Indium nitride has many applications as a semiconductor. High quality films of indium nitride can be grown using Chemical Vapour Deposition (CVD) and Atomic Layer Deposition (ALD), but the availability of precursors and knowledge of the underlaying chemical reactions is limited. In this study the gas phase decomposition of a new indium precursor, N,N-dimethyl-N',N''-diisopropylguanidinate, has been investigated by quantum chemical methods for use in both CVD and ALD of indium nitride. The computations showed significant decomposition at around 250°C, 3 mbar indicating that the precursor is unstable at ALD conditions. A computational study of the surface chemical mechanism of the adsorption of trimethylindium and ammonia on indium nitride was also performed as a method development for other precursor surface mechanism studies. The results show, in accordance with experimental data, that the low reactivity of ammonia is a limiting factor in thermal ALD growth of indium nitride with trimethylindium and ammonia.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / This work presents the synthesis and crystallographical study of indium organometallic compounds series in II and III oxidation states. Br2In(diox)2CH2Br and tetrahedral indium cluster, In4R4 [R = C(SiMe3)3], were adopted as starting materials of this work. We have made two different systematic studies: (a) reaction of Br2In(diox)2CH2Br with dialkylselenides R1SeR2 (R1 = CH3, R2 = CH2Ph; R1 = C2H5, R2 = CH2Ph; R1 = R2 = CH2Ph) and (b) reaction between the tetrahedral indium cluster and different chalcogenide donor ligands, such as PhEEPh (E = S, Se and Te), ArTeTeAr (Ar = CH3C6H4) and PhEBr (E = Se and Te), and haloforms as well, CHX3 (X = Cl, Br and I). The haloforms were applied as mild halogen donors. Br2In(diox)2CH2Br is obtained by the direct reaction between InBr and CH2Br2 in 1,4-dioxane. The Br3InCH2Se(CH3)CH2Ph (1), Br3InCH2Se(C2H5)CH2Ph (2) and Br3InCH2Se(CH2Ph)2 (3) derivatives are obtained by the reaction between Br2In(diox)2CH2Br and their own dialkylselenides. Tetrahedral indium cluster is obtained by the reaction between InBr and C(SiMe3)3·2THF in equivalent amounts. The new organoindium subhalides, R2In2Cl2 (4), R2In2Br2 (5), R2In2I2 (6), and the new indium(III) dimeric compounds as well, [RIn(SPh)2]2 (7), [RIn(SePh)2]2 (8), [RIn(TePh)2]2 (9) and [RIn(ArPh)2]2 (10), [RIn(Br)SePh]2 (11), [RIn(Br)TePh]2 (12), were obtained by the direct reaction of tetrahedral indium cluster and their respective halide or chalcogenide donors. / Este trabalho apresenta a síntese e o estudo cristalográfico de uma série de compostos organometálicos de índio nos estados de oxidação II e III. Os materiais de partida utilizados neste trabalho foram o Br2In(diox)2CH2Br e o cluster tetraédrico de índio, In4R4 [R = C(SiMe3)3]. Realizou-se dois tipos de estudos sistemáticos: (a) reação de Br2In(diox)2CH2Br com dialquilselenetos R1SeR2 (R1 = CH3, R2 = CH2Ph; R1 = C2H5, R2 = CH2Ph; R1 = R2 = CH2Ph) e (b) reação do cluster de índio com diferentes ligantes contendo calcogênios, como PhEEPh (E = S, Se e Te), ArTeTeAr (Ar = CH3C6H4) e PhEBr (E = Se e Te) e com halofórmios, CHX3 (X = Cl, Br e I). Os halofórmios foram utilizados como doadores de halogênio moderados. Br2In(diox)2CH2Br é obtido através da reação entre InBr e CH2Br2 em 1,4-dioxano. Os derivados Br3InCH2Se(CH3)CH2Ph (1), Br3InCH2Se(C2H5)CH2Ph (2) e Br3InCH2Se(CH2Ph)2 (3) são obtidos através da reação entre Br2In(diox)2CH2Br e seus respectivos dialquilselenetos. O cluster tetraédrico de índio é obtido a partir da reação de InBr e C(SiMe3)3·2THF em quantidades equivalentes. Os novos derivados de halogênio, R2In2Cl2 (4), R2In2Br2 (5), R2In2I2 (6), e os novos compostos diméricos de índio(III), [RIn(SPh)2]2 (7), [RIn(SePh)2]2 (8), [RIn(TePh)2]2 (9) e [RIn(ArPh)2]2 (10), [RIn(Br)SePh]2 (11), [RIn(Br)TePh]2 (12), foram obtidos através da reação direta do cluster de índio com seus respectivos doadores de halogênio ou calcogênio.

