Made available in DSpace on 2014-10-09T12:26:40Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:23Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:51:12Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:53Z (GMT). No. of bitstreams: 0 / Neste trabalho investigou-se o comportamento sistemático do campo hiperfino magnético nos compostos intermetálicos Gd(Ni,Pd,Cu)In , Tb(Ni,Pd)In, Dy(Ni,Pd)In e Ho(Ni,Pd)In, com a técnica de Correlação Angular γ-γ Perturbada, nos sítios dos elementos terras raras com o núcleo de prova 140Ce e no sítio do In com o núcleo de prova 111Cd. Os resultados obtidos da dependência com a temperatura do Campo Hiperfino Magnético (Bhf) de cada composto foram primeiramente comparados com a teoria do campo molecular por meio da função de Brillouin, da qual foram extrapolados os valores de saturação de Bhf para cada composto estudado. Os valores extrapolados a zero Kelvin de Bhf (Bhf(T=0)) para os compostos estudados neste trabalho foram usados na comparação com valores de Bhf da literatura para outros compostos contendo o mesmo elemento R (R=Terra Rara). O resultado mostrou uma dependência linear com a temperatura de ordenamento magnético, o mesmo previsto pelo modelo RKKY o que indica que a principal contribuição para Bhf vem da polarização dos elétrons de condução (CEP) via interação de contato de Fermi. O comportamento de Bhf saturado para cada família de compostos de terras raras pesados RNiIn e RPdIn como função da projeção do spin 4f do elemento R mostrou também uma relação linear, com exceção dos resultados para os compostos RNiIn obtidos com 111Cd onde foi observado um leve desvio da linearidade. Foi feita uma investigação dos parâmetros hiperfinos elétricos em função da temperatura para os compostos RPdIn e GdNiIn com o núcleo de prova 111Cd, e os resultados mostram que para o composto GdPdIn pode ocorrer desordem Gd-In a altas temperaturas. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:26:40Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:23Z (GMT). No. of bitstreams: 0 / O presente trabalho estudou os efeitos das intera»c~oes hiper¯nas em dois sistemas de ¶oxidos: RCoO3 (R = Gd e Tb) com estrutura perovskita e ¯lmes ¯nos monocristalinos de HfO2 por meio da t¶ecnica de Correla»c~ao Angular Gama-Gama Perturbada (CAP), com o objetivo de fazer um estudo sistem¶atico do comportamento da varia»c~ao do gradiente de campo el¶etrico em fun»c~ao da temperatura. Para realiza»c~ao das medidas de intera»c~oes de quadrupolo el¶etrico utilizamos como de pontas de prova os n¶ucleos 111In ¡!111 Cd e o 181Hf ¡!181 Ta. As amostras de perovskitas foram confeccionadas por meio de um processo qu¶³mico denominado Sol-Gel e as an¶alises foram realizadas com aux¶³lio de difra»c~ao de raios-X. As pontas de prova foram inseridas nas solu»c~oes qu¶³micas durante o preparo das amostras. Os ¯lmes ¯nos foram fornecidos pelo Laborat¶orio de Intera»c~oes Hiper¯nas da Universidade de Lisboa e a ponta de prova de 181Hf foi ativada por meio da irradia»c~ao do ¯lme ¯no no reator IEA-R1 do IPEN no tempo adequado a espessura do ¯lme. As medidas foram realizadas na faixa de temperatura de 10 - 1560 K. Os resultados das medidas das amostras de perovskita indicam uma depend^encia do GCE com o s¶³tio de ocupa»c~ao dos ¶atomos da ponta de prova e uma varia»c~ao do GCE com a temperatura, que pode ser explicada por transi»c~oes de spins no ¶atomo de Co. As medidas do GCE dos ¯lmes ¯nos com mesma espessura apresentam uma segunda fra»c~ao, al¶em daquela correspondente a freqÄu^encia da HfO2 em amostras de bulk. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Conselho Nacional de Desenvolvimento Científico e Tecnológico / Indium(III) benzenechalcogenolates (chalcogen = sulfur, selenium) prepared from elemental indium and diphenyl dichalcogenide provide an alternative synthetic route to produce carbon-chalcogen bonds. These compounds promote the regioselective hydrochalcogenation of terminal aminoalkynes to produce the Markovnikov adducts; provide a pratical method to prepare organyl phenyl chalcogenides from organyl halides; and their reaction with vinylarenes in aqueous media produces the respectives β-hydroxy selenides. Ditellurides present a different performance compared to others studied dichalcogenides. Indium(I) salts react with tellurium compounds and through extrusion of one tellurium atom produce diaryl tellurides. This work presents new synthetic methodologies and discusses the general aspects and limitations of indium chalcogenolates in the different systems investigated. / Fenilcalcogenolatos de índio(III) (calcogênio = enxofre e selênio), preparados a partir de índio metálico e difenil dicalcogenetos, são uma alternativa em síntese para geração de ligações carbono-calcogênio. Estes compostos promovem a hidrocalcogenação Markovnikov de alquinilaminas terminais com rigorosa regiosseletividade; conduzem, de modo prático, ao preparo de organil fenilcalcogenetos frente a haletos orgânicos; e na reação com estirenos possibilitam a síntese de β-hidroxisselenetos em meio aquoso. Já os diteluretos empregados apresentam comportamento diferenciado em relação aos demais dicalcogenetos estudados. A reação de sais de índio(I) com os compostos de telúrio conduzem a extrusão de telúrio e a obtenção de diaril teluretos. O trabalho desenvolvido, além de apresentar novas metodologias sintéticas, discute as generalidades e limitações dos calcogenolatos de índio nos diferentes sistemas investigados.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / This work is composed of two parts. The first one describes the synthesis of organometallic compounds derived from Br2InCH2Br and dichalcogenoether ligands, RE(CH2)nER (E = Se, Te; n = 1, 3; R = Ph, p-C6H4NMe2), compounds 1 to 6, that are considered chemical intermediates with potential application in organic synthesis; and the second part describes the preparation of a series of InIII-E-MI ternary clusters (E = S, Se; MI = Cu, Ag; compounds 7 11), which show potential applications as semiconductors or photocatalysts. In the first part, bimetallic compounds Br3InCH2E(R)(CH2)nE(R)CH2InBr3 were obtained where n = 3, E = Se, Te e R = Ph, p-C6H4NMe2 (compounds 1, 3 and 6). Where n = 1, the compounds obtained have only one InIII atom, Br3InCH2E(Ph)CH2EPh (compounds 2 and 4); and also the bimetallic compound Br3InCH2Te(Ph)CH2Te(Ph)CH2InBr3 (5) could be obtained. Compounds 1 6 were characterized by Nuclear Magnetic Resonance of the corresponding chalcogen, and by Mass Spectrometry. In the second part, the InIII-E-MI ternary clusters (E = S, Se, MI = Cu, Ag) were synthesized from indium(III) chalcogenolates: In(EPh)3 (compounds 7 10) or BrIn(p-SeC6H4NMe2)2 (compound 11). Compounds 7 to 11 were characterized by X-ray Diffraction, Infrared Spectroscopy, and had their optical band gaps evaluated, in the solid state, by Ultraviolet/Visible Spectroscopy. Finally, compound 9 was used as sensitizing agent of TiO2, and used as photocatalyst to obtain hydrogen by visible light induced water splitting. The sensitizing process of TiO2 with compound 9 improved considerably the H2 evolution when compared with the use of pure TiO2 in the studied conditions. / Este trabalho é composto por duas partes: a primeira trata da síntese de compostos derivados do organometálico Br2InCH2Br com ligantes dicalcogenoéteres, RE(CH2)nER (E = Se, Te; n = 1, 3; R = Ph, p-C6H4NMe2), compostos 1 a 6, considerados intermediários químicos com potencial aplicação em síntese orgânica; a segunda parte trata do preparo de uma série de clusters ternários InIII-E-MI (E = S, Se; MI = Cu, Ag; compostos 7 11), com potencial aplicação como semicondutores ou fotocatalisadores. Na primeira parte, compostos bimetálicos do tipo Br3InCH2E(R)(CH2)nE(R)CH2InBr3 são obtidos quando n = 3, E = Se, Te e R = Ph, p-C6H4NMe2 (compostos 1, 3 e 6). Já quando n = 1, são obtidos compostos com apenas um átomo de InIII, Br3InCH2E(Ph)CH2EPh (compostos 2 e 4); e também o composto bimetálico Br3InCH2Te(Ph)CH2Te(Ph)CH2InBr3 (5). Os compostos 1 6 foram caracterizados por Ressonância Magnética Nuclear do calcogênio correspondente e por Espectrometria de Massas. Na segunda parte, os clusters