun i ett speciellt klimatrum. Klimaten som papper undersöktes i då var extremt torrt och extremt fuktigt och dessa resultat jämfördes med resultat från normalt provtagningsklimat.</p><p>Papperskvalitéerna som undersöktes var 45 g/m2 standard tidningspapper från PM 11 och 52 g/m2 SC-papper (obestruket journalpapper) från Kvarnsvedens nya maskin PM 12. Det som undersöktes var de kritiska parametrarna där det föreligger risk för att papper måste kasseras. De kritiska egenskaperna som har kassaktionsgräns är ytvikt, ljushet, nyans och i även vissa fall ytråhet och rivstyrka.</p><p>Resultaten visade att vid extrema klimatförhållanden från undersökningen på Stora Enso Research Center hade många prover påverkats till den grad att de hade lett till kassaktion. För SC-papper var ytråheten den egenskap som var mest kritisk vid extremt torrt klimat och vid fuktigt klimat var ytvikt den mest känsliga egenskapen. För standard tidningspapper var ytvikt och rivstyrka de egenskaper som påverkades mest av extremt klimat och pappret hade fått kasseras vid både extremt torrt och fuktigt klimat.</p><p>Vid undersökningen på Kvarnsveden visade resultaten att fukthalten i pappret påverkades mer än vad papprets övriga egenskaper gjorde. Förändringarna i papprets övriga egenskaper var endast marginella och höll sig inom respektive gränsvärde för kassaktion. Nyans och de andra optiska egenskaperna hade marginella förändringar för både varierande och extrema klimatförhållanden och förändringarna kan i de flesta fall anses försumbara för produktionen.</p><p>I de fall där det råder extrema klimatförhållanden som det kan göra vid vissa årstider är det mycket viktigt att operatörens hantering av stickprov sker på ett korrekt sätt. Då gäller det att stickproverna skickas ner till laboratoriet så snabbt som möjligt där påverkan är mindre än vad den kan vara inne i maskinhallen.</p> / <p>In paper production demands are set not only on quality and quantity, but it is also required that samples from the production are taken out and handled in a correct way. From the moment when a sample is taken out and up to the point when it is examined in the laboratory of the mill, a number of factors may affect the sample and thus the test result. Such changes can arise from the handling of samples from the paper machine and the transport of the samples to the laboratory and also from the handling of the samples in the laboratory. Another factor that can influence the samples is the climate and the seasons spring and autumn is the times when the samples are influenced most. Samples are examined with even intervals from finished papers and is used for calibration of on-line measurement on the paper machine and some of the sample results are sent directly to the costumer in the form of an analysis certificate.</p><p>The purpose of this project was to analyze certain error sources in the sample handling and the impact of the climate on the sample result. It was examined how varying climates on the paper machine could influence the sample results for samples that were examined directly and compared with samples that were conditioned for one hour on the laboratory in a permanent climate (23°C, 50% RH). Samples that were conditioned were either taken directly to the lab or left by the paper machine for an extended period of time. In the work, it was included that seasons would be simulated and it was carried out on Stora Enso Research centre in Falun in a climate room. The climates that papers were examined in then were extreme dry and extreme damp and these results were compared with results from normal climate for testing paper.</p><p>The paper qualities that were examined where 45 g/m2 standard newspaper from papermachine 11 and 52 g/m2 SC-paper (uncoated journal papers) from the new papermachine 12 in Kvarnsveden. What were examined were the critical parameters were it exists risk to rejection of papers. The critical properties that have a limit when the papers are rejected are grammage, ISO-brightness and nuance and in certain cases also roughness and tear strength.</p><p>The results showed that at extreme climate relations from the studies on Stora Enso Research centre samples had been influenced to that degree that many of the samples had to be rejected. For SC-paper roughness was the property that was most critical at extremely dry climate and at damp climate the grammage was the most sensitive property. Standard newspaper was very sensitive at both extremely damp and dry climates for grammage and tearing strength.</p><p>The study on Kvarnsveden showed that the moisture content in the paper was influenced more than the other properties but its changes were only marginal and within the respective limit for rejection. Nuance and the other optic properties had only marginal changes for both varying and extreme climates and the changes can in most cases be considered negligible for the production.</p><p>In those cases when there are extreme climates, like during certain seasons, it is very important that the operator handles the samples correctly. Then, it is important that the samples are sent down to the laboratory as fast as possible where the impact is smaller than if the samples stay in the machine room.</p>

