The goal of this Thesis is to study the electronic and optical properties of semiconductor nanostructures by employing different theories. The work present in this Thesis is divided into three parts. Part I is devoted to the effective-mass theory and its several applications. A general description of the effective mass theory and several ways of solving the effective-mass Schrodinger equation with an emphasis on the potential morphing method are given in the first chapter. In the following few chapters, we apply these theories in many realistic systems for the study of many properties. They include: i) the binding energy of hydrogentic donor impurity in semiconductor quantum dots under the influence of static electric field and/or magnetic field, ii) the linear and nonlinear optical properties associated with intraband transitions in semiconductor quantum dots, core shell quantum dots and quantum-dot-quantum-ring systems. Part II is devoted to the pseudopotential theory and its several applications. The background theories primarily regarding to the empirical pseudopotential method and configuration interaction approach are described in the first chapter. In the following few chapters, we employ these theories for the study of the electronic and optical properties of many nanostructures of group II-VI materials. The optical properties studied herein include the band gap, Stokes shift, exciton fine structure, optical polarization and absorption spectra. Part III is devoted to the appendix, where twelve published papers are presented. / Στόχος της παρούσας διατριβής είναι η μελέτη των ηλεκτρονικών και οπτικών ιδιοτήτων νανοδομών ημιαγωγών κάνοντας χρήση κατάλληλων υπολογιστικών μεθόδων και τεχνικών. Η διατριβή χωρίζεται σε τρία μέρη. Το πρώτο μέρος εστιάζει στην θεωρία της ενεργούς μάζας (Effective-mass Theory) και τις εφαρμογές της. Στο πρώτο κεφάλαιο παρουσιάζεται το απαραίτητο θεωρητικό υπόβαθρο και δίνεται μία συνοπτική περιγραφή των συνηθέστερων μεθόδων επίλυσης της μονοηλεκτρονιακής εξίσωσης του Schrodinger,δίνοντας ιδιαίτερη έμφαση στην μέθοδο μορφοποίησης δυναμικού (Potential Morphing Method). Στα επόμενα κεφάλαια του πρώτου μέρους οι τεχνικές και μέθοδοι που περιγράφηκαν χρησιμοποιούνται για την μελέτη κρίσιμων ιδιοτήτων και παραμέτρων σε νανοσυστήματα ημιαγωγών. Μεταξύ αυτών είναι: i) η ενέργεια δέσμευσης υδρογονοειδών προσμίξεων τύπου δότη υπό την επίδραση στατικού ηλεκτρικού ή/και μαγνητικού πεδίου, ii) γραμμικές και μη γραμμικές οπτικές ιδιότητες που συνδέονται με intraband μεταβάσεις εντός ζώνης σε κβαντικές τελείες ημιαγωγών, κβαντικές τελείες με δομή πυρήνα-φλοιού και σε μεικτά συστήματα κβαντικής τελείας – κβαντικού δακτυλίου. Το δεύτερο μέρος εστιάζει στην θεωρία των ψευδοδυνάμικών και τις εφαρμογές της. Αρχικά παρουσιάζεται το απαραίτητο θεωρητικό υπόβαθρο της μεθόδου εμπειρικών ψευδοδυναμικών (Empirical Pseudopotential Method) καθώς επίσης και της μεθόδου αλληλεπίδρασης διαμορφώσεων (Configuration Interaction). Στην συνέχεια, οι προαναφερθείσες τεχνικές εφαρμόζονται στην μελέτη των ηλεκτρονικών και οπτικών ιδιοτήτων σε μία πληθώρα νανοδομών ημιαγωγών II-VI. Μεταξύ των ιδιοτήτων αυτών είναι: το ενεργειακό χάσμα, η μετατόπιση Stokes, η λεπτή δομή των εξιτονίων, η οπτική πόλωση και τα φάσματα απορρόφησης. Το τρίτο μέρος της διατριβής περιλαμβάνει το παράρτημα, στο οποίο παρατίθενται οι δώδεκα δημοσιευμένες εργασίες.

