O presente trabalho tem como objetivo contribuir para o conhecimento da morfologia, microestrutura e modulação composicional (perfil da composição química) de recobrimentos NbN/CrN multicamadas nanoestruturados com diferentes periodicidades (entre 4 e 20 nm) depositado por PVD pela técnica de arco catódico. Foi alcançada espessura total do recobrimento de 30 ?m mantendo-se a homogeneidade da periodicidade ao longo de toda a espessura. Análises de difração de Raios-X, aliadas a modelamento computacional (difração dinâmica), e análise de microscopia eletrônica de transmissão (MET), permitiram a determinação da periodicidade das multicamadas e a espessura das camadas individuais de NbN e CrN e análise qualitativa da coerência entre as camadas. O modo de varredura (SMET) acoplado com espectroscopia de perda de energia de elétrons (EELS), permitiu medir a variação da composição química ao longo das nano-camadas individuais. A análise por EELS mostrou que, mesmo para a menor periodicidade estudada - 4nm, não há eliminação da modulação composicional. Assim, um modelo de Análise de Elementos Finitos (FEA) foi utilizado para avaliar a componente das tensões residuais intrínsecas ao longo das multicamadas, alimentado com o cáculo da deformação do parâmetro de rede, que pela Lei de Vergards varia em função da modulação química, ao longo das camadas de NbN e CrN. A microindentação instrumentada e o teste de riscamento mostraram aumento de dureza e maior resistência ao risco com a redução da periodicidade das multicamadas nanoestruturadas de NbN/CrN. O cruzamento dos resultados das diversas técnicas empregadas permitiu análise detalhada da estrutura e morfologia destes recobrimentos e a influência das periodicidades na modulação química das camadas individuais, possibilitando o desenvolvimento de um modelo qualitativo. Este aprendizado irá permitir a deposição de recobrimentos multicamadas nanoestruturados com melhor controle das propriedades mecânicas objetivadas em função da aplicação final do produto. / The present work aims at contributing to the knowledge, microstructure and compositional modulation (Chemical composition profile) of NbN/CrN multilayer nanostructured coatings with different periodicities (between 4 and 20nm) deposited by cathodic arc technique. It was reached a total coating thickness of 30 ?m preserving the periodicity homogeneity along the thickness. X-Ray Diffraction analisys, combined with computational modeling (dinamic diffraction) and Transmission Eletron Microscopy analysis (TEM), allowed the multilayer periodicity determination, the individual NbN and CrN layer thicknesses as well as the qualitative analysis of coherency among layers. The scanning mode (STEM) combined with Electron Energy Loss Spectroscopy (EELS), allowed the measurement of the chemical composition variation along the individual nanolayers. The EELS analysis showed that, even for the lowest periodicity studied - 4nm, there is no elimination of the compositional modulation. Thus, the Finite Element Analysis model (FEA) was used to evaluate the intrinsic residual stress component along the multilayers, fed with the lattice parameter deformation calculation, which, by Vegards Law varies as a function of the chemical modulation, along the NbN and CrN layers. The instrumented microindentation and the Scratch test showed hardness increase and higher scratch resistance as periodicity decreases on the nanostructured multilayer of NbN/CrN. The cross-linking data of the several techniques employed enabled a detailed analysis of the structure and morphology of such coatings and the influence of the periodicities on the individual layer chemical modulation, allowing the development of a qualitative model. This learning will allow multilayer nanostructured coatings deposition with a better control of desired mechanical properties as a function of the final product application.