Fundação de Amparo a Pesquisa no Estado do Rio Grande do Sul / Because of the constant introduction of new technologies to market growth of electronic waste generation has gained importance on the world stage, among these residues are cell phones. Deliver useful life increasingly short. Mobile phones are made up of several components, including LCD screens. In these screens there is a mixture of indium oxide (In) and tin (Sn), known as ITO, which 80-90% consists of In and 10-20% by Sn. There are already several studies that show ideal conditions for comminution and leaching of LCD screens, therefore, this study aims to establish an effective method for concentrating In present in aqueous solution coming from the acid leaching processes and thus regain In the form metal. Tests were conducted electrodialysis (ED), using synthetic solution In2(SO4)3 in order to work with a more environmentally acceptable method. Thus, initially tested for different current densities in a time of 120 minutes, monitoring pH and conductivity and varying the concentration of In every 30 minutes. The In concentration was determined by atomic absorption (AAS). The optimal current density was 0.96 mA/cm2, where was obtained 62.77% current efficiency. After setting the optimal current density applied in the same test of 131 hours, which resulted in a concentration of 521 mg/L In. Despite the use of electrodialysis have been able to concentrate the solution, the value of 521 mg/L is still not enough to recover In for electrowinning. Thus, we apply the solvent extraction method. Was used as DEHPA extractant diluted in commercial kerosene and evaluated the best contact time between the aqueous phase (A) and organic (O), pH, ratio A:O, better DEHPA concentration in the organic phase. For stripping evaluated the best molar concentration of HCl, relative A:O and contact time between phases. The best conditions laid down have been applied in real solution In, obtained leaching LCD screens, with concentration 32.44 mg/L. The best conditions are obtained in the extraction ratio A:O of 40:1, in 20 minutes, at pH 0,5 e obtained a 96,67% efficiency applied after the stripping in the loaded organic solution with In, with respect to 1:10 with concentration of HCl 4M in 10 minutes, resulting in a efficiency of 61,10% and concentration of 7,712 g/L In. Also performed were tests electrowinning (EO) evaluated three different current densities, and 150 A/m² was obtained a 50.71% efficiency at a concentration of 7 g/L. Therefore, two further phases in In recovery process were developed in recovering In its metallic form giving opportunity for new applications, reducing the consumption of natural resources. / Devido a constante introdução de novas tecnologias no mercado, o crescimento da geração de resíduos eletroeletrônicos tem ganhado importância no cenário mundial, dentre esses resíduos estão os telefones celulares. Estes equipamentos apresentam um tempo de vida útil cada vez mais curto. Os celulares são constituídos por diversos componentes, dentre eles as telas de LCD. Nessas telas há uma mistura de óxido de índio (In) e estanho (Sn), conhecida como ITO, onde de 80-90% é composta por In e 10-20% por Sn. Já existem diversos estudos que mostram condições ideais para cominuição e lixiviação das telas de LCD, assim sendo, este trabalho tem por objetivo estabelecer um método eficaz para concentrar o In presente em solução aquosa oriunda dos processos de lixiviação ácida e assim recuperar o In na forma metálica. Foram realizados testes de eletrodiálise (ED), utilizando solução sintética de In2(SO4)3, a fim de trabalhar com um método mais ambientalmente aceitável. Desta forma, inicialmente testou-se diferentes densidades de corrente em um tempo de 120 minutos, monitorando pH e condutividade e variação da concentração do In a cada 30 minutos. A concentração de In foi determinada por absorção atômica (AAS). A densidade de corrente mais adequada dentro das condições experimentais foi de 0,96 mA/cm2, onde se obteve 62,77% de eficiência de corrente. Após a definição da densidade de corrente ideal aplicou-se a mesma num ensaio de 131 horas, onde resultou em uma concentração 521 mg/L de In. Apesar do emprego da eletrodiálise ter conseguido concentrar a solução, o valor de 521 mg/L ainda não é suficiente para recuperar o In por eletro-obtenção. Desta forma, aplicou-se o método de extração por