Ο όρος μη-γραμμική οπτική αντιπροσωπεύει τον κλάδο της οπτικής ο οποίος μελετά την αλληλεπίδραση της ύλης με ακτινοβολία πολύ ισχυρής έντασης. Όταν ένα υλικό εκτεθεί σε ακτινοβολία υψηλής έντασης όπως αυτή του laser, οι οπτικές του ιδιότητες αλλάζουν εξαιτίας της πόλωσης που επάγεται στα δομικά υλικά του και το αποτέλεσμα είναι η αλλαγή των οπτικών του ιδιοτήτων. Αυτό με τη σειρά του οδηγεί σε μία πληθώρα φαινομένων τα οποία μας βοηθούν στη κατανόηση της δομής του υλικού άλλα και των φυσικών μηχανισμών που κρύβονται πίσω από αυτά. Υλικά με μεγάλες μη-γραμμικες οπτικές ιδιότητες είναι πολύ χρήσιμα στην έρευνα και την ανάπτυξη πολλών κλάδων της τεχνολογίας. Σαν παράδειγμα μπορεί να αναφερθεί η ανάπτυξη των οπτικών και κβαντικών υπολογιστών, αλλά και τεχνολογιών οι οποίες μπορούν να βρουν εφαρμογή στις τηλεπικοινωνίες. Στη παρούσα εργασία μελετώνται οι μη-γραμμκές οπτικές ιδιότητες υλικών με μορφή διαλυμάτων. Η διάρθρωση της εργασίας είναι ως εξής: Στο πρώτο κεφάλαιο γίνεται μία εισαγωγή και παρουσιάζονται κάποιες βασικές έννοιες της μη-γραμμικής οπτικής. Έπειτα παρουσιάζεται ο τρόπος που μπορούν να εξαχθούν οι σχέσεις οι οποίες περιγράφουν τις μη-γραμμικές οπτικές ιδιότητες των υλικών όπως τη μη-γραμμική επιδεκτικότητα τρίτης τάξης με βάση τη κλασσική Φυσική και τη κβαντομηχανική. Το κεφάλαιο κλείνει παρουσιάζοντας μερικά φαινόμενα τα οποία οφείλονται στη μη-γραμμική επιδεκτικότητα τρίτης τάξης. Στο δεύτερο κεφάλαιο γίνεται η παρουσίαση των πειραματικών τεχνικών που χρησιμοποιήθηκαν για τη διεξαγωγή των πειραμάτων, αλλά και η διαδικασία που ακολουθήθηκε για την εξαγωγή των μη-γραμμικών οπτικών ιδιοτήτων από τα πειραματικά δεδομένα. Στα κεφάλαια που ακολουθούν παρουσιάζονται τα πειραματικά αποτελέσματα των συστημάτων που μελετήθηκαν. Πιο συγκεκριμένα στο τρίτο κεφάλαιο παρουσιάζονται τα πειραματικά αποτελέσματα που προέκυψαν από τη μελέτη νανοσωματιδίων οξειδίων του σιδήρου καλυμμένων με πολυμερή αλλά και ακάλυπτων όταν διεγείρονταν με παλμούς laser χρονικής διάρκειας 35 ps και 4 ns και μήκη κύματος 532 nm και 1064 nm. Στόχος της μελέτης ήταν ο προσδιορισμός αν το πολυμερές που βρίσκεται αγκυροβολημένο στην επιφάνεια του νανοσωματιδίου ή απουσία αυτού έχει κάποια επίδραση στις μη-γραμμικές οπτικές ιδιότητες αυτών. Στο τέταρτο κεφάλαιο παρουσιάζονται τα πειραματικά αποτελέσματα της μελέτης των μικκυλιακών συστημάτων Pd για μήκη κύματος διέγερση 532 nm και 1064 nm. Η μελέτη έγινε για χρονικό εύρος παλμού laser 35 ps και 4 ns. Τα συμπολυμερή τα οποία σχημάτιζαν το μικκύλιο απέτρεπαν τη συσσωμάτωση των νανοσωματιδίων Pd και τη δημιουργία σταθερών κολλοειδών διαλυμάτων. Τα συμπολυμερή που χρησιμοποιήθηκαν επίσης δημιουργούσαν νανοδομές οι οποίες είχαν καλά ορισμένες διαστάσεις και σχήματα. Στόχος της μελέτης ήταν να διαπιστωθεί το κατά πόσο η διάσταση, το σχήμα καθώς και η αλλαγή του συμπολυμερούς επηρεάζουν τις μη-γραμμικές οπτικές των νανοδομών. Στο πέμπτο κεφάλαιο παρουσιάζονται τα αποτελέσματα που προέκυψαν από τη μελέτη οργανομεταλλικών ενώσεων διθειολενικών συμπλόκων. Η επίδραση των υποκαταστών του σκελετού του μορίου καθώς και του κεντρικού ατόμου της ένωσης εξετάστηκαν για παλμούς laser χρονικής διάρκειας 35 ps και μήκους κύματος 532 nm και 1064 nm. Στο έκτο και τελευταίο κεφάλαιο παρουσιάζονται τα πειραματικά αποτελέσματα που προέκυψαν από τη μελέτη δυαδικών συστημάτων φουλλερενίων δότη-αποδέκτη ηλεκτρονίων για παλμούς laser 35 ps και μήκους κύματος 532 nm. Τα αποτελέσματα δείχνουν ότι αυτά τα συστήματα έχουν πολύ αυξημένες μη-γραμμικές οπτικές σε σχέση με τα απλά φουλλερένια καθιστώντας τα υποψήφια για πιθανές εφαρμογές σε διατάξεις οπτικών αισθητήρων και οπτικών πυλών. / The field of optics that examines the