The emperical pseudopotential method in the large basis approach was used to calculate the electronic bandstructures of bulk semiconductor materials and layered semiconductor heterostructures. The crucial continuous atomic form factor potentials needed to carry out such calculations were determined by using Levenberg-Marquardt optimization in order to obtain optimal cubic spline interpolations of the potentials. The optimized potentials were not constrained by any particular functional form (such as a linear combination of Gaussians) and had better convergence properties for the optimization. It was demonstrated that the results obtained in this work could potentially lead to better agreement between calculated and empirically determined band gaps via optimization / Physics / M. Sc. (Physics)

Esta tese compõe-se de contribuições à física das propriedades eletrônicas das heteroestruturas semicondutoras. São investigadas propriedades eletrônicas das duas hetero­estruturas básicas: o poço quântico e a super-rede. Considera-se o poço quântico dopado com impurezas rasas e estudam-se as suas propriedades eletrônicas nos regimes de poço fraca e altamente dopado. No caso de baixa densidade de impurezas é feita uma simulação Monte Carlo. É utilizado um modelo semi-clássico de band de impureza. A interação elétron-elétron é incluída de forma exata e são calculadas as seguintes propriedades do estado fundamental à temperatura zero: densidade de estados de uma partícula, distribuição de carga, energia de Fermi e distribuição do campo elétrico sobre os doadores neutros, todas em função do grau de compensação, da densidade de impurezas e da largura do poço. É observada uma. grande dependência com a compensação. Os resultados são explicados à luz da competição entre os efeitos de desordem e confinamento. É observada a ocorrência de Coulomb Gap característico de sistemas bidimensionais. Mostra-se que a. distribuição de carga possui largura e constante de decaimento determinados independentemente pela compensação e pela concentração de impurezas, respectivamente. Tais resultados são importantes para a caracterização de poços quânticos puros. No limite altamente dopado parte-se de um modelo light-binding desordenado e calcula­se a densidade de estados de uma partícula formada devido ao overlapping entre os estados localizados; utiliza-se o método de Matsubara e Toyosawa. para a obtenção da média sobre configurações. Discutem-se os efeitos da desordem diagonal introduzida pelo potencial de confinamento os quais são comparados com os da. desordem não-diagonal. São apresentados resultados para a densidade de estados em função do grau de confinamento e concentração de impurezas para poços e fios quânticos. Sâo estudadas as propriedades eletrônicas das super-redes sob campo magnético transversal à direção de crescimento. Mostra-se que esta configuração é ideal para o estudo das características básicas das super-redes: a estrutura de mini bandas e o tunelamento. Calculam-se as sub-bandas de condução utilizando a teoria de massa efetiva de muitas bandas. Introduz-se a idéia de massa efetiva renormalizada para barreiras semicondutoras. Comparam-se os resultados com dados experimentais de ressonância ciclotrônica. A ótima concordância obtida demonstra a grande importância e a utilidade do conceito de massa efetiva renormalizada para barreiras semicondutoras, que é uma maneira nova e simples de lidar com as soluções evanescentes. / This thesis is composed of contributions to the theory of electronic properties of semicon­ ductor heterostructures. Electronic properties of the basic two heterostructures (quantum well and superlattice) are investigated. A quantum well doped with shallow impurities is considered and its electronic properties are studied in both limits: lightly and heavily doped. In the first case a Monte Carlo simula­ tion technique is used. A semiclassical impurity band model is used . The electron-electron interaction is included exactly and properties of the ground state such as the density of single particle states, the charge distribution, the Fermi energy and the electric field di tribution on the neutra/ donors are calculated, all of them as a function of the degree of compensation, the impurity concentration and the width of the well. A great dependency with the compensation is observed. The results are explained by the competition between the effects of disorder and confinement. The existence of a Coulomb Gap is verified . The charge distribution is shown to have a width and decay rate given by the degree of compensation and impurity concentration, in this order. Such results are important to characterize pure quantum wells. On the heavily doped limit, a disordered tight-binding model is used and the density of states that is formed by the overlapping of localized states is calculated by using the method of Matsubara and Toyosawa for the configuration average. The diagonal disord er effect introduced by the confinement potential is considered and compared to that of the non­ diagonal disorder. Results of the density of states as a function of the degree of confinement and impurity concentration for quantum wells and wires are presented. The electronic propertie s of a superlattice under a magnetic field which is transversal to the growth direction are studied. Jt is shown that this configuration is id eal for the study of the basic characteristics of the superlattices: the subband structure and the tunneling. The conduction subbands are calculated by using the theory of many bands effective mass. The idea of renormalized effective mass for barriers is introduced. The obtained level spacings are compared with cyclotron resonance experimental data (infrared absorption). The good agreement obtained demonstrates the importance and usefulness of the renormalized effective mass, which is a new and simple way to handle evanescent waves.

This work investigates the defect energies, band alignments, and charge carrier recombination in polycrystalline Cu(In1-xGax)(Se1-ySy)2 chalcopyrite thin films and the interrelationship with the alloy composition. Photoluminescence spectroscopy of investigated Cu-poor Cu(In,Ga)(Se,S)2 layers generally shows broad emission lines with the corresponding maxima shifting towards higher energies under decreasing temperature or under increasing excitation power. Admittance spectroscopy of Cu-poor ZnO/CdS/Cu(In,Ga)(Se,S)2 chalcopyrite devices shows that the activation energies of the dominant defect distributions involving donors at the CdS/absorber interface and deep acceptors in the chalcopyrite bulk, increase upon alloying CuInSe2 with S. The band alignments within the Cu(In1-xGax)(Se1-ySy)2 system are determined using the energy position of the bulk acceptor state as a reference. The band gap enlargement under Ga alloying is accommodated almost exclusively in the rise of the conduction band edge, whereas the increase of band gap upon alloying with S is shared between comparable valence and conduction band offsets. The extrapolated band discontinuities [delta]EV(CuInSe2/CuInS2) = -0.23 eV, [delta]EC(CuInSe2/CuInS2) = 0.21 eV, [delta]EV(CuInSe2/CuGaSe2) = 0.036 eV, and [delta]EC(CuInSe2/CuGaSe2) = 0.7 eV are in good agreement with theoretical predictions. Current-voltage analysis of Cu-poor ZnO/CdS/Cu(In,Ga)(Se,S)2 devices reveals recombination barriers which follow the band gap energy of the absorber irrespective of alloy composition, as expected for dominant recombination in the chalcopyrite bulk. In turn, the recombination at the active junction interface prevails in Cu-rich devices which display substantially smaller barriers when compared to the band gap energy of the absorber. The result indicates that the Cu-stoichiometry is the driving compositional parameter for the charge carrier recombination in the chalcopyrite heterojunctions under investigations.