O presente trabalho tem como objetivo contribuir para o conhecimento da morfologia, microestrutura e modulação composicional (perfil da composição química) de recobrimentos NbN/CrN multicamadas nanoestruturados com diferentes periodicidades (entre 4 e 20 nm) depositado por PVD pela técnica de arco catódico. Foi alcançada espessura total do recobrimento de 30 ?m mantendo-se a homogeneidade da periodicidade ao longo de toda a espessura. Análises de difração de Raios-X, aliadas a modelamento computacional (difração dinâmica), e análise de microscopia eletrônica de transmissão (MET), permitiram a determinação da periodicidade das multicamadas e a espessura das camadas individuais de NbN e CrN e análise qualitativa da coerência entre as camadas. O modo de varredura (SMET) acoplado com espectroscopia de perda de energia de elétrons (EELS), permitiu medir a variação da composição química ao longo das nano-camadas individuais. A análise por EELS mostrou que, mesmo para a menor periodicidade estudada - 4nm, não há eliminação da modulação composicional. Assim, um modelo de Análise de Elementos Finitos (FEA) foi utilizado para avaliar a componente das tensões residuais intrínsecas ao longo das multicamadas, alimentado com o cáculo da deformação do parâmetro de rede, que pela Lei de Vergards varia em função da modulação química, ao longo das camadas de NbN e CrN. A microindentação instrumentada e o teste de riscamento mostraram aumento de dureza e maior resistência ao risco com a redução da periodicidade das multicamadas nanoestruturadas de NbN/CrN. O cruzamento dos resultados das diversas técnicas empregadas permitiu análise detalhada da estrutura e morfologia destes recobrimentos e a influência das periodicidades na modulação química das camadas individuais, possibilitando o desenvolvimento de um modelo qualitativo. Este aprendizado irá permitir a deposição de recobrimentos multicamadas nanoestruturados com melhor controle das propriedades mecânicas objetivadas em função da aplicação final do produto. / The present work aims at contributing to the knowledge, microstructure and compositional modulation (Chemical composition profile) of NbN/CrN multilayer nanostructured coatings with different periodicities (between 4 and 20nm) deposited by cathodic arc technique. It was reached a total coating thickness of 30 ?m preserving the periodicity homogeneity along the thickness. X-Ray Diffraction analisys, combined with computational modeling (dinamic diffraction) and Transmission Eletron Microscopy analysis (TEM), allowed the multilayer periodicity determination, the individual NbN and CrN layer thicknesses as well as the qualitative analysis of coherency among layers. The scanning mode (STEM) combined with Electron Energy Loss Spectroscopy (EELS), allowed the measurement of the chemical composition variation along the individual nanolayers. The EELS analysis showed that, even for the lowest periodicity studied - 4nm, there is no elimination of the compositional modulation. Thus, the Finite Element Analysis model (FEA) was used to evaluate the intrinsic residual stress component along the multilayers, fed with the lattice parameter deformation calculation, which, by Vegards Law varies as a function of the chemical modulation, along the NbN and CrN layers. The instrumented microindentation and the Scratch test showed hardness increase and higher scratch resistance as periodicity decreases on the nanostructured multilayer of NbN/CrN. The cross-linking data of the several techniques employed enabled a detailed analysis of the structure and morphology of such coatings and the influence of the periodicities on the individual layer chemical modulation, allowing the development of a qualitative model. This learning will allow multilayer nanostructured coatings deposition with a better control of desired mechanical properties as a function of the final product application.