interaction of matter with very high intensity radiation is called nonlinear optics. When a material is exposed to radiation with high intensity such as the radiation emitted by a laser, the optical properties of the material change as a result of the induced polarization that occurs in the atoms or the molecules that constitute the material. This in turn can lead to a variety of phenomena that helps us to understand and establish relations between the structure and the physical mechanisms that take place when light interacts with matter. Materials with large nonlinear optical properties are considered possible candidates for applications in a wide range of technology such us optical or quantum computers or even in the field of telecommunications. In this work the nonlinear optical properties of metallic nanoparticles, organometallic molecules and fullerene derivates is examined. The investigated systems were in form of solutions and the nonlinear optical properties were determined with the use of Z-scan and OKE techniques. The laser pulse duration was 35 ps and 4 ns, while the excitation wavelength was 532 nm and 1064 nm respectively. In the first chapter an introduction is presented to some elements of the field of nonlinear optics. Then the derivation of the relations that describe the nonlinear optical parameters like the third order susceptibility (χ(3)) with the use of electromagnetic theory and quantum mechanics is presented. At the end some interesting phenomena that occur as a result of third order susceptibility are described. The second chapter is devoted to the experimental techniques that were used to determine the nonlinear optical properties of the investigated systems that are presented in this work. The Z-scan and OKE techniques are described thoroughly as well and the process of the determination of the nonlinear optical properties from the experimental data. In the next four chapters, experimental results are presented of the nonlinear optical properties for all the systems that were studied during this work. At the third chapter the results for γ-Fe2O3 nanoparticles are presented. Those systems were either covered or uncovered with polymeric brushes, and had different sizes of the nanoparticle core. The results show that the presence or not of the polymeric brushes, as well and the size of the core has an impact on the nonlinear optical properties those systems. In chapter four are presented the results from the investigation of the nonlinear optical properties of Pd nanoparticles encapsulated into amphiphilic block copolymer micelles. The investigation was done under 35 ps and 4 ns laser pulse duration at excitation wavelengths of 532 and 1064 nm. It is concluded that the NLO response of the systems is depending on the size of the micelle, the shape but also from the metallic load of the micelle. In the final two chapters they are presented the results regarding the NLO properties of organometallic and fullerene derivates molecules. In chapter five the investigation of the nonlinear optical properties of various dithiolene complexes is presented, under 35 ps laser pulse duration at 532 and 1064 nm. The results shows that the central atom attached to the molecule is playing crucial role to the NLO response but also and the number and the nature of substituent attached to the molecule. At the final chapter the determined NLO properties of some donor – acceptor fullerene derivatives are presented. The results show that functionalized fullerene derivatives have greater NLO response than the neat fullerene making them promising candidates for applications in optoelectronics and all-optical switching.

