Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / O desenvolvimento de semicondutores magnÃticos tÃm despertado crescente interesse dos pesquisadores devido suas promissoras aplicaÃÃo na spintrÃnica. Estes semicondutores podem ser produzidos a partir da dopagem de semicondutor nÃo magnÃtico com Ãons de metais de transiÃÃo. Neste trabalho, difraÃÃo de raios-x e espectroscopia no infravermelho foram utilizados para estudar as caracterÃsticas estruturais de Ãxidos semicondutores magnÃticos diluÃdos nanoestruturados do tipo SnO2 dopados com Fe, Co ou Mn, produzidos pelo mÃtodo sol-gel proteico. PadrÃes nanoestruturados de SnO2 sem dopagem foram produzidos com temperaturas de calcinaÃÃo de 300, 350 e 400ÂC para servir de base de comparaÃÃo. Foram sintetizadas sÃries de amostras com fÃrmula geral Sn1−x Mx O2−δ , onde M Ã o elemento magnÃtico (Fe, Co ou Mn) e x a concentraÃÃo de dopante, com as mesmas temperaturas de calcinaÃÃo e com trÃs concentraÃÃes de dopante (5, 10 e 20%). A difraÃÃo de raios-x foi utilizada para identificar as fases do composto assim como calcular os parÃmetros estruturais, tamanhos de cristalito e microdeformaÃÃes residuais. A anÃlise indicou que a sÃntese resultou na obtenÃÃo de compostos com estrutura SnO2 com dimensÃes nanomÃtricas. Amostras calcinadas a 400ÂC apresentaram a presenÃa de fases espÃrias. A dopagem foi confirmada pela variaÃÃo dos parÃmetros de rede dos compostos em funÃÃo do tipo e concentraÃÃo dos dopantes. Os modos vibracionais das ligaÃÃes quÃmicas nos compostos foram identificados por espectroscopia infravermelho. Com base nesta anÃlise, foi possÃvel estudar o comportamento energÃtico das ligaÃÃes iÃnicas quando os elementos dopantes estÃo incorporados em sÃtios de Ãons Sn4+ na matriz hospedeira. / The development of magnetic semiconductors has arisen growing attention due to their promising applications in spintronics. These materials can be produced by doping of a non-magnetic semiconductor with magnetic ions of transition metals. In this work, x-ray diffraction and infrared spectroscopy were used to study the structural characteristics of nanostructured Fe, Co or Mn-doped SnO2 oxide diluted magnetic semiconductors. The material was produced by a protein based sol-gel method called proteic sol-gel. To provide a basis for comparison, nanostructured standards of undoped SnO2 were produced with calcination temperatures of 300, 350 and 400◦ C. Samples of Sn1−x Mx O2−δ , where M is the magnetic dopant (Fe, Co or Mn) and x the dopant concentration, were prepared with the same calcination temperatures and x = 5, 10 and 20%. X-ray diffraction was used to identify the crystalline phases in the samples as well as to calculate structural parameters, particle sizes and residual microstrain. The analysis indicated that the synthesis resulted in nanosized compounds with the SnO2 structure. Samples calcined at 400◦ C presented the presence od spurious phases. Doping was confirmed by the variation of lattice parameters of compounds as a function of type and concentration of dopants. Vibrational modes of chemical bonds were identified by infrared spectroscopy. Based on this analysis, it was possible to study the energetic behavior of ionic bonds when doping elements are incorporated in Sn4+ sites in the host matrix.