La détection IR quantique met classiquement en jeu l'absorption de photons dans le matériau semi-conducteur II-VI CdHgTe. Cet alliage présente la particularité de permettre un ajustage du gap du semi-conducteur aux longueurs d'onde couvrant toute la gamme IR en jouant simplement sur la composition de l'alliage, ce qui en fait un matériau de choix. Cependant,les petits gaps en jeu ici imposent un refroidissement des plans focaux à des températures généralement cryogéniques (typiquement la centaine de Kelvins). Ce refroidissement représente naturellement une limite importante dans l'exploitation, l'encombrement et le coût de tels détecteurs.Un des grands défis à venir dans le domaine de la détection IR quantique est la détection à plus haute température. Une figure de mérite populaire pour examiner le fonctionnement de ces détecteurs est le courant d'obscurité qui reflète son bruit, dans le cas d'un détecteur limité par le bruit de courant (shot noise). Or, du fait des propriétés électriques du matériau semi-conducteur utilisé, ce courant d'obscurité augmente fortement avec le réchauffement du détecteur et rend son utilisation impossible à haute température. De plus, un autre phénomène apparaît également limiter le fonctionnement de nos photo-détecteurs : à hautes températures apparaît du bruit 1/f dont l'origine n'est pas parfaitement comprise aujourd'hui (matériau bulk ou interfaces, le débats reste ouvert…).Ce travail de thèse a pour objectif de comprendre les phénomènes physique régissant le bruit 1/f dans les photodiodes CdHgTe à travers la variation d'un bon nombre de paramètres physique et géométriques en vue de mettre en évidence la ou les corrélations de ce bruit avec ces variantes. / The IR sensor makes quantum conventionally involves the absorption of photons in the semiconductor CdHgTe II -VI material . This alloy has a feature to allow an adjustment of the gap of the semiconductor at wavelengths covering the whole IR range by simply varying the composition of the alloy, which makes it a material of choice . However, small gaps at stake here impose a focal cooling to cryogenic temperatures generally planes ( typically hundred Kelvins ) . This cooling naturally represents an important limitation in the operation , the size and cost of such detectors .One of the great challenges ahead in the field of quantum IR detection is the detection at higher temperatures . A figure of merit for popular review the operation of these sensors is the dark current , which reflects its sound , in the case of a noise-limited current ( shot noise) detector. However, because the electrical properties of the semiconductor material used , the dark current increases sharply with the heating of the detector and makes it impossible to use at high temperature . In addition, another phenomenon also appears to limit the functionality of our photo-detectors: high temperature appears on the 1 / f noise whose origin is not fully understood today ( or bulk material interfaces , the debate remains open ... ) .To understand the physical phenomena governing the 1 / f noise in HgCdTe photodiodes through the variation this thesis aims to lots of physical and geometrical parameters in order to highlight the correlations or noise with these variants .

Conselho Nacional de Desenvolvimento Científico e Tecnológico / In the last decades, several applications of niobium nitride thin films has been proposed or effectively implemented. In the cubic δ − NbN phase, the bulk material presents a Tc for the superconducting transition near 17 K, what is far larger than those found in other normal (BCS) superconductors and useful in, for example, Josephson tunnel junctions. More recently, other phases have been also focus of interest, like the hexagonal δ-NbN phase. The hardness and resistance to chemical corrosion make this material well fitted for mechanically improved surface. Thin film preparation or deposition of niobium nitrides by physical methods (PVD) is not a trivial task. Stoichiometry, crystal structure and morphology of the resulting films are strongly affected by the deposition conditions, and even a qualitative model for the growth mechanisms of niobioum nitride is still lacking. In this work we have studied the effect of some parameters on the structural and morphologic properties of NbN thin films. The samples have been produced by reactive magnetron sputtering for different nitrogen partial pressures, substrate temperatures, bias voltages and deposition times. The crystallographic structure, preferred orientations, grain sizes and surface roughness were stablished by XR diffraction and, for some samples, atomic force microscopy. The