In this thesis, we investigate the nonlinear optical properties of four different physical systems: tellurite glasses, castor oil, ionic liquids and colloids of gold nanoparticles. Using Zscan and I-scan techniques, it was possible to determine the values of the electronic (n2 e) and thermal (n2 t) contributions of nonlinear refractive index of these systems as well as evaluating their respective thermo-optical coefficients (dn/dT). We use the I-scan technique to characterize five tellurite glass samples with different compositions. In this experiment we employ a Ti:sapphire laser operating in the modelocked regime, tuned at , delivering pulses, with a repetition rate that was controlled by a pulse selector. These glasses presented an ultra-fast self-focusing nonlinearity. The figure of merit 810 nm 200 fs 1kHz max 0 W= Δn λα was evaluated, and the condition was obtained for four of the five studied samples, displaying the potentiality of these glasses for ultra-fast all-optical switching applications, for example. Castor oil is a natural organic compound with a wide range of applications in industry. In the nanotechnology field, this oil has been exploited as very efficient dispersant and stabilizer agent for metallic gold nanoparticles in colloidal systems. However, a lack of data in literature concerning nonlinear optical properties of this material exists. In this work, we use the Z-scan technique to measure the nonlinear optical response of castor oil for laser excitation at 514 and 810 nm. In the visible region, the measurements had been carried out in the CW regime, using an Argon laser. In the infrared region, a Ti:sapphire laser, operating in the modelocked regime, producing pulses of 200 fs, with low (1 kHz) and high (76 MHz) repetition rate was employed instead. The castor oil presented a self-defocusing nonlinear refraction for both the laser wavelengths. The influence of the electronic and thermal contributions for nonlinearity was evaluated and the results indicate that the thermal effects are the main responsible for the observed nonlinear refraction. The thermo-optical coefficient ( ) of this compound was also measured for both wavelengths. We observe that castor oil thermo-optical coefficient is approximately an order of magnitude larger for the excitation tuned at 514 nm than at 810 nm. The nonlinear optical properties of two kinds of ionic liquids, BMI.BF4 and BMI.PF6, had been investigated. These materials are organic salts that present a low melting temperature and negligible vapor pressure. Although they have interesting physical-chemistry properties, and have been used in several applications, their nonlinear optical properties had been little investigated. In this work, we use the Z-scan technique at W > 0.27 dn / dT 514 nm and . Both ionic liquids displayed high self-defocusing nonlinearity, of thermal origin. We observed that the change of anion by anion modify the optical properties of these compounds. The ionic liquids had also presented a dispersion behavior in their thermo-optical coefficients in the spectral range studied. Although thermo-optical nonlinearities are a problem for the development of ultra-fast photonic devices, they can present a nonlocal character as a consequence of the process of heat conduction. Nonlinear effects in nonlocal media have been investigated in diverse branches of the physics, in particular in phenomena such as light pulses nonlinear propagation, as well as in generation and interaction of spatial solitons. Thus, these results suggest that castor oil and ionic liquids are promising candidates for investigation of nonlinear effects in nonlocal media. In the characterization of the colloidal systems of gold nanoparticles dispersed in castor oil, we evaluate the nonlinear refractive index, nonlinear absorption coefficient, as well as the thermo-optical coefficient in function of the filling factor f. Using Z-scan technique, for the laser excitation tuned at , we observe that the colloids presented an ultra-fast selfdefocusing refractive nonlinear response. Using the generalized Maxwell-Garnett model for composite materials it was possible to explain the behavior of the nonlinear refractive index of the colloid as a function of the filling factor, as well as estimate the value of the real part of the gold nanoparticles third-order nonlinear susceptibility. We also observe that the presence of gold nanoparticles dispersed in castor oil increased the absolute value of the linear absorption coefficient, the nonlinear refraction index of thermal origin and the thermo-optical coefficient. Our results indicate that the presence of gold nanoparticles modifies significantly local and nonlocal nonlinearities of a colloidal system. Moreover, the amount of nanoparticles is an extremely important factor for the development of new nanostructured materials aiming ultra-fast optical and nonlocal applications. 