A investigação das propriedades ópticas e sua relação com as propriedades magnéticas dos semicondutores é de grande interesse para a comunidade científica, em virtude da enorme demanda por novas tecnologias e funcionalidades que podem surgir dessas pesquisas. Os calcógenos de európio são semicondutores intrinsecamente magnéticos, transparentes na região visível do espectro eletromagnético e integráveis em matrizes de silício e nitreto de gálio, sendo assim fortes candidatos a aplicações tecnológicas envolvendo magnetismo e óptica. Neste trabalho são investigados os espectros de absorção e fotoluminescência dos calcógenos de európio, com base no modelo 4f -> 5d(\'t IND. 2g\') da transição óptica de dipolo elétrico, o qual mostrou-se totalmente adequado para a descrição da absorção óptica nos calcógenos de európio em função do campo magnético aplicado, explicando a presença de linhas de absorção estreitas e dicróicas nos espectros em campo alto e a forma larga dos espectros de absorção em campo nulo. Nos espectros de fotoluminescência do EuTe, entretanto, foram detectados estados eletrônicos não contemplados pelo modelo 4f -> 5d(\'t IND. 2g\') , em especial uma banda de emissão denominada \'MX IND. 0\', acoplada a modos vibracionais da rede. Uma linha zero-fônon correspondente a uma transição que não produz fônons pôde ser bem definida e a partir do deslocamento dessa linha em função do campo magnético foi possível detectar inequivocamente a formação de polarons magnéticos no EuTe pela primeira vez; o raio polarônico foi estimado como R = 3.6a, onde a é o parâmetro de rede e a energia de ligação desse polaron foi estimada em \'E IND. p\' = 45 meV, um resultado que foi confirmado através de medidas do deslocamento da linha zero-fônon em função da temperatura. Adicionalmente procurou-se identificar o estado eletrônico associado à emissão \'MX IND. 0\': a partir de medidas da intensidade da fotoluminescência em função da potência de excitação foi possível sugerir que a emissão \'MX IND. 0\' provem de estados eletrônicos ligados a defeitos da rede e foi possível estimar a concentração desses defeitos como menor que 0.1 ppm. / Investigation of optical properties and their relation to magnetic properties of semiconductors is of great interest to scientific community, due to the large demand for new technologies and features that can arise from these studies. Europium chalcogenides are intrinsically magnetic semiconductors, transparent in the visible region of electromagnetic spectrum and integrable into silicon and gallium nitride matrices, beeing strong candidates for technological applications involving magnetism and optics. The present study investigates absorption and photoluminescence spectra of europium chalcogenides, based on the 4f -> 5d(t2g) model of the electric dipole optical transition, which proved to be entirely appropriate to describe polarized optical absorption in europium chalcogenides as a function of magnetic field, explaining the presence of narrow dichroic lines at high fields and the broad shape of the zero-field absorption spectrum. However, in photoluminescence spectra of EuTe, electronic states not covered by the 4f -> 5d(t2g) model were detected, in particular an emission band labeled MX0, which is coupled to vibrational modes of the lattice. A transition without production of phonons, corresponding to a zero-phonon line, could be well resolved and from the displacement of the zero-phonon line as a function of magnetic field the formation of magnetic polarons in EuTe could be detected unambiguously for the first time. The polaronic radius is estimated as R = 3:6a, where a is the lattice parameter, and the polaron binding energy is estimated as Ep = 45 meV, a result that was confirmed by measurements of zero-phonon line displacement as a function of temperature. Additionally, we sought to identify the electronic state associated with MX0 emission: from measurements of the photoluminescence intensity as a function of excitation power, it was possible to suggest that MX0 emission comes from an electronic state coupled to lattice defects of low concentration, which we estimate to be of less than 0.1 ppm.

The properties of RNiSb compounds were studied from various points of view: Magnetism, transport, electronic structure. The compounds with a light rare earth are metallic, while the cubic phases with a heavy rare earth element have the semi-Heusler structure and are narrow gap semiconductors. A giant magnetoresistance effect was found at low temperatures, the larger as the density of charge carriers is weak. It was explained by the polarisation of the impurity levels situated within the band gap of the semiconductor under the field of the magnetic moment of the 4f shell. The crystal field, as well as the magnetic order at low temperatures, were studied by neutron scattering and diffraction. Particular magnetic properties (absence of magnetic order in the Pr compound, antiferromagnetic structure in the second group, orientation of the moments) have been explained, at least qualitatively. CeNiSb is a Kondo-type compound with a Kondo temperature of about 8 K. Photoemission measurements have allowed to analyse the electronic structure in the valence band of these compounds, in agreement with band structure calculations. By resonant photoemission of TbNiSb and GdCu, different resonance channels have been resolved, which depend on the spin configuration of the excited states.

No description available.

Magnetic ordering of dopants in diamond holds the prospect of exploiting diamond’s unique properties in the emerging field of spintronics. Several transition metal defects have been reported to order ferromagnetically in various semiconductors, however, low Curie temperatures and lack of other fundamental material properties have hindered practical implementation in room temperature spintronic applications. In this Thesis, we consider the energetic stability of 3d transition metal doped-diamond and its magnetic ordering properties at various lattice sites and charge states using ab initio Density Functional Theory methods. We find the majority of 3d transition metal impurities in diamond at any charge state to be energetically most stable at the divacancy site compared to substitutional or interstitial lattice sites, with the interstitial site being highly unstable (by ~8 - 10 eV compared to the divacancy site). At each lattice site and charge state, we find the formation energies of transition metals in the middle of the 3d series (Cr, Mn, Fe, Co, Ni) to be considerably lower compared to those early or late in the series. The energetic stability of transition metal impurities across the 3d series is shown to be strongly dependent on the position of the Fermi level in the diamond band gap, with the formation energies at any lattice site being lower in p-type or ntype diamond compared to intrinsic diamond. Further, we show that incorporation of isolated transition metal impurities into diamond introduces spin polarised impurity bands into the diamond band gap, while maintaining its semiconducting nature, with band gaps in both the spin-up and spin-down channels. These impurity bands are shown to originate mainly from s, p-d hybridization between carbon sp 3 orbitals with the 3d orbitals of the transition metal. In addition, the 4p orbitals contribute significantly to hybridization for transition metal atoms at the substitutional site, but not at the divacancy site. In both cases, the spin polarisation and magnetic stabilization energies are critically dependent on the lattice site and charge state of the transition metal impurity. By allowing magnetic interactions between transition metal atoms, we find that ferromagnetic ordering is likely to be achieved in divacancy Cr+2, Mn+2, Mn+1 and Co0 as well as in substitutional Fe+2 and Fe+1, indicating that transition metal-doped diamond is likely to form a diluted magnetic semiconductor which may successfully be considered for room temperature spintronic applications. In addition, these charge states correspond to p-type diamond, except for divacancy Co0, suggesting that co-doping with shallow acceptors such as B ( will result in an increase of charge concentration, which is likely to enhance mediation of ferromagnetic spin coupling. The highest magnetic stabilization energy occurs in substitutional Fe+1 (33.3 meV), which, also exhibits half metallic ferromagnetic ordering at the Fermi level, with an induced magnetic moment of 1.0 μB per ion, thus suggesting that 100 % spin polarisation may be achieved in Fe-doped diamond. / Physics / D. Litt. et Phil. (Physics)

Nanotechnology is the science and engineering of creating functional materials by precise control of matter at nanometer (nm) length scale and exploring novel properties at that scale. It is vital to understand the quantum mechanical phenomena manifested at nanometer scale dimensions since that will enable us to precisely engineer quantum mechanical properties to realize novel device functionalities. This dissertation investigates optical and electronic properties of compound and transition metal doped compound semiconductor nanowires with a view to exploiting them for a wide range of applications in semiconductor electronic and optical devices. In this dissertation work, basic concepts of optical and electronic properties at low dimensional structures will be discussed in chapter 1. Chapter 2 discusses the nanofabrication technique employed to fabricate highly ordered nanowires. Using this method, which is based on electrochemical self-assembly techniques, we can fabricate highly ordered and size controlled nanowires and quantum dots of different materials. In Chapter 3, we report size dependent fluorescence spectroscopy of ZnSe and Mn doped ZnSe nanowires fabricated by the above method. The nanowires exhibit blue shift in the emission spectrum due to quantum confinement effect, which increases the effective bandgap of the semiconductor. We found that the fluorescence spectrum of Mn doped ZnSe nanowires shows high luminescence efficiency, which seems to increase with increasing Mn concentration. These results are highly encouraging for applications in multi spectral displays. Chapter 4 investigates field emission results of highly ordered 50 nm tapered ZnO nanowires that were also fabricated by electrochemical self-assembly. Subsequent to fabrication, the nanowires tips are exposed by chemical etching which renders the tips conical in shape. This tapered shape concentrates the electric field lines at the tip of the wires, and that, in turn, increases the emission current density while lowering the threshold field for the onset of field emission. Measurement of the Fowler-Nordheim tunneling current carried out in partial vacuum indicates that the threshold electric field for field emission in 50-nm diameter ZnO nanowires is 15 V/µm. In this study we identified the key constraint that can increase the threshold field and reduce emission current density. In Chapter 5 we report optical and magnetic measurement of Mn-doped ZnO nanowires. Hysterisis measurements carried out at various temperatures show a ferromagnetic behavior with a Curie temperature of ~ 200 K. We also studied Mn-doping of the ZnO nanowires. The room temperature fluorescence spectroscopy of Mn-doped ZnO nanowires shows a red-shift in the spectra compared to the undoped ZnO nanowires possibly due to strain introduced by the dopants in the nanowires. Finally, in Chapter 6, we report our study of the ensemble averaged transverse spin relaxation time (T2*) in InSb thin films and nanowires using electron spin resonance (ESR) measurement. Unfortunately, the nanowires contained too few spins to produce a detectable signal in our apparatus, but the thin films contained enough spins (> 109/cm2) to produce a measurable ESR signal. We found that the T2* decreases rapidly with increasing temperature between 3.5 K and 20 K, which indicates that spin-dephasing is primarily caused by spin-phonon interactions.

Le développement des dispositifs issus de l'électronique de spin nécessite de nouveaux matériaux qui permettent d'injecter de manière efficace le courant polarisé en spin dans des semiconducteurs. Parmi de nombreux matériaux utilisés comme injecteurs de spin, les semiconducteurs ferromagnétiques dilués (DMS), obtenus en dopant des semiconducteurs avec des impuretés magnétiques tels que Mn ou Co, sont considérés comme des candidats potentiels pour l'injection de spin. Ces matériaux dopés deviennent ferromagnétiques tout en conservant leurs propriétés semiconductrices. Par conséquent, ils présentent une similarité d'impédance électrique par rapport aux substrats semiconducteurs, ce qui rend efficace l'injection de courant polarisé en spin dans ces derniers. Dans ce contexte, l'objectif principal de cette thèse consiste à étudier la cinétique de croissance des semiconducteurs ferromagnétiques dilués GeMn. Nous cherchons à déterminer les paramètres clés de la croissance des couches de GeMn, à savoir la température du substrat, et la concentration en Mn. Pour la fabrication de dispositifs électroniques fonctionnels, le challenge crucial est d'obtenir des DMS ayant une température de Curie (TC) bien supérieure à la température ambiante. Nous nous sommes donc concentrés sur la cinétique de formation de la phase nanocolonnaire GeMn possédant une TC au-delà de 400 K. / The development of active spintronic devices requires new materials, which enable to efficiently inject spin-polarized currents into non-magnetic semiconductors. Among numerous materials that can be used as spin injectors, diluted magnetic semiconductors (DMS), obtained by doping standard semiconductors with magnetic impurities, such as Mn or Co, have emerged as potential candidates for spin injection. The materials become ferromagnetic while conserving their semiconducting properties. They exhibit therefore natural impedance match to host semiconductors and are expected to efficiently inject spin-polarized currents into semiconductors. In this context, the main objectives of this thesis work consist in studying the growth kinetics of GeMn-based diluted magnetic semiconductors. We aim at determining the main growth parameters, such as the substrate temperature and the Mn concentration, that govern the growth process of GeMn layers. Since for device applications it is crucial to obtain DMS exhibiting a Curie temperature (TC) well above room temperature, we have focused our attention to the kinetic formation of the GeMn nanocolumn phase, which exhibits a Curie temperature higher than 400 K.