results have shown that without bias voltage cubic NbN thin films are obtained, with or without substrate heating, when the partial pressure of N2 in the reactive atmosphere is between 13 and 25 %. Films produced with 17 % N2 are preferentially oriented in the <200> direction and this texture is enhanced by substrate heating. The analysis of the results in two samples with different thickness clearly indicates that for cubib NbN, the growth is remarkable different in the <111> and <200> directions. A possible mechanism to explain this difference is presented. The main effect of the voltage bias was to induce a hexagonal δ - NbN structure even for voltages as low as -10 V. These films present larger densities values than those found in the films with cubic phase, being the highest density achieved with -70V bias. All samples deposited with bias present a compressive stress and small grain size. The connections between stress, grain size and density are presented and discussed. In summary, we have identified a group of key parameters that makes possible the deposition of NbN thin films by reactive magnetron sputtering, either for superconductivity or tribological applications. / Nas últimas décadas, têm sido propostas e implementadas muitas aplicações para filmes finos de nitreto de nióbio. Na fase cúbica δ − NbN, o material na sua forma bulk apresenta Tc de transição supercondutora próxima a 17 K, o qual é de longe muito maior do que os valores encontrados para outros supercondutores normais (BCS). E, proveitoso, por exemplo, para junções túnel Josephson. Mais recentemente, outras fases também têm sido foco de interesse, como a hexagonal δ0 − NbN. A dureza e resistência à corrosão química fazem deste material bem equipado para melhoramento mecânico de superfícies. A preparação de filmes finos de nitretos de nióbio por PVD não é uma tarefa trivial. Estequiometria, estrutura cristalina e morfologia dos filmes resultantes são fortemente afetadas pelas condições de deposição. E, mesmo um modelo qualitativo para os mecanismos de crescimento do nitreto de nióbio ainda está faltando. Neste trabalho estudamos o efeito de alguns parâmetros sobre as propriedades estruturais e morfológicas de filmes finos de NbN. As amostras foram produzidas por magnetron sputtering reativo com diferentes pressões parciais de nitrogênio, temperaturas do substrato, voltagem bias e tempos de deposição. Os resultados mostraram que sem bias aplicado são obtidos filmes finos de NbN na fase cúbica, com ou sem aquecimento do substrato, quando a pressão parcial de N2 na atmosfera reativa está entre 13 e 25%. Filmes produzidos com 17% de N2 estão preferencialmente orientados na direção (200) e sua textura é aumentada por aquecimento do substrato. A análise dos resultados em duas amostras com diferentes espessuras indicou claramente que, para NbN cúbico, o crescimento é notavelmente diferente nas direções (111) e (200). Um possível mecanismo capaz de explicar esta diferença é proposto neste trabalho. O efeito significativo da aplicação do bias foi induzir a estrutura hexagonal δ − NbN mesmo para voltagens pequenas como -10 V. Estes filmes apresentam valores de densidade maiores do que para os filmes com fase cúbica, sendo a maior densidade alcançada para -70 V de bias. Todas amostras depositadas com aplicação de bias apresentaram estresse compressivo e tamanho de grãos pequeno. As conexões entre estresse, tamanho de grão e densidade são apresentados e discutidos. Em resumo, identificamos um grupo de parâmetros chave que tornam possível a deposição de filmes finos de NbN por magnetron sputtering reativo, seja para supercondutividade seja para aplicações tribológicas.

Combining solution-based and surface-assisted synthesis, we demonstrate the first synthesis of NBN-doped bis-tetracene (NBN-BT) and peri-tetracene (NBN-PT). The chemical structures are clearly elucidated by high-resolution scanning tunneling microscopy (STM) in combination with noncontact atomic force microscopy (nc-AFM). Scanning tunneling spectroscopy (STS) characterizations reveal that NBN-BT and NBN-PT possess higher energy gaps than bis-tetracene and peri-tetracene. Interestingly, NBN-BT can undergo stepwise one-electron oxidation and convert into its corresponding radical cation and then to its dication. The energy gap of the NBN-BT dication is similar to that of bis-tetracene, indicating their isoelectronic relationship. Moreover, a similar energy gap between the NBN-PT dication and peri-tetracene can be predicted by DFT calculations. This work provides a novel synthesis along with characterizations of multi-NBN-doped zigzag-edged peri-acenes with tunable electronic properties.