ternários InIII-E-MI (E = S, Se, MI = Cu, Ag) são obtidos a partir de calcogenolatos de índio(III): In(EPh)3 (compostos 7 10) ou BrIn(p-SeC6H4NMe2)2 (composto 11). Os compostos 7 a 11 foram caracterizados por difração de raios X em monocristal, Espectroscopia Vibracional na região do Infravermelho e tiveram seus band gaps óticos avaliados, no estado sólido, através de Espectroscopia Ultravioleta/Visível. Por fim, o composto 9 foi utilizado como agente sensibilizador do TiO2 e testado como fotocatalisador da fotólise da água utilizando a luz visível para geração de hidrogênio. A sensibilização do TiO2 com o composto 9 aumentou consideravelmente a produção de H2 quando comparada a utilização do TiO2 puro nas condições estudadas.

Pour réaliser des fonctions électroniques sur support souple, le transistor en couches minces (TFT) est indispensable. Cette thèse a pour objectif d’approfondir les connaissances sur ces dispositifs.L’état de l’art est synthétisé dans le chapitre 1. Cette partie présente tout d’abord les TFT et justifie l’utilisation de l’oxyde d’indium gallium zinc (IGZO). Ensuite les propriétés de cet oxyde semi-conducteur amorphe sont traitées ; et enfin le chapitre fait état des résultats obtenus avec des TFT en IGZO.Le chapitre 2 établie un lien entre les propriétés de l’IGZO et le dépôt par pulvérisation cathodique. L’étude des films a été réalisée par ellipsométrie spectroscopique. Celle-ci a mis en évidence des variations dans les propriétés optiques dues au temps de dépôt, à la concentration en oxygène et à la position sur le substrat. Ces résultats ont été comparés à des mesures de résistivité, pour comprendre plus précisément la cause de ces variations.Le chapitre 3 élabore un procédé complet permettant de réaliser des TFT sur support souple. Le choix des différents matériaux est discuté, et les différents outils de procédés sont adaptés afin de réaliser ces dispositifs. Les TFT obtenus sont caractérisés en fonction du temps de recuit et sous flexion. Ils ont atteint des mobilités 10 cm².V-1.s-1.Le chapitre 4 étudie le dépôt d’IGZO par impression jet d’encre. Une encre a été formulée et les différents paramètres d’impression ajustés. Afin de comparer les différentes techniques de dépôt, des TFT avec canal en IGZO imprimé ont été réalisé et les films imprimés ont été caractérisé par ellipsométrie spectroscopique. Ces dispositifs ont atteint des mobilités de 0,4 cm2.V-1.s-1. / In order to carry out electronics functions on flexible substrate, thin film transistor is essential. The aim of this thesis is to increase knowledge on this device.State of art of IGZO TFT is summarized in chapter 1. This part presents thin film transistor and justify the choice of IGZO as the semiconductor material. Then, properties of this amorphous oxide semiconductor are discussed. Finally, this chapter presents the results obtained in the literature for IGZO based thin film transistor.Chapter 2 establishes a link between IGZO properties and sputtering deposition. Films are studied by spectroscopic ellipsometry. Experiments show variations in optical properties due to deposition time, oxygen content and position on the wafer. Resistivity measurements are carried out to understand more deeply the causes of these variations.Chapter 3 develops a complete process to achieve TFT on flexible substrate. The choice of different materials and processes is discussed. The performances of the TFT are investigated versus the annealing time and characterized under mechanical stress. Mobility up to 10 cm2.V-1.s-1 can be achieved after an annealing at 300°C during 1h30. Mechanical stresses show a degradation of the transistor induced by cracks in the oxide layer.Chapter 4 focuses on IGZO's deposition by inkjet printing. An ink is formulated using metallic salts and a solvents mixture. The parameters of the printing system are also optimized. To compare the different techniques of deposition, printed IGZO TFTs are characterized and compared with the one fabricated with the standard PVD deposition technique. Mobility is relatively lower and equals 0.4 cm2.V-1.s-1.