solventes. Utilizou-se como extrator DEHPA diluído em querosene comercial e avaliou-se o melhor tempo de contato entre as fases aquosa (A) e orgânica (O), pH, relação A:O, melhor concentração de DEHPA na fase orgânica. Para a re-extração avaliou-se a melhor concentração molar de HCl, relação A:O e tempo de contato entre as fases. As melhores condições estabelecidas foram aplicadas em solução real de In, obtida de lixiviação de telas de LCD, com concentração 32,44 mg/L. As melhores condições obtidas foram na extração a relação A:O de 40:1, em 20 minutos, com pH 0,5 e obteve-se uma eficiência de 96,67%, após aplicou-se a re-extração na solução orgânica carregada com o In, com relação de 1:10, HCl com concentração 4 M em 10 minutos, resultando em uma eficiência de 61,10% e uma concentração de 7,712 g/L de In. Também foram realizados testes de eletro-obtenção (EO), avaliando três diferentes densidades de corrente, sendo que com 150 A/m² obteve-se uma eficiência de 50,71%, com concentração de 7 g/L. Sendo assim, duas novas etapas no processo de recuperação de In foram desenvolvidas, recuperando In em sua forma metálica dando oportunidade para novas aplicações, reduzindo o consumo de recursos naturais.

Philosophiae Doctor - PhD / When the amorphous silicon (a-Si) dangling bonds are bonded to hydrogen the concentration of the dangling bond is decreased. The resulting film is called hydrogenated amorphous silicon (a-Si:H). The reduction in the dangling bonds concentration improves the optoelectrical properties of the film. The improved properties of a-Si:H makes it possible to manufacture electronic devices including a solar cell. A solar cell device based on the hydrogenated amorphous silicon (a-Si:H) was fabricated using the Hot-Wire Chemical Vapour Deposition (HWCVD). When an n-i-p solar cell configuration is grown, the norm is that the p-doped layer is deposited from a mixture of silane (SiH4) gas with diborane (B2H6). The boron atoms from diborane bonds to the silicon atoms and because of the number of the valance electrons, the grown film becomes a p-type film. Aluminium is a group 3B element and has the same valence electrons as boron, hence it will also produce a p-type film when it bonds with silicon. In this study the p-doped layer is grown from the co-deposition of a-Si:H from SiH4 with aluminium evaporation resulting in a crystallized, p-doped thin film. When this thin film is used in the n-i-p cell configuration, the device shows photo-voltaic activity. The intrinsic layer and the n-type layers for the solar cell were grown from SiH4 gas and Phosphine (PH3) gas diluted in SiH4 respectively. The individual layers of the solar cell device were characterized for both their optical and electrical properties. This was done using a variety of experimental techniques. The analyzed results from the characterization techniques showed the films to be of device quality standard. The analysed results of the ptype layer grown from aluminium showed the film to be successfully crystallized and doped. A fully functional solar cell was fabricated from these layers and the cell showed photovoltaic activity. / South Africa

Philosophiae Doctor - PhD / When the amorphous silicon (a-Si) dangling bonds are bonded to hydrogen the concentration of the dangling bond is decreased. The resulting film is called hydrogenated amorphous silicon (a-Si:H). The reduction in the dangling bonds concentration improves the optoelectrical properties of the film. The improved properties of a-Si:H makes it possible to manufacture electronic devices including a solar cell.A solar cell device based on the hydrogenated amorphous silicon (a-Si:H) was fabricated using the Hot-Wire Chemical Vapour Deposition (HWCVD). When an n-i-p solar cell configuration is grown, the norm is that the p-doped layer is deposited from a mixture of silane (SiH4) gas with diborane (B2H6). The boron atoms from diborane bonds to the silicon atoms and because of the number of the valance electrons, the grown film becomes a p-type film. Aluminium is a group 3B element and has the same valence electrons as boron, hence it will also produce a p-type film when it bonds with silicon.In this study the p-doped layer is grown from the co-deposition of a-Si:H from SiH4 with aluminium evaporation resulting in a crystallized, p-doped thin film. When this thin film is used in the n-i-p cell configuration, the device