Superconducting nanowire single-photon detectors (SNSPDs) are nanodevices usually made from thin niobium nitride (NbN) films. Operated at liquid helium temperature, they can exhibit high detection efficiency with low dark-counts associated with a fast response time and a low timing jitter. Covering a broad detection range from ultraviolet to mid-infrared, SNSPDs are a very attractive alternative to silicon or gallium arsenide based semiconductor detectors for fiber based telecommunication when single-photon sensitivity and high counting rates are necessary. Efficient packaging and fiber coupling of a SNSPD is in itself a real challenge and is often a limiting factor in reaching high system quantum efficiency. Our approach makes use of a controlled expansion alloy which has been adequately heat treated to enhance its characteristics for cryogenic operation. This insures the integrity of the optical coupling at cryogenic temperatures while done at room temperature. It also provides a good attenuation for electromagnetic interference due to the high relative permeability of the nickel-iron alloy. The small form factor of this pigtailed optical fiber package makes it versatile and could be easily integrated with a commercial cryogen-free system or simply dipped into a standard helium transport Dewar. We report on our theoretical and experimental methodology to evaluate the optical coupling quality and present the optoelectronic characterization of two devices packaged in this way. Electrical simulation is studied to understand the speed limitation factor inherent to these devices and preliminary speed and jitter measurements are reported.

Superconducting nanowire single-photon detectors (SNSPDs) are nanodevices usually made from thin niobium nitride (NbN) films. Operated at liquid helium temperature, they can exhibit high detection efficiency with low dark-counts associated with a fast response time and a low timing jitter. Covering a broad detection range from ultraviolet to mid-infrared, SNSPDs are a very attractive alternative to silicon or gallium arsenide based semiconductor detectors for fiber based telecommunication when single-photon sensitivity and high counting rates are necessary. Efficient packaging and fiber coupling of a SNSPD is in itself a real challenge and is often a limiting factor in reaching high system quantum efficiency. Our approach makes use of a controlled expansion alloy which has been adequately heat treated to enhance its characteristics for cryogenic operation. This insures the integrity of the optical coupling at cryogenic temperatures while done at room temperature. It also provides a good attenuation for electromagnetic interference due to the high relative permeability of the nickel-iron alloy. The small form factor of this pigtailed optical fiber package makes it versatile and could be easily integrated with a commercial cryogen-free system or simply dipped into a standard helium transport Dewar. We report on our theoretical and experimental methodology to evaluate the optical coupling quality and present the optoelectronic characterization of two devices packaged in this way. Electrical simulation is studied to understand the speed limitation factor inherent to these devices and preliminary speed and jitter measurements are reported.

Cette thèse a permis le développement et l'optimisation de jonctions Josephson SNS (Supraconducteur–métal Normal–Supraconducteur) à électrodes NbN et barrière TaxN de haute résistivité. On a montré une bonne reproductibilité des propriétés des couches TaxN en fonction des paramètres du dépôt. Les tricouches NbN/TaxN/NbN présentent la température critique élevée attendue (16K). Les jonctions présentent une dépendance claire du produit RnIc (courant Josephson x résistance normale, indicateur de la fréquence Josephson maximale) en fonction de la pression d'azote dans le dépôt. On a ainsi obtenu sur des collections de jonctions des produits RnIc très élevés, jusqu'à 3,74mV à 4,2K pour des densités de courant critique Jc voisines de 15kA/cm2. Les jonctions présentent les comportements Josephson attendus, (diffraction de Fraunhofer et marches de Shapiro) jusqu'à 14K. La dépendance du Jc des jonctions en fonction de la température a été interpolée en utilisant le modèle des jonctions SNS longues dans la limite sale, donnant une longueur de cohérence du métal normal autour de 3,8nm à 4,2K. Nous avons enfin étudié un procédé de fabrication multiniveaux adapté aux circuits RSFQ (Rapid Single Flux Quantum), comprenant un plan de masse commun et des résistances de polarisation. Pour conclure, nous avons montré la supériorité de performances des jonctions NbN/TaxN/NbN sur les jonctions actuelles en niobium et leur intérêt pour réaliser des circuits numériques RSFQ compacts. En effet ces jonctions s'affranchissent des résistances d'amortissement des jonctions Nb, et peuvent fonctionner jusqu'à des fréquences d'horloge supérieures à 150 GHz et jusqu'à 10K (contre 50 GHz en Nb à 4,2K).