Ce travail porte sur l'étude des propriétés opto- et magnéto-électroniques des oxydes et fluorures de zinc. Dans une première partie, nous avons étudié les propriétés d'absorption/réflexion dans le proche-IR de poudres d'oxyde de zinc dopées de manière aliovalente par l'aluminium ou le gallium. Une grande partie du travail a consisté en la détermination précise du taux de dopant introduit pour les différentes conditions expérimentale utilisées. Les taux de dopant déterminés ont ensuite été corrélés aux propriétés optiques mesurées par spectrométrie de réflexion diffuse. Nous avons voulu réaliser le même travail sur le fluorure de zinc mais nous avons été confrontés à la difficulté de doper ce composé par l'aluminium à cause de la grande stabilité chimique du fluorure AlF3. En revance, une étude structurale approfondie a été réalisée sur un hydroxyfluorure de zinc ZnOHF, précurseur pouvant être dopé de manières aliovalente. Dans la dernière du manuscrit, nous avons utilisé nos compétences relatives au suivi du dopage pour étudier l'effet des porteurs libres sur les propriétés magnétiques des oxydes de zinc dopés au cobalt. D'un point de vue expérimental, aucun effet des porteurs n'a été recensé, seul un comportement paramagnétique ayant été observé. / This work deals with the opto-electronic and magnetic properties of zinc oxides and fluorides. In a first part, NIR absorption / reflection properties of aluminium and gallium doped zinc oxides powders have been studied. Dopant rates have been accurately determined for different experimental conditions and correlated with optical properties which were measured by diffuse reflection spectrometry. The same investigation has been performed on zinc fluoride but this compound could not have been doped by aluminium because of high chemical stability of aluminium fluoride. However, a structural study has been carried out on zinc hydroxyfluoride, which can be doped by aluminium. The last part of this dissertation deals with the investigation of carriers effect, which can be followed by diffuse reflection, on magnetic properties of cobalt doped zinc oxide. Free carriers have beeb no effect, only a paramagnetic behaviour has been observed.

Le développement de nouveaux dispositifs spintroniques à base de semi-conducteurs (SC) nécessite la création d'une population électronique polarisée en spin dans ces matériaux. De ce point de vue, le germanium est un matériau prometteur pour les applications en spintronique à cause de la forte mobilité des porteurs de charge ainsi que de la symétrie d'inversion du cristal diamant à l'origine de temps de vie de spin très longs. Dans ce manuscrit, nous discutons deux approches pour l'injection et la détection électrique de spins dans le germanium. La première approche consiste à utiliser une barrière tunnel et un métal ferromagnétique (FM) comme injecteur de spin. L'insertion d'une barrière tunnel à l'interface FM/SC permet de résoudre le problème fondamental du désaccord de conductivité. Nous avons utilisé deux injecteurs différents : Py/Al2O3 et CoFeB/MgO. Les mesures sont réalisées en géométrie à trois contacts et l'accumulation de spins dans le germanium est démontrée par la mesure de l'effet Hanle. Dans le cas d'une barrière d'Al2O3, les spins injectés s'accumulent sur des états localisés à l'interface oxyde/Ge et cette accumulation est observée jusqu'à 220 K. Dans le cas d'une barrière de MgO, les spins sont réellement injectés dans le canal de Ge et un signal de 20-30 µV est encore observé à température ambiante. Nous discutons dans la deuxième approche l'utilisation du semi-conducteur magnétique (Ge,Mn) comme injecteur de spins dans le Ge. Nous avons tout d'abord étudié les propriétés structurales et magnétiques de films minces de (Ge,Mn) fabriqués par épitaxie par jets moléculaires à basse température. En faisant varier les paramètres de croissance, nous avons pu observer des nanocolonnes de GeMn cristallines ou amorphes, ainsi que des films et des nanoparticules de Ge3Mn5. Nous nous sommes concentrés sur l'anisotropie magnétique de ces nanostructures. Finalement, la croissance de (Ge,Mn) sur GOI a été optimisée en vue de son utilisation comme injecteur de spins dans le germanium et différentes méthodes d'intégration de ce matériau dans les dispositifs de spintronique « tout semi-conducteur » sont discutées. / Creation of spin polarization in non-magnetic semiconductors is one of the prerequisite for creation of spintronics based semiconductor devices. Germanium is interesting for spintronics applications due to its high carrier mobilities and its inversion symmetry that gives long spin lifetimes. In this manuscript, we discuss two approaches for electrical spin injection and detection in Germanium. The first approach is to use a tunnel barrier and a ferromagnetic metal as a spin injector. The tunnel barrier at the interface circumvents the conductivity mismatch problem. Two different spin injectors are used: Py/Al2O3 and CoFeB/MgO. The measurements are performed in three-terminal geometry and the proof of spin accumulation is given by Hanle measurements. In case of Al2O3, the spin accumulation is predicted to be in localized states at the oxide/Ge interface and the spin signal is observed up to 220 K. However in MgO based devices, true injection in Ge channel is predicted and spin signal of 20-30 µV is observed at room temperature. The second approach of using ferromagnetic semiconductor (Ge,Mn) as spin injector is also discussed. The structural and magnetic properties of (Ge,Mn) thin-films grown by low-temperature molecular beam epitaxy (LT-MBE) are studied. Depending on the growth parameters, crystalline/amorphous GeMn nanocolumns and Ge3Mn5 thin films or nanoclusters have been observed. Magnetic anisotropy in these nanostructures is also studied. Finally, the growth of (Ge,Mn) films on GOI substrates is shown and different ways to use (Ge,Mn) as a spin injector in Ge are discussed to achieve all-semiconductor based spintronics devices.

O presente trabalho é um estudo sobre a importância da informação dos orbitais atômicos no cálculo de propriedades optoeletrônicas de heteroestruturas semicondutoras de baixa dimensionalidade. O trabalho é dividido em duas partes: na primeira parte, é estudada a simetria de reversão temporal no hamiltoniano k . p, analisando a preservação da informação de spin presente nos orbitais atômicos. O hamiltoniano obtido é inserido na equação de massa efetiva expandida para superredes. São calculadas estruturas de bandas de alguns poços quânticos de semicondutores III-V e grupo-IV. Compara-se o novo método com os tradicionais, e então são analisadas algumas grandezas que apresentam alteração significativa entre os métodos usados; A segunda parte é composta por um estudo detalhado do potencial de troca-correlação em semicondutores dopados. A matriz que descreve este potencial é escrita usando a distribuição de portadores presentes nos orbitais atômicos da rede cristalina, e os coeficientes desta matriz foram calculados usando quatro modelos para a correção de muitos corpos, baseadas nas aproximações LDA (Local density approximation) e LSDA (Local spin density approximation), com o objetivo de comparar as diversas parametrizações. Usando o método k . p tradicional, expandido para superredes, foram simulados sistemas δ-doped e hMni-δ-doped de Si, através de um cálculo autoconsistente baseado na equação de Poisson. A magnetização dos portadores é descrita por um modelo de campo médio. Foram analisados os perfis de potencial, estruturas de bandas, polarização de portadores e espectros de fotoluminescência para determinar as diferenças entre as aproximações utilizadas. / This work is a study about the atomic orbitals information importance in the calculation of optoelectronics properties of low dimensionality semiconductors. The work is divided in two parts. In the first one, a study of the time reversal symmetry of the k . p Hamiltonian is realized analyzing the preservation of the spin information present in the atomic orbitals. The obtained Hamiltonian is applied in the effective mass equation expanded to superlattices. Some calculations of quantum wells band structures are made using III-V and group-IV semiconductors, comparing the new method with the conventional ones to obtain an analysis of the difference of some physics properties. The second part is a detailed study of the exchangecorrelation potential in doped semiconductors. The matrix coefficients are calculated using the charge distribution of the crystalline lattice atomic orbitals, applied in some LDA (Local density approximation) and LSDA (Local spin density approximation) parameterizations to compare them. Using the conventional k . p method expanded to superlattices, Si δ-doped and hMni-δ-doped systems were calculated through a self consistent calculation based on Poissons equation. The carriers magnetization is described by an average field model. The potential profiles, band structures, carrier polarization and photoluminescence spectra were analyzed to obtain the difference between the approaches.