The research carried out here employed analytical and imaging transmission electron microscopy and scanning transmission electron microscopy to gain a good understanding of local structure and composition of semiconductor nanocrystals and quantum dots for electronics and optoelectronics applications. One of the world's most advanced analytical scanning transmission electron microscopes in the field, the Daresbury SuperSTEM, was used to scrutinise the structure and composition of the samples. Three nanostructure systems are investigated in this thesis: 1. Structures consisting of Ge-nanocrystals (NCs) in alumina. Here HRTEM suggests relaxed and twinned smaller NCs grown annealed at lower temperature compared to elongated non-faulty bigger NCs annealed at higher temperature. HRTEM also suggests a polycrystalline structure of the matrix. 2. With regards to the InAs/GaAs quantum dots (QD) the study aims in particular at elucidating QD formation by investigating samples grown with and without growth interrupt (GI). Diffraction contrast TEM shows formation of buried dots in the sample prepared with GI whereas for the sample without GI the immediate growth of GaAs after InAs inhibits diffusion and segregation of In adotoms, and no footprint of buried dots has been observed. HRTEM and HAADF show coherent QDs in the sample with GI and abrupt InAs/GaAs interfaces in the sample without GI. In executing energy electron loss spectroscopy (EELS) and geometric phase analysis (GPA) the distribution of In in InGaAs/GaAs QDs has been obtained in samples grown in the critical thickness regime for quantum dot formation. The highest In percentage achieved in the dots grown with a nominal fraction of 100% was ~70%. EELS shows variations in the In concentration within the QD structure and wetting layer 3. In the case of Er-doped Si-NCs in silica this research tries to provide an understanding of structure, composition and position of excess Si and Er in the silica matrix of materials prepared under different growth conditions and to correlate this information with the PL emission, all with the aim to find preparation routes for optimum optical efficiency for applications of this materials system in silicon photonics. High spatial correlation between Si-NCs, Er and O in the Er and Si co-implanted sample with strong indication of an Er-oxide/Si core-shell structure had been found. The lack of an Er-oxide plasmon indicates, however, that the shell structure and its interface with the SiNCs is highly defective and a likely cause for non-radiative recombination. The sample with similar excess Er and Si concentrations but prepared in a two-stage implantation and annealing process shows a 10 times improvement in the optical emission. Here no spatial correlation between Er and Si-NCs was found in core loss EELS. EELS and HAADF evidenced more highly, near-atomically dispersed Er in the matrix with no formation of a core-shell structure as compared to the co-implanted sample. No footprint of Er-silicide plasmon was observed by low loss valence band EELS investigation in the co-implanted sample.

<div>In this thesis, we propose a model to predict the interfacial delamination in a flexible solar cell. The interface in a multilayer Copper Indium Gallium Diselenide (CIGS) flexible solar cell was studied applying the principles of fracture mechanics to a fixed-arm-peel test. </div><div>The principles of fracture mechanics ( J-integral and cohesive model) were implemented in a finite element software to compare the experimental with the numerical peeling force. A fixed-arm-peel test was used to obtain the peeling force for different peeling angles. This peel force and material properties from the CIGS solar cell were processed in several non-linear equations, so the energy required to start the delamination was obtained.The accuracy of the model was compared by fitting the experimental and numerical peeling force, which had a difference of 0.08 %. It is demonstrated that the peeling process for 90-degree could be replicated in COMSOL® software for a CIGS solar cell.</div>

<p>Predmet istraživanja ove doktorske disertacije&nbsp;su prahovi litijum-indijum oksida dopirani&nbsp;različitim jonima retkih zemalja (Eu³⁺; Sm³⁺;&nbsp;Er³⁺; Yb³⁺), sintetisani reakcijom u &nbsp;čvrstoj fazi.&nbsp;Litijum-indijum oksid ima raznovrsne&nbsp;potencijalne primene u viduscintilatora, &nbsp;matrice&nbsp;fosfora za jone retkih zemalja, za&nbsp; čuvanje i&nbsp;konverziju energije i u fotokatalizi. U&nbsp;<br />istraživanju je ustanovljena optimalna metoda&nbsp;sinteze fazno&nbsp; čistih prahova novih fosfora&nbsp;<br />LiInO₂:RE^3+&nbsp;i izvr&scaron;ena njihova detaljna&nbsp;karakterizacija primenom difrakcije X-zraka,&nbsp;<br />skenirajuće elektronske mikroskopije,&nbsp;termogravimetrije i diferencijalno termijske&nbsp;analize, Ramanske spektroskopije i difuzno-refleksione spektroskopije. &nbsp;Fotoluminescentna&nbsp;spektroskopija je primenjena u cilju ispitivanja&nbsp;osobina presudnih za &nbsp;primenu ovih materijala.&nbsp;Emisioni spektri i vrednosti vremena života&nbsp;pokazuju efikasne potencijalne fosfore, dok&nbsp;ispitivanja emisije uzorka LiInO₂:Er^3+&nbsp;na&nbsp;različitim temperaturama ukazuju na to da je u&nbsp;pitanju veoma dobar temperaturni senzor u&nbsp;<br />oblasti temperatura (10-300) K.</p> / <p>The subject of this dissertation are powders of&nbsp;lithium-indium oxide doped with different rare&nbsp;earth ions (Eu³⁺; Sm³⁺; Er³⁺; Yb³⁺), synthesized&nbsp;by solid-state reaction. Lithium-indium oxide&nbsp;has a variety of potential applications in the&nbsp;form of scintillators, phosphor matrixes for rare-earth ions, storage and energy conversion&nbsp;devices and photocatalysts. In this study the&nbsp;optimal method of synthesis of pure-phased&nbsp;powders of new phosphors LiInO₂:RE^3+&nbsp;was&nbsp;determined. Also, their detailed characterization&nbsp;<br />using the X-ray diffraction, scanning electron&nbsp;microscopy, thermogravimetry and &nbsp;differential&nbsp;thermal analysis, Raman spectroscopy and&nbsp;diffuse-reflection spectroscopy &nbsp;was performed.&nbsp;Photoluminescence spectroscopy was applied to&nbsp;investigate the properties crucial for the&nbsp;application of these materials. Emission spectra&nbsp;and lifetime values, showed these materials are&nbsp;potential efficient phosphors. Examining the&nbsp;emission of LiInO₂:Er^3+&nbsp;sample at different&nbsp;temperatures indicated that this is a very good&nbsp;temperature sensor in the temperature range (10-300) K.</p>

Title Interaction of Organic Molecules with Metal Passivated Silicon Surfaces Studied via STM Author Petr Zimmermann Department Department of Plasma and Surface Science Supervisor Doc. RNDr. Pavel Sobotík, CSc. Department of Plasma and Surface Science Abstract Organic molecules offer a wide range of optical, electronic or chemical properties. Coupling them to silicon could pave way to novel applications and devices, however, a controlled molecular functionalization of silicon remains challenging due to the presence of highly reactive dangling bonds on its surfaces. We attempt to decrease the reactivity of low index silicon surfaces with an ultra-thin layer of a metal adsorbates and study their interaction with organic molecules via scanning tunnelling microscopy. In the first part we investigate the interaction of ethylene, a small unsaturated molecule, with tin and indium 1D chains grown on Si(001) - 2 × 1. The chains consist of dimers structurally analogous to the dimers of the underlying Si(001) - 2 × 1 surface. Aided by photoelectron spectroscopy we find that the Sn chains are less reactive than the Si(001) surface and that the absence of a π dimer bond renders indium chains inert. In the second part we study the interaction of copper phthalocyanine, a small macrocyclic heteroaromatic compound, with the...