abstract: This work demonstrates novel nBn photodetectors including mid-wave infrared (MWIR) nBn photodetectors based on InAs/InAsSb type-II superlattices (T2SLs) with charge as the output signal, and visible nBn photodetectors based on CdTe with current output. Furthermore, visible/MWIR two-color photodetectors (2CPDs) are fabricated through monolithic integration of the CdTe nBn photodetector and an InSb photodiode. The MWIR nBn photodetectors have a potential well for holes present in the barrier layer. At low voltages of < −0.2 V, which ensure low dark current <10-5 A/cm2 at 77 K, photogenerated holes are collected in this well with a storage lifetime of 40 s. This charge collection process is an in-device signal integration process that reduces the random noise significantly. Since the stored holes can be readout laterally as in charge-coupled devices, it is therefore possible to make charge-output nBn with much lower noise than conventional current-output nBn photodetectors. The visible nBn photodetectors have a CdTe absorber layer and a ZnTe barrier layer with an aligned valence band edge. By using a novel ITO/undoped-CdTe top contact design, it has achieved a high specific detectivity of 3×1013 cm-Hz1/2/W at room temperature. Particularly, this CdTe nBn photodetector grown on InSb substrates enables the monolithic integration of CdTe and InSb photodetectors, and provides a platform to study in-depth device physics of nBn photodetectors at room temperature. Furthermore, the visible/MWIR 2CPD has been developed by the monolithic integration of the CdTe nBn and an InSb photodiode through an n-CdTe/p-InSb tunnel junction. At 77 K, the photoresponse of the 2CPD can be switched between a 1-5.5 μm MWIR band and a 350-780 nm visible band by illuminating the device with an external light source or not, and applying with proper voltages. Under optimum conditions, the 2CPD has achieved a MWIR peak responsivity of 0.75 A/W with a band rejection ratio (BRR) of 52 dB, and a visible peak responsivity of 0.3 A/W with a BRR of 18 dB. This 2CPD has enabled future compact image sensors with high fill-factor and responsivity switchable between visible and MWIR colors. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2016

Ce travail porte sur la réalisation d'un microspectromètre SWIFTS (Stationary Wave Integrated Fourier Transform Spectrometer) incluant des compteurs de photons SNSPD (Superconducting Nanowire Single Photon Detector). Il met en œuvre un interféromètre intégré à guide d'onde en arête bouclé, en SiN, sous lequel sont disposés 24 nanofils supraconducteurs SNSPD en NbN échantillonnant les interférences au pas de 160nm, à une longueur d'onde centrée sur 1.55µm. La conception, l'étude des composantes optique et électronique, la fabrication et la caractérisation à 4.2K sont décrites, jusqu'à la mise en évidence d'une modulation de puissance lumineuse dans le guide conformément à la formation attendue d'interférences. Le SWIFTS-SNSPD constitue le premier dispositif optoélectronique supraconducteur à part entière, doublement intégré. Sa capacité unique d'échantillonnage direct de franges d'interférences ouvre de nombreuses perspectives, pour des applications allant de l'astrophysique aux télécoms. / This work presents the realization of a SWIFTS (Stationary Wave Integrated Fourier Transform Spectrometer) micro-spectrometer with SNSPD (Superconducting Nanowire Single Photon Detector) photon counters. The device features an integrated interferometer made of a SiN loop ridge-waveguide, with an array of 24 NbN-nanowire SNSPD underneath that samples at a 160nm period the interferogram of a laser light, at a wavelength centred on 1.55µm. The conception, preliminary studies of integrated optics and electronics, fabrication and characterization at 4.2K of the final device are described, in particular the observation of the detected signal modulation in the waveguide in agreement with the expected interference formation. The SWIFTS-SNSPD constitutes the first stand-alone, fully integrated superconducting optoelectronic device. Its unique capability of direct sampling of light interferogram opens numerous perspectives, with possible applications ranging from astrophysics to telecommunications.