810 nm − 4 BF − 6 PF 800 nm / Fundação de Amparo a Pesquisa do Estado de Alagoas / Nesta tese, investigamos as propriedades ópticas não lineares de quatro sistemas físicos distintos: vidros teluretos, óleo de mamona, líquidos iônicos e colóides de nanopartículas de ouro. Utilizando as técnicas de varredura Z (Z-scan) e varredura de intensidade (I-scan) foi possível determinar os valores das contribuições de origem eletrônica (n2e) e térmica (n2t) do índice de refração não linear dos sistemas estudados, bem como avaliar os seus respectivos coeficientes termo-ópticos (dn/dT). Usamos a técnica de varredura de intensidade para caracterizar cinco amostras de vidros teluretos com diferentes composições. Neste experimento utilizamos um laser de Titânio de Safira operando no regime modelocked, sintonizado em , emitindo pulsos de de duração, com a taxa de repetição ajustada em através de um seletor de pulsos. Os vidros apresentaram uma não linearidade auto-focalizadora ultra-rápida. A figura de mérito 810 nm 200 fs 1 kHz max 0 W= Δn λα foi avaliada, ea condição foi obtida para quatro das cinco amostras estudadas, demonstrando a potencialidade destes vidros para aplicações em chaveamento totalmente óptico ultra-rápido, por exemplo. O óleo de mamona é um composto orgânico natural com uma ampla gama de aplicações na indústria. No campo da nanotecnologia, este óleo tem sido explorado como um agente dispersante e estabilizante muito eficiente para sistemas coloidais de nanopartículas metálicas de ouro. Entretanto, existe uma carência de dados na literatura acerca das propriedades ópticas não lineares deste material. Neste trabalho, utilizamos a técnica de varredura Z para medir a resposta óptica não linear do óleo de mamona para excitações em 514 nm e 810 nm. Na região visível, as medidas foram realizadas no regime CW, utilizando um laser argônio. No infravermelho, um laser de Titânio de Safira, operando no regime modelocked, produzindo pulsos de , com baixa ( ) e alta ( ) taxa de repetição foi utilizado. O óleo de mamona apresentou uma refração não linear autodesfocalizadora, em ambos os comprimentos de onda. A influência das contribuições eletrônica e térmica para a não linearidade medida foi avaliada e os resultados obtidos indicam que os efeitos térmicos são os principais responsáveis pela refração não linear observada. O coeficiente termo-óptico (W > 0,27 200 fs 1kHz 76 MHz dn dT ) deste composto também foi medido para os dois comprimentos de onda. Observamos que o dn dT do óleo de mamona é aproximadamente uma ordem de magnitude maior para a excitação sintonizada em 514 nm que em 810 nm. As propriedades ópticas não lineares de dois tipos de líquidos iônicos, BMI.BF4 e BMI.PF6, também foram investigadas. Estes materiais são sais orgânicos que se caracterizam por apresentar uma baixa temperatura de fusão e pressão de vapor desprezível. Apesar de possuir propriedades físico-químicas interessantes, e serem usados em diversas aplicações, suas propriedades ópticas não lineares foram pouco investigadas. Neste trabalho, usamos a técnica de varredura Z para excitação em 514 nm e 810 nm. Ambos os líquidos iônicos apresentaram uma grande não linearidade auto-desfocalizadora, de origem térmica. Observamos que a mudança do ânion pelo ânion modifica as propriedades ópticas destes compostos. Os líquidos iônicos também apresentaram uma dispersão nos seus coeficientes termo-ópticos no intervalo espectral estudado. Apesar de ser um problema para o desenvolvimento de dispositivos fotônicos ultra-rápidos, não linearidades termo-ópticas podem apresentar um caráter de não localidade como uma conseqüência do processo de condução de calor. Efeitos não lineares em meios não locais vêm sendo abordados em diversos ramos da física, em particular em fenômenos de propagação não linear de pulsos de luz, e na geração e interação de sólitons espaciais. Os resultados obtidos sugerem que tanto o óleo de mamona, quanto os líquidos iônicos são candidatos promissores para investigação de efeitos não lineares não locais. Na caracterização dos sistemas coloidais de nanopartículas de ouro dispersas em óleo de mamona avaliamos o índice de refração não linear, coeficiente de absorção não linear, bem como o coeficiente termo-óptico em função do fator de preenchimento f. Fazendo uso da técnica de