I papperstillverkning ställs det krav inte bara på kvalité och kvantitet utan också att stickprov från produktion utförs och tas hand om på ett korrekt sätt. Från det att ett stickprov tas ut och undersöks på brukets laboratorium kan en del källor till förändringar på provresultatet uppstå. Sådana förändringar kan uppstå för det första vid hanteringen av stickprov från pappersmaskin och provens transportering till laboratoriet och för det andra vid laboratoriets hantering och uppföljning av kvalitén. En annan faktor som kan påverka stickproven är klimatet. Årstiderna vår och höst är de tider som proverna kan påverkas mest. Prover undersöks med jämna mellanrum från färdigt papper och används till kalibrering av on-line mätning på pappersmaskin. Vissa av provresultaten skickas direkt till kunden i form av ett analyscertifikat. I detta examensarbete var syftet att analysera vissa felkällor i provhanteringen och vad klimatet hade för påverkan på provresultatet. Det undersöktes hur varierande klimatförhållanden på pappersmaskin kunde påverka provresultaten för prov som undersöktes direkt på laboratoriet. Resultat från de proven har sen jämförts med prov som konditionerades en tid på laboratoriet i ett fast klimat (23°C, 50 % RH). Prov konditionerades både efter att provet tagits ut direkt och efter att provet hade legat uppe i maskinhallen under en längre tid. I arbetet ingick det att årstider skulle simuleras och det utfördes på Stora Enso Research Center i Falun i ett speciellt klimatrum. Klimaten som papper undersöktes i då var extremt torrt och extremt fuktigt och dessa resultat jämfördes med resultat från normalt provtagningsklimat. Papperskvalitéerna som undersöktes var 45 g/m2 standard tidningspapper från PM 11 och 52 g/m2 SC-papper (obestruket journalpapper) från Kvarnsvedens nya maskin PM 12. Det som undersöktes var de kritiska parametrarna där det föreligger risk för att papper måste kasseras. De kritiska egenskaperna som har kassaktionsgräns är ytvikt, ljushet, nyans och i även vissa fall ytråhet och rivstyrka. Resultaten visade att vid extrema klimatförhållanden från undersökningen på Stora Enso Research Center hade många prover påverkats till den grad att de hade lett till kassaktion. För SC-papper var ytråheten den egenskap som var mest kritisk vid extremt torrt klimat och vid fuktigt klimat var ytvikt den mest känsliga egenskapen. För standard tidningspapper var ytvikt och rivstyrka de egenskaper som påverkades mest av extremt klimat och pappret hade fått kasseras vid både extremt torrt och fuktigt klimat. Vid undersökningen på Kvarnsveden visade resultaten att fukthalten i pappret påverkades mer än vad papprets övriga egenskaper gjorde. Förändringarna i papprets övriga egenskaper var endast marginella och höll sig inom respektive gränsvärde för kassaktion. Nyans och de andra optiska egenskaperna hade marginella förändringar för både varierande och extrema klimatförhållanden och förändringarna kan i de flesta fall anses försumbara för produktionen. I de fall där det råder extrema klimatförhållanden som det kan göra vid vissa årstider är det mycket viktigt att operatörens hantering av stickprov sker på ett korrekt sätt. Då gäller det att stickproverna skickas ner till laboratoriet så snabbt som möjligt där påverkan är mindre än vad den kan vara inne i maskinhallen. / In paper production demands are set not only on quality and quantity, but it is also required that samples from the production are taken out and handled in a correct way. From the moment when a sample is taken out and up to the point when it is examined in the laboratory of the mill, a number of factors may affect the sample and thus the test result. Such changes can arise from the handling of samples from the paper machine and the transport of the samples to the laboratory and also from the handling of the samples in the laboratory. Another factor that can influence the samples is the climate and the seasons spring and autumn is the times when the samples are influenced most. Samples are examined with even intervals from finished papers and is used for calibration of on-line measurement on the paper machine and some of the sample results are sent directly to the costumer in the form of an analysis certificate. The purpose of this project was to analyze certain error sources in the sample handling and the impact of the climate on the sample result. It was examined how varying climates on the paper machine could influence the sample results for samples that were examined directly and compared with samples that were conditioned for one hour on the laboratory in a permanent climate (23°C, 50% RH). Samples that were conditioned were either taken directly to the lab or left by the paper machine for an extended period of time. In the work, it was included that seasons would be simulated and it was carried out on Stora Enso Research centre in Falun in a climate room. The climates that papers were examined in then were extreme dry and extreme damp and these results were compared with results from normal climate for testing paper. The paper qualities that were examined where 45 g/m2 standard newspaper from papermachine 11 and 52 g/m2 SC-paper (uncoated journal papers) from the new papermachine 12 in Kvarnsveden. What were examined were the critical parameters were it exists risk to rejection of papers. The critical properties that have a limit when the papers are rejected are grammage, ISO-brightness and nuance and in certain cases also roughness and tear strength. The results showed that at extreme climate relations from the studies on Stora Enso Research centre samples had been influenced to that degree that many of the samples had to be rejected. For SC-paper roughness was the property that was most critical at extremely dry climate and at damp climate the grammage was the most sensitive property. Standard newspaper was very sensitive at both extremely damp and dry climates for grammage and tearing strength. The study on Kvarnsveden showed that the moisture content in the paper was influenced more than the other properties but its changes were only marginal and within the respective limit for rejection. Nuance and the other optic properties had only marginal changes for both varying and extreme climates and the changes can in most cases be considered negligible for the production. In those cases when there are extreme climates, like during certain seasons, it is very important that the operator handles the samples correctly. Then, it is important that the samples are sent down to the laboratory as fast as possible where the impact is smaller than if the samples stay in the machine room.