shows photo-voltaic activity.The intrinsic layer and the n-type layers for the solar cell were grown from SiH4 gas and Phosphine (PH3) gas diluted in SiH4 respectively. The individual layers of the solar cell device were characterized for both their optical and electrical properties. This was done using a variety of experimental techniques. The analyzed results from the characterization techniques showed the films to be of device quality standard. The analysed results of the ptype layer grown from aluminium showed the film to be successfully crystallized and doped.A fully functional solar cell was fabricated from these layers and the cell showed photovoltaic activity.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / A study of InP nanowires with an oxide layer, as well as the initial steps of the oxidation process is pursued through first principles calculations and molecular dynamics simulations within the Density Functional Theory. An InP nanowire in the wurtzite phase in an environment containing a O2 molecular gas is used to simulate the initial steps of the nanowire oxidation process. The molecular dynamics simulations reveal that the O2 molecules dissociate preferentially in reactions with the P atoms and that that they are incorporated into the nanowire, mainly at the superficial layers. The molecular dynamics simulation of the already oxidated InP nanowire reveals a pair distribution function very close to that of the pure nanowire, although there is a disarrangement of the local crystalline phase. The defects generated by the atoms lead to the closure of the energy gap, due mainly to the contribuition coming rom the In atoms bond to oxygen. / Um estudo de nanofios de InP oxidados, assim como das etapas iniciais do processo de oxidação é realizado usando cálculos de primeiros princípios e dinâmica molecular a 300K, dentro da Teoria do Funcional da Densidade. Um nanofio de InP na fase wurtzita num ambiente contendo um gás de moléculas O2 é usado para simular as etapas iniciais do processo de oxidação do nanofio. A dinâmica molecular revela que as moléculas de O2 se dissociam preferencialmente em reações com átomos de P, com os átomos de oxigênio sendo incorporados em suas camadas superficiais. A simulação de dinâmica molecular do nanofio de InP já oxidado revela uma função distribuição de pares muito próxima à do fio puro, embora haja desestruturação da fase cristalina local. Os defeitos gerados pela presença dos átomos de oxigênio levam a um fechamento do gap de energia, devido principalmente à contribuições vindas dos átomos de In ligados ao oxigênio.

High quality and accurate computational data was obtained through first principle quantum mechanical calculations originated from density functional theory without the inclusion of empirical data (ab initio). The support of the computing facility NGS allows us to carry out our research involving large scale atomistic simulations. The data we recently obtained clearly shows piezoelectricity in GaAs and InAs are proved to be non linear in relation to a general strain.The high order fitting equation obtained through the parameterization procedure allowed us to directly evaluate higher order piezoelectric coefficients. By comparing with other linear and non linear models and also experimental data, we reached the conclusion that the validity of our model is correct in the limitation of small shear strain, particularly in case of (111) grown semiconductors. Such limitation however is not restricted under pseudomorphic growth in (001) direction where typically shear strain is small.We further validate our model through elasticity theory to demonstrate the sign of the polarization is found to be opposite to bulk values for an InAs semiconductor layer grown in the (001) direction of growth and subject to 6-7% of lattice mismatch. This is additionally supported with experimental evidence (optical absorption spectra).Furthermore our model provides a direct way in evaluating the polarization for any crystal structure described on the atomic level. This is mainly beneficial to researchers who use molecular dynamics and empirical methods for predicting bandstructure.The fundamental performance for semiconductor devices can be improved through the use of the small polarization created from strain and is likely to bring advantages in future photovoltaics devices.

No description available.

Le phosphure d’indium (InP) est un semiconducteur III-V aux propriétés adaptées aux applications optoélectroniques. Toutefois, son oxydation spontanée à l’air engendre une dégradation de ses propriétés électriques. La passivation de sa surface devient donc une étape clé pour son intégration dans des dispositifs optoélectroniques attractifs. Dans le cadre de ce travail de thèse, nous nous sommes intéressés à l’étude de la passivation de surface de InP par nitruration. Nous avons réalisé de manière reproductible la formation d’un film de type polyphosphazène ( H2N-P=NH )n sur InP par voie électrochimique dans l’ammoniac liquide (-55°C). Le suivi de la croissance du film sur InP a été effectué grâce au couplage systématique de mesures électrochimiques (J = f(E), J = f(t), E = f(t) et C = f(E)) avec des analyses de composition chimique de surface par XPS (X-ray photoelectron spectroscopy). Chacune de ces techniques apporte des éléments sur la compréhension du mécanisme de nitruration de la surface de InP en solution (anodisation en milieu NH3 liq), nous permettant ainsi de proposer un mécanisme de formation du film de phosphazène de type ECE « Electrochimique-Chimique-Electrochimique ». L’étude par XPS de la stabilité à l’air de la composition chimique de surface de InP traité a révélé le caractère protecteur du film. La valeur élevée de la capacité interfaciale après traitement anodique suggère que l’interface modifiée (de type Electrolyte-Insulator-Semiconductor) est en régime d'accumulation et se comporte comme un « vrai » condensateur. / Indium phosphide (InP) is a III-V semiconductor, which represents an ideal candidate for optoelectronic applications. However, its spontaneous oxidation in air leads to the loss of its electrical properties. The surface passivation becomes a key step for its integration in attractive optoelectronic devices. As part of this thesis, we are interested in studying the passivation of the InP surface by nitridation. We reproducibly realized the formation of a polyphosphazene-like (H2N-P=NH)n film on InP by electrochemical treatment in liquid ammonia (-55°C). The monitoring of the film formation was performed using a systematic coupling between electrochemical measurements (J = f(E), J = f(t), E = f(t), and C = f(E)) and XPS analysis (X-ray photoelectron spectroscopy) to follow the chemical composition of the surface. These techniques provide some answers about the nitridation mechanism of InP surface by a wet process (anodization in NH3 liq), leading to the formation of the phosphazene film through an ECE mechanism “Electrochemical-Chemical-Electrochemical”. The study of the air ageing of the modified surface using XPS analysis revealed the protective nature of the film. The high value of the interfacial capacity after the anodic treatment suggests that the modified interface (Electrolyte-Insulator-Semiconductor-like) is in accumulation state and behaves like a "real" capacitor.

Volatile organic compounds (VOCs) in the indoor air have adverse effects on the dwellers residing in a building or a vehicle. One of these effects is called sick building syndrome (SBS). SBS refers to situations in which the users of a building develop acute health effects and discomfort depending on the time they spend inside some buildings without having any specific illness. Furthermore, monitoring volatile organic compounds could lead to early diagnosis of specific illnesses through breath analysis. Among those VOCs formaldehyde, acetaldehyde can be listed. In this thesis, VOC detecting thin film sensors have been investigated. Such sensors have been manufactured using semiconducting metal oxides, ligand activated gold nanoparticles and Graphene/TiO2 mixtures. Advanced gas deposition unit, have been used to produce NiO thin films and Au nanoparticles. DC magnetron sputtering has been used to produce InSnO and VO2 thin film sensors. Graphene/TiO2 sensors have been manufactured using doctor-blading. While presenting the results, first, material characterization details are presented for each sensor, then, gas sensing results are presented. Morphologies, crystalline structures and chemical properties have been analyzed using scanning electron microscopy, X-ray diffraction and X-ray photo electron spectroscopy. Furthermore, more detailed analyses have been performed on NiO samples using extended X-ray absorption fine structure method and N2 adsorption measurements. Gas sensing measurements were focused on monitoring formaldehyde and acetaldehyde. However, responses ethanol and methane were measured in some cases to monitor selectivity. Graphene/TiO2 samples were used to monitor NO2 and NH3. For NiO thin film sensors and Au nano particles, fluctuation enhanced gas sensing is also presented in addition to conductometric measurements.