varredura Z, para o laser de excitação sintonizado em , observamos que os colóides apresentaram uma resposta refrativa não linear autodesfocalizadora ultra-rápida. Utilizando o modelo de Maxwell-Garnett generalizado para materiais compostos foi possível explicar o comportamento do índice de refração não linear do colóide em função do fator de preenchimento, bem como estimar o valor da parte real da susceptibilidade não linear de terceira ordem das nanopartículas de ouro. Observamos também que a presença de nanopartículas de ouro dispersas no óleo de mamona aumentou o valor absoluto do coeficiente de absorção linear, do índice refração não linear de origem térmica e do coeficiente termo-óptico. Nossos resultados indicam que a presença de nanopartículas de ouro altera significativamente as respostas não lineares locais e não locais de um sistema coloidal. Desta forma, a quantidade de nanopartículas é um fator extremamente importante para o desenvolvimento de novos materiais nanoestruturados visando aplicações ópticas tanto ultra-rápidas, quanto não locais.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In this work we present the results of L-asparagine H2O crystal growth and the study of their optical properties, linear and nonlinear, of crystal as grown and after being submitted to high doses of X-ray. Crystals were grown in aqueous solution by the method of slow evaporation of the solvent. Measurements optical absorption, Raman, thermal analysis and efficiency of second harmonic generation were carried out. The results demonstrate the good optical quality of the crystals for use in optical devices, comparable to that of KDP (KH2PO4). . / Neste trabalho apresentamos os resultados do crescimento de cristais de L-Asparagina-H2O e do estudo de suas propriedades ópticas, lineares e não lineares, do cristal como é crescido e após ser submetido a altas doses de raios-X. Os cristais foram crescidos em solução aquosa pelo método de evaporação lenta do solvente. Foram realizadas medidas de absorção óptica, Raman, análise térmica e eficiências de geração de segundo harmônico. Os resultados demonstram as boas qualidades ópticas dos cristais para aplicação em dispositivos ópticos, comparáveis ao do KDP (KH2PO4).

In the quest for ultrathin materials compatible with CMOS technology for all-optical signal processing applications in integrated photonics, graphene appears to be a promising candidate, with broadband1 optical properties and a high and broadband optical nonlinearity. However, researchers do not agree on the value of its nonlinear refractive index, and commonly used characterization methods do not provide a clear picture of the optical nonlinearity, in terms of its tensor nature or relaxation time. In the first part of this thesis, apart from the previously used Z-scan method, we have also used the ultrafast Optical Kerr Effect method coupled to Optical Heterodyne Detection (OHD-OKE) for the characterization of the third order optical nonlinearity of monolayer CVD graphene at telecom wavelengths. This method allows to separately measure the real and the imaginary part of the third-order nonlinearity, as well as their dynamics. With respect to the Z-scan method, OHD-OKE presents the major advantage of being robust against inhomogeneities of the sample. As such, we have demonstrated that graphene has a negative nonlinear refractive index, contrary to previously reported results. In addition, we have studied the real and imaginary part of graphene’s nonlinearity, when electrostatic gating is applied to change the chemical potential of graphene. Furthermore, we have proposed an enhanced version of the OHD-OKE method, together with the appropriate theoretical framework, in order to extract the tensor elements of the nonlinearity including the out-of-plane tensor elements. In particular, we have measured separately the time response of the two main tensor elements of the nonlinear susceptibility and we have experimentally verified that the out-of-plane tensor components are negligible. In the second part of this thesis, we have investigated, from an experimental point of view, the use of the nonlinear optical response of graphene for all-optical switching applications in integrated photonics. Namely, we have designed simple silicon nitride waveguide structures that constitute basic building blocks of switching devices, which were then fabricated and covered by graphene patches. Finally, we have experimentally tested the graphene-covered structures at low and high power levels and discussed the results. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished