Materiais com luminescência persistente são normalmente baseados em aluminatos e silicatos dopados com íons Eu2+, portanto buscam-se novos materiais com diferentes dopantes. Consequentemente, os materiais BaAl2O4:Eu2+,TR3+ (R: La-Lu) foram preparados pelo método de combustão com temperaturas de ignição entre 400 e 600 °C, assim como pelo método cerâmico a 1500 °C. Os sistemas mais versáteis CdSiO3:TR3+ foram preparados apenas pelo método cerâmico a 950 °C. Para estudar a estrutura e a pureza de fase dos materiais utilizou-se espectroscopia de absorção no infravermelho, difração de raios X (método do pó) e microscopia eletrônica de varredura. Os estados de oxidação e o ambiente ao redor dos íons terras raras foram investigados com a espectroscopia de absorção de raios X com radiação Síncrotron (XANES e EXAFS). As propriedades da luminescência persistente dos fósforos foram investigadas com as técnicas de termoluminescência (TL), fotoluminescência e espectroscopia com radiação Síncrotron na região do UV-UV vácuo. Baseado nas medidas de TL, a estrutura dos defeitos dos materiais BaAl2O4:Eu2+,TR3+ (TR: Nd e Dy) e CdSiO3:TR3+ (TR: Pr, Gd e Tb) mostrou-se ideal para a luminescência persistente a temperatura ambiente. Os espectros de XANES indicaram a presença dos estados divalente e trivalente do Eu dopado na matriz BaAl2O4, enquanto que apenas íons TR3+ co-dopantes foram observados (exceto CeIV). O íon Eu3+ pode estar presente devido ao processo de migração do elétron do íon Eu2+ para a banda de condução durante o processo de excitação. Em contraste, para o sistema CdSiO3:TR3+, foram observadas apenas as espécies trivalentes TR3+, excluindo, portanto, a oxidação direta TR3+→TRIV. Apenas a transição interconfiguracional 4f65d1→4f7 do íon Eu2+ foi observada na luminescência persistente dos materiais BaAl2O4:Eu2+,TR3+. Por outro lado, para a matriz CdSiO3 dopada com íons Pr3+ e Tb3+, apenas as transições 4fn-4fn foram observadas, sem a presença da banda de emissão defeitos observada tanto no espectro de emissão sob excitação no UV como no espectro de luminescência persistente do CdSiO3:Gd3+. O band gap das matrizes BaAl2O4 (6,5 eV) e CdSiO3 (5,28 eV) foi obtido com a espectroscopia de excitação no UV-UV vácuo. A posição dos níveis de energia dos íons TR2+/3+ determinada com o auxílio da banda de transferência de carga ligante metal (LMCT) O2-(2p)Eu3+ confirmou o papel dos elétrons como carregadores de carga no mecanismo da luminescência persistente dos íons Eu2+, Pr3+ e Tb3+. Por fim, os mecanismos da luminescência persistente foram desenvolvidos, e, apesar de serem diferentes, os mecanismos para os íons Eu2+, Tb3+ e Pr3+ apresentaram princípios similares. Esta semelhança confirma a solidez da interpretação dos dados experimentais dos materiais com luminescência persistentes dopados com Eu2+ e encoraja a expansão de modelos similares para outros materiais com luminescência persistente no futuro. Cálculos teóricos com, por exemplo, método DFT poderão no futuro ser utilizados para refinar o modelo, diminuir o trabalho experimental e para descobrir novos modelos para sistemas que o atual modelo não pode ser aplicado, como no caso dos materiais dopados com Eu3+. / Persistent luminescent materials are usually based on Eu2+ doped aluminates or silicates, though novel materials with different dopants are seeked for. Accordingly, BaAl2O4:Eu2+,R3+ (R: La-Lu) materials were prepared by the combustion method with ignition temperatures between 400 and 600 °C as well as with the solid state reaction at 1500 °C. The more versatile CdSiO3:R3+ systems were prepared only with the solid state reaction at 950 °C. Infrared absorption spectroscopy, X-ray powder diffraction and Scanning Electron Microscopy techniques were used to study the structure and phase purity of the materials. The oxidation states of the rare earths and their environment were investigated with synchrotron radiation X-ray absorption spectroscopy (XANES and EXAFS). The persistent luminescence properties of the phosphors were investigated with thermoluminescence (TL), photoluminescence and synchrotron radiation UV-VUV spectroscopy. Based on the TL measurements, the trap structure for BaAl2O4:Eu2+,R3+ (R: Nd and Dy) and CdSiO3:R3+ (R: Pr, Gd and Tb) is ideal for room temperature persistent luminescence. The XANES spectra indicated the presence of both divalent and trivalent europium doped in the BaAl2O4 host, while only trivalent rare earth co-dopants were observed (except CeIV). Eu3+ may be present because of in situ charging of persistent luminescence. In contrast for the CdSiO3:R3+ system, only the trivalent R3+ species were observed, thus excluding the direct R3+→RIV (R: Pr and Tb) oxidation. Only the typical interconfigurational 4f65d1→4f7 transition of Eu2+ ion was observed in the persistent luminescence of BaAl2O4:Eu2+,R3+ materials. On the other hand, for the Pr3+ and Tb3+ doped CdSiO3, only 4fn-4fn transitions were observed with no traces of the defect band emission observed in either the conventional UV excited or persistent luminescence spectra of CdSiO3:Gd3+. The band gap energy for the hosts BaAl2O4 (6.5 eV) and CdSiO3 (5.28 eV) were obtained with the UV-VUV excitation spectroscopy. The R2+/3+ energy levels positions determined with the aid of the O2-(2p)→Eu3+ ligand to metal charge transfer transition (LMCT) confirmed the role of electrons as the charge carriers in the mechanism of Eu2+, Pr3+ and Tb3+ persistent luminescence. Finally, the persistent luminescence mechanisms were constructed and, despite the differences, the mechanisms for Eu2+, Tb3+ and Pr3+ proved to be rather similar. This similarity confirms the solidity of the interpretation of experimental data for the Eu2+ doped persistent luminescence materials and encourages the expansion of similar models for other persistent luminescence materials in the future. Theoretical calculations by e.g. DFT method can be used to refine the model, to decrease experimental work and to find different models for systems where the present model evidently fails, e.g. Eu3+ doped materials.

Made available in DSpace on 2014-06-11T19:32:52Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-02-12Bitstream added on 2014-06-13T19:03:33Z : No. of bitstreams: 1 dias_fc_dr_jabo.pdf: 950154 bytes, checksum: 170fddcca2fc4c7004161e93f093a97f (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / A ocorrência de anticorpos neutralizantes contra os genótipos do vírus da diarréia viral bovina (BVDV 1 e BVDV 2) foi verificada, pelo teste de virusneutralização (VN), em 260 amostras de soro sangüíneo de 26 rebanhos não vacinados contra o BVDV, provenientes dos Estados de Minas Gerais e São Paulo. Do total de amostras, 102 (39,2%) reagiram ao BVDV, das quais 81 (31,1 %) foram reagentes ao BVDV 1 e ao BVDV 2, sete (2,7%) reagiram apenas ao BVDV 1 e 14 (5,4%) reagiram apenas ao BVDV 2. Nos mesmos rebanhos, verificou-se também a presença sugestiva de animais persistentemente infectados (PI) por meio da pesquisa de anticorpos neutralizantes em cinco amostras de soro sangüíneo de bezerros sentinelas com idade entre 6 e 12 meses. A ocorrência de animais PI foi pesquisada em três dos 26 rebanhos, dos quais foram colhidas amostras pareadas de sangue de todos os animais do rebanho. Todas as amostras foram submetidas ao teste de VN contra o BVDV 1 e o BVDV 2, e naquelas não reagentes a pelo menos um dos genótipos, bem como nas amostras provenientes de bovinos com menos de seis meses de idade, foi realizada a pesquisa do vírus pela RT-PCR. Em um dos rebanhos foram detectados dois animais PI, cujas estirpes foram caracterizadas geneticamente como pertencentes ao subgenótipo eVOV 1 b. A infecção natural pelo BVDV foi monitorada nos três rebanhos selecionados para a pesquisa de animais PI, sendo que em dois deles constatou-se a eliminação do BVDV. No entanto, a infecção permaneceu no rebanho em que haviam sido detectados dois animais PI, pois foram diagnosticados posteriormente um animal transitoriamente infectado (TI) e novos animais reagentes ao vírus. Foram submetidos à análise estatística os resultados dos testes de VN contra o BVDV 1 e o BVDV 2, realizados em 1925 amostras de soro sangüíneo obtidas no período de execução... / The occurrence of neutralizing antibodies against to bovine viral diarrhoea virus genotypes (BVDV 1 and BVDV 2) has been confirmed by virusneutralization test (VN) in 260 samples of blood serum undertaken in the states of Minas Gerais and São Paulo, Brazil. Samples were retrieved from 26 cattle herds which were not BVDV vaccinated. One hundred and two samples (39.2%) were reagents to BVDV, or rather, 81 (31.1%) were reagents to BVDV 1 and BVDV 2, seven (2.7%) were reagents to BVDV 1 only and 14 (5.4%) were reagents to BVDV 2 only. In the same herds, the significant presence of persistently infected (PI) animais was also verified by a research involving neutralizing antibodies in five samples of blood serum in 6 to 12¬month-old calves. The occurrence of PI animais was researched in three out of 26 herds by paired blood samples of total animais in the herdo Ali samples were analyzed by VN test against to BVDV 1 and BVDV 2, and virus research was undertaken by RT-PCR in samples which were not reagent to at least one of the genotypes and in samples of less than 6-month-old cattle. Two PI animais, genetically characterized as belonging to BVDV 1 b subgenotype, were detected in one of the herds. BVDV natural infection was monitored in three herds selected for PI animais research. BVDV was eliminated in two herds. However, infection remained in the herd in which two PI animais were diagnosed, because a transiently infected animal (TI) and other virus-reagent animais were detected later on. Statistical analysis evaluated VN test results against BVDV 1 and BVDV 2 with 1925 samples of blood serum obtained during the research period. Although no significant ditterences were found between BVDV 1 reagent bovines and BVDV 2 reagent ones (p>0.05), a significant ditterence was detected among titles of antibodies from samples which were reagent to both genotypes (p<0.0001).

Despite measures on the European level to increase the compatibility between the HE sectors of the member states, the recent literature exposes variations in their efficiencies. To gain insights into these differences we split the efficiency term according to the two management levels each university is confronted with. Utilizing a recent advancement in the method to measure efficiency, we separate short-term (transient) and long-term (persistent) efficiency, while controlling for unobserved institution specific heterogeneity. While the first term reflects the efficiency of the individual universities working within the country, the second term echoes the influence of the country specific overall HE structure. The cross-country comparison displays if the overall efficiency difference between countries is related to individual performance of their universities or their HE structure. This allows more purposeful policy recommendation and expands the literature regarding the efficiency of universities in a fundamental way. Choosing Italy and Germany as two important illustrative examples we can take advantage of a novel dataset including characteristics of institutions in both countries for an exceptional long period of time from 2001 to 2011. We show that the Italian universities exhibit a higher overall efficiency value than their German counterparts. With the individual universities working at the upper bound of efficiency in both countries, the overall inefficiency as well as the gap between the countries is caused by persistent, structural inefficiency. To expedite a true European Area of Higher Education future measures should hence aim at the country specific structure, not solely at affecting the activities of single universities.

Dans cette thèse, nous présentons les risques posés par les Menaces Persistentes Avancées (APTs) et proposons une approche en deux temps pour distinguer les attaques qui en font partie. Ce travail fait partie d'Akheros, un Système de Détection d'Intrusion (IDS) autonome développé par trois doctorants. L'idée est d'utiliser l'apprentissage machine pour détecté des évènements inattendus et vérifier s'ils posent un risque de sécurité. La dernière étape, et le sujet de cette thèse, est de mettre en évidence les APT. Les campagnes d'APT sont particulièrement dangereuses car les attaquants sont compétents et ont un but précis ainsi que du temps et de l'argent. Nous partons des résultats des parties précédentes d'Akheros: une liste d'évènements traduisible en flux d'information et qui indique quand des attaques sont détectées. Nous faisons ressortir les liens entre attaques en utilisant le Suivi de Flux d'Information: nous ajoutons une nouvelle teinte pour chaque attaque. Lors de la propagation, si une teinte se trouve en amont d'un flux qui fait partie d'une attaque, alors les deux attaques sont liés. Certaines attaques se trouvent liées par erreur car les évènements que nous utilisons ne sont pas assez précis, d'où l'approche en deux temps. Dans le cas où certaines attaques ne sont pas détectées, la teinte de cette attaque n'est pas créée, cependant, les autres teintes sont propagées normalement, et l'attaque précédent l'attaque non détectée sera liée à l'attaque lui faisant suite. Le deuxième temps de l'approche est de retirer les liens erronés. Nous utilisons un Modèle de Markov Caché pour représenter les APTs et retirons les campagnes qui ne suivent pas le modèle. Ceci fonctionne car les APTs, quoique toutes différentes, passent par les mêmes phases. Ces phases sont les états cachés du modèle. Les observations sont les types d'attaques effectuées pendant ces phases. De plus, les actions futures des attaquants dépendent des résultats de l'action en cours, ce qui satisfait l'hypothèse de Markov. Le score utilisé pour classer les campagnes potentielles de la plus proche d'une APT à la plus éloigné est basé sur un algorithme de Viterbi modifié pour prendre en compte les attaques non détectées potentielles. / In this thesis, we present the risks posed by Advanced Persitent Threats (APTs) and propose a two-step approach for recognising when detected attacks are part of one. This is part of the Akheros solution, a fully autonomous Intrusion Detection System (IDS) being developed in collaboration by three PhD students. The idea is to use machine learning to detect unexpected events and check if they present a security risk. The last part, and the subject of this thesis, is the highlighting of APT. APTs campaigns are particularly dangerous because they are performed by skilled attackers with a precise goal and time and money on their side.We start with the results from the previous part of the Akheros IDS: a list of events, which can be translated to flows of information, with an indication for events found to be attacks. We find links between attacks using Information Flow Tracking. To do so, we create a new taint for each detected attack and propagate it. Whenever a taint is on the input of an event that is part of another attack, then the two attacks are linked. However, the links are only potential because the events used are not precise enough, which leads to erroneously propagated taints. In the case of an undetected attack, no taint is created for that attack, but the other taints are still propagated as normal so that previous attack is still linked to the next attack, only skipping the undetected one. The second step of the approach is to filter out the erroneous links. To do so, we use a Hidden Markov Model to represent APTs and remove potential attack campaign that do not fit the model. This is possible because, while each APT is different, they all go through the same phases, which form the hidden states of our model. The visible observations are the kind of attacks performed during these phases. In addition, the results in one phase dictate what the attackers do next, which fits the Markov hypothesis. The score used to rank potential attack campaign from most likely an APT to least likely so is based on a customised Viterbi algorithm in order to take into account potentially undetected attacks.

O método cerâmico é a rota de síntese mais utilizada na produção de materiais luminescentes no estado sólido dopados com íons terras raras. Porém, as altas temperaturas necessárias para a formação dos compostos somada ao longo tempo de síntese levantam questões sobre a viabilidade energética desse método. Nos dias atuais, há grande interesse em buscar alternativas mais sustentáveis que gastem menos energia, e produtos com performances cada vez melhores. Nesse cenário, foi proposta a síntese dos materiais com luminescência persistente em forno de micro-ondas doméstico, por se tratar de um equipamento relativamente barato, que gasta muito menos energia que um forno tubular convencional, e tem um tempo de síntese muito menor. Os materiais SrS:Eu2+,TR3+ (TR = Ce, Nd, Sm, Dy, Er e Yb) foram produzidos pelo método de síntese no estado sólido assistida por micro-ondas, e para validação e comparação do método, os materiais SrS:TR (TR = Eu2+, Ce3+, Sm3+ e Yb2+/3+) foram preparados por ambos os métodos cerâmico e assistido por micro-ondas. Estudos de estrutura e morfologia dos materiais preparados foram realizados com medidas de DRX em pó e XANES na borda-LIII dos íons terras raras e na borda-K do enxofre. As propriedades luminescentes dos materiais foram investigadas com medidas de termoluminescência, luminância, espectroscopia UVVisível, espectroscopia UV-Vácuo e XEOL. Todos os materiais dopados com Eu2+ têm uma banda larga de emissão centrada em 620 nm atribuída à transição 4f65d1&#8594;4f7 com forte efeito nefelauxético. Além do Eu2+, foram observadas transições 5d&#8594;4f para o Ce3+ e o Yb2+. Estudos de luminescência persistente mostraram que a co-dopagem do SrS:Eu2+ com íons TR3+ aumentaram a duração do tempo de emissão de luz dos materiais após cessada a fonte de irradiação em mais de 400 %. Além disso, não se observou diferença na duração do fenômeno para os diferentes íons co-dopantes, mostrando que o mecanismo de luminescência persistes nesse material é governado pelo armadilhamento de elétrons em defeitos pontuais na matriz. Um novo fenômeno foi observado com a intensa luminescência persistente gerada após irradiação com raios X. Por fim, foram realizados testes de aplicação dos materiais com luminescência persistente em iluminação no estado sólido para geração de luz branca, mostrando que eles podem ser utilizados em LEDs persistentes. / Hitherto, the ceramic method is the most employed synthesis route on the production of solid-state luminescent materials doped with rare-earth ions. However, the high temperatures required for the compounds formation added up to the long synthesis time give rise to questions about the energetic viability of this method. Nowadays there is a great interest in finding more sustainable alternatives which demands less energy and provides products with better performances. Is this scenario, the synthesis of the persistent luminescence materials in a domestic microwave oven was proposed, because it is a relatively cheap equipment that spends much less energy than a conventional tubular furnace and has a shorter synthesis time. Thus, the materials SrS:Eu2+,TR3+ (TR = Ce, Nd, Sm, Dy, Er e Yb) were prepared via the microwaveassisted solid-state synthesis, and, for validation and comparison between methods, the materials SrS:TR (TR = Eu2+, Ce3+, Sm3+ and Yb2+/3+) were prepared via both the ceramic and microwave-assisted methods. Studies of structure and morphology of the prepared materials were undertaken with XRD and XANES at LIII-edge of rare-earth ions and K-edge of sulfur measurements. The luminescent properties of the materials were explored with thermoluminescence, luminance, UV-Vis spectroscopy, VUV spectroscopy and XEOL measurements. All the Eu2+-doped materials have a large emission band centered at 620 nm assigned to the 4f65d1&#8594;4f7 transition with strong nephelauxetic effect. Besides Eu2+, 5d&#8594;4f transitions were observed for Ce3+ and Yb2+ as well. Persistent luminescence studies showed that co-doping SrS:Eu2+ with TR3+ have improved the light emission timespan in over 400 % after removing the irradiation source. Moreover, no difference was detected on the emission timespan for the different co-dopant ions, showing that the persistent luminescence mechanism for this material is governed by electron trapping on the matrix point defects. A new phenomenon with high-intensity persistent luminescence was observed in these materials after irradiation with X-ray. At last, tests of application of the persistent luminescent materials with solid-state white-lighting were made, showing that they can be used in persistent LEDs.

Materiais com luminescência persistente são normalmente baseados em aluminatos e silicatos dopados com íons Eu2+, portanto buscam-se novos materiais com diferentes dopantes. Consequentemente, os materiais BaAl2O4:Eu2+,TR3+ (R: La-Lu) foram preparados pelo método de combustão com temperaturas de ignição entre 400 e 600 °C, assim como pelo método cerâmico a 1500 °C. Os sistemas mais versáteis CdSiO3:TR3+ foram preparados apenas pelo método cerâmico a 950 °C. Para estudar a estrutura e a pureza de fase dos materiais utilizou-se espectroscopia de absorção no infravermelho, difração de raios X (método do pó) e microscopia eletrônica de varredura. Os estados de oxidação e o ambiente ao redor dos íons terras raras foram investigados com a espectroscopia de absorção de raios X com radiação Síncrotron (XANES e EXAFS). As propriedades da luminescência persistente dos fósforos foram investigadas com as técnicas de termoluminescência (TL), fotoluminescência e espectroscopia com radiação Síncrotron na região do UV-UV vácuo. Baseado nas medidas de TL, a estrutura dos defeitos dos materiais BaAl2O4:Eu2+,TR3+ (TR: Nd e Dy) e CdSiO3:TR3+ (TR: Pr, Gd e Tb) mostrou-se ideal para a luminescência persistente a temperatura ambiente. Os espectros de XANES indicaram a presença dos estados divalente e trivalente do Eu dopado na matriz BaAl2O4, enquanto que apenas íons TR3+ co-dopantes foram observados (exceto CeIV). O íon Eu3+ pode estar presente devido ao processo de migração do elétron do íon Eu2+ para a banda de condução durante o processo de excitação. Em contraste, para o sistema CdSiO3:TR3+, foram observadas apenas as espécies trivalentes TR3+, excluindo, portanto, a oxidação direta TR3+&#8594;TRIV. Apenas a transição interconfiguracional 4f65d1&#8594;4f7 do íon Eu2+ foi observada na luminescência persistente dos materiais BaAl2O4:Eu2+,TR3+. Por outro lado, para a matriz CdSiO3 dopada com íons Pr3+ e Tb3+, apenas as transições 4fn-4fn foram observadas, sem a presença da banda de emissão defeitos observada tanto no espectro de emissão sob excitação no UV como no espectro de luminescência persistente do CdSiO3:Gd3+. O band gap das matrizes BaAl2O4 (6,5 eV) e CdSiO3 (5,28 eV) foi obtido com a espectroscopia de excitação no UV-UV vácuo. A posição dos níveis de energia dos íons TR2+/3+ determinada com o auxílio da banda de transferência de carga ligante metal (LMCT) O2-(2p)Eu3+ confirmou o papel dos elétrons como carregadores de carga no mecanismo da luminescência persistente dos íons Eu2+, Pr3+ e Tb3+. Por fim, os mecanismos da luminescência persistente foram desenvolvidos, e, apesar de serem diferentes, os mecanismos para os íons Eu2+, Tb3+ e Pr3+ apresentaram princípios similares. Esta semelhança confirma a solidez da interpretação dos dados experimentais dos materiais com luminescência persistentes dopados com Eu2+ e encoraja a expansão de modelos similares para outros materiais com luminescência persistente no futuro. Cálculos teóricos com, por exemplo, método DFT poderão no futuro ser utilizados para refinar o modelo, diminuir o trabalho experimental e para descobrir novos modelos para sistemas que o atual modelo não pode ser aplicado, como no caso dos materiais dopados com Eu3+. / Persistent luminescent materials are usually based on Eu2+ doped aluminates or silicates, though novel materials with different dopants are seeked for. Accordingly, BaAl2O4:Eu2+,R3+ (R: La-Lu) materials were prepared by the combustion method with ignition temperatures between 400 and 600 °C as well as with the solid state reaction at 1500 °C. The more versatile CdSiO3:R3+ systems were prepared only with the solid state reaction at 950 °C. Infrared absorption spectroscopy, X-ray powder diffraction and Scanning Electron Microscopy techniques were used to study the structure and phase purity of the materials. The oxidation states of the rare earths and their environment were investigated with synchrotron radiation X-ray absorption spectroscopy (XANES and EXAFS). The persistent luminescence properties of the phosphors were investigated with thermoluminescence (TL), photoluminescence and synchrotron radiation UV-VUV spectroscopy. Based on the TL measurements, the trap structure for BaAl2O4:Eu2+,R3+ (R: Nd and Dy) and CdSiO3:R3+ (R: Pr, Gd and Tb) is ideal for room temperature persistent luminescence. The XANES spectra indicated the presence of both divalent and trivalent europium doped in the BaAl2O4 host, while only trivalent rare earth co-dopants were observed (except CeIV). Eu3+ may be present because of in situ charging of persistent luminescence. In contrast for the CdSiO3:R3+ system, only the trivalent R3+ species were observed, thus excluding the direct R3+&#8594;RIV (R: Pr and Tb) oxidation. Only the typical interconfigurational 4f65d1&#8594;4f7 transition of Eu2+ ion was observed in the persistent luminescence of BaAl2O4:Eu2+,R3+ materials. On the other hand, for the Pr3+ and Tb3+ doped CdSiO3, only 4fn-4fn transitions were observed with no traces of the defect band emission observed in either the conventional UV excited or persistent luminescence spectra of CdSiO3:Gd3+. The band gap energy for the hosts BaAl2O4 (6.5 eV) and CdSiO3 (5.28 eV) were obtained with the UV-VUV excitation spectroscopy. The R2+/3+ energy levels positions determined with the aid of the O2-(2p)&#8594;Eu3+ ligand to metal charge transfer transition (LMCT) confirmed the role of electrons as the charge carriers in the mechanism of Eu2+, Pr3+ and Tb3+ persistent luminescence. Finally, the persistent luminescence mechanisms were constructed and, despite the differences, the mechanisms for Eu2+, Tb3+ and Pr3+ proved to be rather similar. This similarity confirms the solidity of the interpretation of experimental data for the Eu2+ doped persistent luminescence materials and encourages the expansion of similar models for other persistent luminescence materials in the future. Theoretical calculations by e.g. DFT method can be used to refine the model, to decrease experimental work and to find different models for systems where the present model evidently fails, e.g. Eu3+ doped materials.

Made available in DSpace on 2014-08-20T14:38:03Z (GMT). No. of bitstreams: 1 dissertacao_clarissa_castro.pdf: 569054 bytes, checksum: b9876922c1664dec56ef9c9d4ff5cb3a (MD5) Previous issue date: 2011-03-31 / The enzootic bovine leukosis is an illness caused by the bovine leukosis virus (BLV) which provokes a persistent infection in cattle and is responsible for significant economical losses to the bovines, mainly dairy cattle. It is widely spread in Brazilian cattle and it can come up in three forms: asymptomatic infection, persistent lymphocytosis and lymphosarcoma. The animals that have antibodies against the BLV must be eliminated or separated from the rest of the cattle, because they are carriers and disseminators of the virus during all their lifetimes. The diagnosis of this disease is essential for control and eradication strategies based on the segregation of infected animals in order to avoid or attenuate the transmission of the virus, and consequently, minimize the economical losses caused by the disease. During the BLV infection antibodies are produced against the main viral proteins, gp 51, gp 30 (envelope glicoproteins) and p24 (capsid protein). The agar gel immunodiffusion (AGID) and the enzyme-linked immunosorbent assay (ELISA) tests are the most used for diagnosis. In this report the immunoperoxidase technique (peroxidase linked assay - PLA) was evaluated in order to detect antibodies against the BLV. The results obtained in the PLA were compared with the AGID test and the specificity of the positive ones was confirmed by the Western blotting (WB) technique. Two hundred and one bovine serum samples of cattle coming from the city of Pelotas were tested: 59% (119) were positive in PLA and 26% (53) were positive in AGID. All the AGID positive samples were also PLA positive. From the 32,8% (66) of the conflicting serum results just eight were confirmed as positive in WB, indicating that the rest of the results were false-positive and showing that AGID failed in identifying 4% of the BLV positive animals. The PLA technique for the diagnosis of the BLV infection demonstrated to be very useful to use in control programs because it was more sensitive when compared to the AGID technique. However, the occurrence of false-positive results by the PLA makes its use unviable in eradication programs that involve the sacrifice of seropositive animals. / A leucose enzoótica dos bovinos (EBL) é uma enfermidade causada pelo vírus da leucose bovina (BLV), que ocasiona uma infecção persistente em bovinos, e é responsável por perdas econômicas significativas à pecuária, principalmente a leiteira. Amplamente disseminada no rebanho brasileiro, pode ser manifestada de três formas: aleucêmica, linfocitose persistente e linfossarcoma. Os animais com anticorpos contra o BLV deverão ser eliminados ou separados do restante do rebanho, pois significa que são portadores e disseminadores do vírus por toda a vida. O diagnóstico desta doença é essencial para estratégias de controle e erradicação baseadas na segregação de animais infectados no intuito de evitar ou amenizar a transmissão do vírus e, consequentemente, minimizar as perdas econômicas causadas pela doença. Durante a infecção pelo BLV são produzidos anticorpos contra as principais proteínas virais, gp51, gp30 (glicoproteínas do envelope) e p24 (proteína do capsídeo). O teste de imunodifusão em gel de ágar (agar gel immunodiffusion AGID) e o ensaio imunoenzimático (enzyme-linked immunosorbent assay ELISA) são os mais utilizados para diagnóstico. No presente trabalho foi avaliada a técnica de imunoperoxidase (peroxidase linked assay PLA) na detecção de anticorpos contra o BLV. Os resultados obtidos na PLA foram comparados com o teste de AGID e a especificidade dos positivos confirmada pela técnica de Western blotting (WB). Foram testadas 201 amostras de soro de bovinos provenientes de propriedades localizadas no município de Pelotas: 59% (119) foram positivos por PLA e 26% (53) positivos por AGID. Todas as amostras positivas na AGID foram também positivas na PLA. Dos 32,8% (66) dos soros com resultados conflitantes apenas oito foram confirmados como positivos no WB, indicando serem falso-positivos os demais resultados e constatando que a AGID falhou em identificar 4% de animais positivos para EBL. A técnica de PLA para diagnóstico de infecção pelo BLV se mostrou muito útil para uso em programas de controle devido à maior sensibilidade da técnica quando comparada com o teste de AGID. Contudo, a ocorrência de resultados falso-positivos pela PLA inviabiliza o seu uso em programas de erradicação que envolva o sacrifício do animal soropositivo.

Im ersten Teil der vorliegenden Arbeit wird der Einfluss der Abscheideparamter von In2S3 Dünnfilmen, die mittels thermischem Verdampfen hergestellt wurden, auf ihre physikalischen Eigenschaften untersucht. Es zeigte sich, dass die Abscheideparameter einen starken Einfluss auf die Oberflächenmorphologie und die strukturellen Eigenschaften haben. Durch eine Optimierung der Herstellungsparameter konnten β-In2S3 Dünnfilme in (103) Orientierung hergestellt werden. Epitaktisches Wachstum von In2S3 Schichten mit jeweils zwei bzw. vier Rotationsdomainen wurden auf c- und a-Saphir erreicht. Die fundamentale optische Bandlücke wurde für alle Dünnfilme zu 2.1 eV bestimmt. Eine starke persistente Photoleitung, welche auf tiefe Defekte innerhalb der Bandlücke zurückgeführt werden konnte, wurde unabhängig von den Abscheideparametern und dem gewählten Substrat beobachtet. Prototypen für Solarzellen wurden aus n-In2S3 und p-Zinkkobaltoxid (ZCO) hergestellt und zeigen ein hohes Sperrverhältniss und photovoltaische Aktivität, welche jedoch durch Absorption im ZCO limitiert wird. Im zweiten Teil der Arbeit wurden In2S3:V Dünnfilme ohne bzw. mit Saat- und Pufferschichten hergestellt, um deren physikalische Eigenschaften zu untersuchen bzw. um Zwischenbandsolarzellen herzustellen. Ein großer Dotierbereich von bis zu 11.4 at-% V, wurde durch einen kombinatorischer Ansatz erziehlt. Für Dünnfilme ohne Saatschicht wurde die Löslichkeitsgrenze von Vanadium in In2S3 zu 3.2 at-% V (auf Saphirsubstraten) bzw. 5.4 at-% V (auf Glassubstraten) bestimmt. Durch die Verwendung einer Saatschicht konnte die In2S3 β-Phase stabilisiert und darüber hinaus die Ausbildung von Fremdphasen unterdrückt werden. In2S3:V Dünnfilme mit über 5.8 at-% V auf Saphirsubstraten zeigten bei Raumtemperatur p-Typ Leitfähigkeit. Für Temperaturen unterhalb einer kritischen Temperatur ergab sich ein Wechsel von p- zu n-Leitung. Darüber hinaus sank die Mobilität dieser Schichten unterhalb der kritischen Temperatur signifikant ab. Die Ladungsträgerdichte blieb jedoch über den gesamte Temperaturbereich hinweg konstant und war mit Werten im Bereich von 1022 cm−3 zudem sehr hoch. Diese elektrischen Eigenschaften sind sehr untypisch für einen gewöhnlichen Halbleiter. Sie konnten jedoch im Rahmen dieser Arbeit durch das Modell der Zwischenbandsolarzelle beschieben werden. Als Schlussfolgerung dessen, wurde die Vanadiumkonzentration, bei der sich das Zwischenband ausbildet zu 3.2 at-% V bestimmt. Da sich herausstellte, das In2S3:V bei Raumtemperatur p-Typ ist, konnten keine Zwischenbandsolarzellen mit p-ZCO hergestellt werden.:1 Introduction 1 2 Theoretical background 3 2.1 Indium sulfide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 2.2 The physics of solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2.3 The concept of intermediate band solar cells . . . . . . . . . . . . . . . 8 2.4 Indium sulfide as intermediate band material . . . . . . . . . . . . . . . 11 2.5 Charge transport . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 2.6 Electronic defect states . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 3 Methods 17 3.1 Growth and structuring techniques . . . . . . . . . . . . . . . . . . . . 17 3.1.1 Thermal evaporation . . . . . . . . . . . . . . . . . . . . . . . . 17 3.1.2 Pulsed laser deposition . . . . . . . . . . . . . . . . . . . . . . . 19 3.1.3 Sputter deposition . . . . . . . . . . . . . . . . . . . . . . . . . 20 3.1.4 Photolithography . . . . . . . . . . . . . . . . . . . . . . . . . . 21 3.2 characterization techniques . . . . . . . . . . . . . . . . . . . . . . . . . 22 3.2.1 X-ray diffraction measurement . . . . . . . . . . . . . . . . . . . 22 3.2.2 Hall effect measurement . . . . . . . . . . . . . . . . . . . . . . 23 3.2.3 Current-voltage measurement . . . . . . . . . . . . . . . . . . . 25 3.2.4 Temperature-dependent current-voltage measurement . . . . . . 26 3.2.5 Resistance measurement . . . . . . . . . . . . . . . . . . . . . . 26 3.2.6 Spectroscopic ellipsometry . . . . . . . . . . . . . . . . . . . . . 26 3.2.7 Energy dispersive X-ray spectroscopy . . . . . . . . . . . . . . . 27 3.2.8 Transmittance and reflection spectroscopy . . . . . . . . . . . . 27 4 Physical properties of undoped In2S3 . . . . . . . . . .29 4.1 Impact of the growth parameters on the composition . . . . . . . . . . 31 4.2 Desorption mechanisms and their influence on the growth rates . . . . . 33 4.3 Surface morphological properties . . . . . . . . . . . . . . . . . . . . . 35 4.4 Structural properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37 4.5 Optical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 4.5.1 Dielectric function and absorption coefficient of In2S3 . . . . . . 43 4.5.2 Impact of the growth parameter . . . . . . . . . . . . . . . . . . 48 4.5.3 Impact of the composition . . . . . . . . . . . . . . . . . . . . . 49 4.5.4 Impact of the substrate crystallinity . . . . . . . . . . . . . . . . 51 4.6 Electrical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52 4.6.1 Persistent photoconductivity . . . . . . . . . . . . . . . . . . . . 52 4.6.2 Temperature dependent resistivity and Hall effect measurements 63 4.7 Device characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . 69 4.7.1 Impact of the growth parameter . . . . . . . . . . . . . . . . . . 70 4.7.2 Impact of the substrate crystallinity . . . . . . . . . . . . . . . . 79 4.8 Solar cell performance . . . . . . . . . . . . . . . . . . . . . . . . . . . 83 4.8.1 Impact of the growth parameter . . . . . . . . . . . . . . . . . . 83 4.8.2 Impact of the substrate crystallinity . . . . . . . . . . . . . . . . 88 5 Physical properties of vanadium-doped In2S3. . . . . . . . . .91 5.1 Vanadium incorporation into the In2S3 thin films . . . . . . . . . . . . 93 5.2 Surface morphological properties . . . . . . . . . . . . . . . . . . . . . 95 5.3 Structural properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96 5.4 Optical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107 5.5 Electrical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109 5.6 Device characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . 120 6 Summary and Outlook . . . . . . . . . .125 List of Abbreviations. . . . . . . . . . 131 List of Symbols. . . . . . . . . . 133 Bibliography . . . . . . . . . .137 List of Own and Contributed Articles . . . . . . . . . .149 Appendix . . . . . . . . . .151 Publikationsliste nach Promotionsordnung § 11(3). . . . . . . . . . 161 Zusammenfassung nach Promotionsordnung § 11(4) . . . . . . . . . .163 / In the first part of the presented work the influence of the growth parameter of In2S3 thin films, grown by physical vapor deposition, on their physical properties is investigated. The deposition parameters were found to have a strong influence on the surface morphology and the structural properties. By choosing appropriate deposition parameters β-phase In2S3 with a pure (103) orientation was achieved. Epitaxial growth with 2 and 4 rotational domains could be induced using c- and a-plane sapphire, respectively. The fundamental optical bandgap was determined to be direct with an energy of 2.1 eV for all In2S3 thin films. A strong persistent photoconductivity, which was attributed to deep defects within the bandgap, was observed for all In2S3 thin films independent of the preparation conditions and independent of the kind of substrate. Solar cells of n-In2S3/p-zinc-cobalt-oxide (ZCO) exhibit high current rectifications and photovoltaic activity but suffer from absorption in the ZCO layer. To study the physical properties of In2S3:V thin films and to implement intermediate band solar cells (IBSC) In2S3:V thin films without and with seed and buffer layers were fabricated, respectively. Using a combinatorial material synthesis approach doping concentrations of up to 11.4 at-% V were achieved. Thin films without seed layers exhibit a solubility limit of vanadium of 3.2 at-% V and 5.4 at-% V for thin films on sapphire and glass substrates, respectively. The In2S3:V β-phase could be stabilized and the formation of secondary phases suppresed by inserting a seed layer. A change of the type of the charge carriers from p-type at room temperature to n-type at low temperatures was observed for thin films with doping concentrations above 5.8 at-% V on sapphire substrates. Furthermore, the mobility decreases significantly below the critical temperature. Contrarily, a very high charge carrier concentration was observed independent of the temperature. This behavior, which is untypical for conventional semiconductors, could be described using the intermediate band (IB) model. According to the results of this work and the IB model, one can conclude, that above a vanadium concentration 3.2 at-% V an IB has formed. Due to the p-type conductivity of In2S3:V thin films at room temperature, rectifying IBSCs could not be implemented using p-type ZCO. Therefore, it should be replaced by an n-type material in future investigations.:1 Introduction 1 2 Theoretical background 3 2.1 Indium sulfide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 2.2 The physics of solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2.3 The concept of intermediate band solar cells . . . . . . . . . . . . . . . 8 2.4 Indium sulfide as intermediate band material . . . . . . . . . . . . . . . 11 2.5 Charge transport . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 2.6 Electronic defect states . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 3 Methods 17 3.1 Growth and structuring techniques . . . . . . . . . . . . . . . . . . . . 17 3.1.1 Thermal evaporation . . . . . . . . . . . . . . . . . . . . . . . . 17 3.1.2 Pulsed laser deposition . . . . . . . . . . . . . . . . . . . . . . . 19 3.1.3 Sputter deposition . . . . . . . . . . . . . . . . . . . . . . . . . 20 3.1.4 Photolithography . . . . . . . . . . . . . . . . . . . . . . . . . . 21 3.2 characterization techniques . . . . . . . . . . . . . . . . . . . . . . . . . 22 3.2.1 X-ray diffraction measurement . . . . . . . . . . . . . . . . . . . 22 3.2.2 Hall effect measurement . . . . . . . . . . . . . . . . . . . . . . 23 3.2.3 Current-voltage measurement . . . . . . . . . . . . . . . . . . . 25 3.2.4 Temperature-dependent current-voltage measurement . . . . . . 26 3.2.5 Resistance measurement . . . . . . . . . . . . . . . . . . . . . . 26 3.2.6 Spectroscopic ellipsometry . . . . . . . . . . . . . . . . . . . . . 26 3.2.7 Energy dispersive X-ray spectroscopy . . . . . . . . . . . . . . . 27 3.2.8 Transmittance and reflection spectroscopy . . . . . . . . . . . . 27 4 Physical properties of undoped In2S3 . . . . . . . . . .29 4.1 Impact of the growth parameters on the composition . . . . . . . . . . 31 4.2 Desorption mechanisms and their influence on the growth rates . . . . . 33 4.3 Surface morphological properties . . . . . . . . . . . . . . . . . . . . . 35 4.4 Structural properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37 4.5 Optical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 4.5.1 Dielectric function and absorption coefficient of In2S3 . . . . . . 43 4.5.2 Impact of the growth parameter . . . . . . . . . . . . . . . . . . 48 4.5.3 Impact of the composition . . . . . . . . . . . . . . . . . . . . . 49 4.5.4 Impact of the substrate crystallinity . . . . . . . . . . . . . . . . 51 4.6 Electrical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52 4.6.1 Persistent photoconductivity . . . . . . . . . . . . . . . . . . . . 52 4.6.2 Temperature dependent resistivity and Hall effect measurements 63 4.7 Device characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . 69 4.7.1 Impact of the growth parameter . . . . . . . . . . . . . . . . . . 70 4.7.2 Impact of the substrate crystallinity . . . . . . . . . . . . . . . . 79 4.8 Solar cell performance . . . . . . . . . . . . . . . . . . . . . . . . . . . 83 4.8.1 Impact of the growth parameter . . . . . . . . . . . . . . . . . . 83 4.8.2 Impact of the substrate crystallinity . . . . . . . . . . . . . . . . 88 5 Physical properties of vanadium-doped In2S3. . . . . . . . . .91 5.1 Vanadium incorporation into the In2S3 thin films . . . . . . . . . . . . 93 5.2 Surface morphological properties . . . . . . . . . . . . . . . . . . . . . 95 5.3 Structural properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96 5.4 Optical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107 5.5 Electrical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109 5.6 Device characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . 120 6 Summary and Outlook . . . . . . . . . .125 List of Abbreviations. . . . . . . . . . 131 List of Symbols. . . . . . . . . . 133 Bibliography . . . . . . . . . .137 List of Own and Contributed Articles . . . . . . . . . .149 Appendix . . . . . . . . . .151 Publikationsliste nach Promotionsordnung § 11(3). . . . . . . . . . 161 Zusammenfassung nach Promotionsordnung § 11(4) . . . . . . . . . .163

The development of organic materials displaying room-temperature phosphorescence is a research field that has attracted more and more attention in the last years. Most studies focus on designing or optimizing emitter molecules to increase the phosphorescent performance in host:emitter systems. Rarely, the overall thin-film preparation routines are compared with respect to their triplet-state luminescence yield. Herein, different film preparation techniques are investigated using the very same emitter molecule. A variation of host polymer, post-annealing temperature, and fabrication procedure is evaluated with respect to the obtained phosphorescent lifetime, photoluminescent quantum yield, and phosphorescence-to-luminescence ratio. This study elaborates the importance of different film preparation techniques and gathers a concise set of data which is helpful to anyone optimizing the phosphorescence of a particular system.

A luminescência persistente é um fenômeno em que o material emite radiação de segundos a várias horas após cessada a irradiação (luz, radiação UV, feixe de elétrons, etc.). No entanto, os mecanismos que geram o fenômeno da luminescência persistente ainda não são totalmente estabelecidos. Neste trabalho os materiais Lu2O3:TR3+,M (TR,M: Pr,HfIV; Eu, Ca2+ ou Tb,Ca2+) foram preparados pelo método de estado-sólido assistido por micro-ondas (MASS) e comparados com aqueles sintetizados pelo método cerâmico. As vantagens do método MASS incluem curto tempo de processamento, aquecimento dielétrico seletivo, baixo consumo de energia e uso de equipamentos de baixo custo (forno micro-ondas doméstico), muitas vezes produzindo produtos de alta pureza e alto rendimento. Os materiais foram caracterizados pelas técnicas de espectroscopia de absorção na região do infravermelho (IR), espectroscopia Raman, difração de raios X método do pó (DRX), microscopia eletrônica de varredura (MEV), X-ray absorption near edge structure (XANES), Extended X-ray absorption fine structure (EXAFS), X-ray Excited Optical Luminescence (XEOL), espectroscopia de fotoluminescência na região do UV-Visível, espectroscopia de fotoluminescência na região do UV-UV vácuo e termoluminescência (TL). Os fósforos Lu2O3:TR3+,M (TR,M: Pr,HfIV; Eu, Ca2+ ou Tb,Ca2+) foram preparados em um curto período de tempo (22-26 min) pelo método MASS utilizando forno micro-ondas doméstico, carvão ativado como susceptor, fluxos (H3BO3 ou Na2CO3) e sem a aplicação de gases. Todos materiais preparados com fluxo de H3BO3 exibem impurezas de LuBO3 que foram quantificadas por refinamento Rietveld. Os fluxos e os dopantes não alteraram consideravelmente a estrutura cristalina da matriz C-Lu2O3. As micrografias MEV sugerem que o fluxo de Na2CO3 e os precursores nitratos geram partículas de Lu2O3 com tamanho menor devido a evolução de gases provenientes da decomposição destes compostos. Por outro lado, quando é usado óxidos como precursores os materiais apresentam maiores tamanhos de partícula e na presença de H3BO3 leva a maior agregação. Os dados de XANES indicam que houve completa redução do íon TbIV &#8594 Tb3+ e parcial do PrIV &#8594 Pr3+, devido ao uso de carvão ativado que gera CO(g) durante o tratamento térmico. Os espectros da luminescência persistente indicam emissões nas regiões do vermelho/NIR, vermelho alaranjado e verde atribuídas as transições 4fN &#8594 4fN características dos íons Pr3+, Eu3+ e Tb3+, respectivamente. As diferenças entre os espectros registrados sob excitação UV e após cessada a irradiação podem ser explicadas pela emissão da luminescência persistente predominante dos íons TR3+ no sítio S6 do que no C2. Além disso, a co-dopagem aliovalente com os íons HfIV e Ca2+ aumentam a intensidade e duração da luminescência persistente. Isto ocorre através da geração de armadilhas provenientes dos dois co-dopantes nos sítios de Lu3+ e por defeitos produzidos na compensação de carga. Os materiais fotônicos preparados pelo método MASS com fluxo de H3BO3 apresentam maior intensidade e duração da luminescência persistente comparados aos preparados pelo método cerâmico ou sem a presença de H3BO3. Os mecanismos da luminescência persistente foram desenvolvidos através de princípios similares baseados nos dados experimentais da energia do band gap, posição dos níveis de energia dos íons TR3+/2+ na matriz e energia das armadilhas. Isto confirma a solidez da interpretação dos dados experimentais dos materiais Lu2O3:TR3+,M exibindo luminescência persistentes e encoraja a expansão de modelos similares para outros materiais apresentando esse fenômeno. Os fósforos Lu2O3:Pr3+,HfIV,Lu2O3:Eu3+(,Ca2+) e Lu2O3:Tb3+,Ca2+) apresentaram sintonização de cores de emissão tanto para o fenômeno da fotoluminescência como da luminescência persistente, podendo atuar como bons candidatos nas aplicações de bioimageamento ou sensibilizadores de células solares. / Persistent luminescence is a phenomenon where the material emits radiation from seconds to several hours after cessation of irradiation (light, UV radiation, electron beam, etc.). The persistent luminescence mechanisms are not entirely established, however. In this work, the materials Lu2O3:TR3+,M (TR,M: PrHfIV; Eu, Ca2+ or Tb,Ca2+) were prepared by MASS method as well as compared to these materials synthetized by ceramic method. The advantages of MASS method include short processing time, selective dielectric heating, low energy consumption and use of inexpensive equipment (domestic microwave oven), often affording high-purity and high-yield products. The materials were characterized by Infrared absorption spectroscopy (IR), Raman spectroscopy, X-ray powder diffraction (XPD), Scanning electron microscopy (SEM), X-ray absorption near edge structure (XANES), Extended X-ray absorption fine structure (EXAFS), X-ray excited optical luminescence (XEOL), photoluminescence spectroscopy in the UV-Visible range, photoluminescence spectroscopy in the UV-UV vacuum region and thermoluminescence (TL). The phosphorsLu2O3:TR3+,M (TR,M: Pr,HfIV; Eu, Ca2+ or Tb,Ca2+) were rapidly (22-26 min) and successfully prepared by MASS method using a domestic microwave oven, carbon as susceptor, fluxes (H3BO3 or Na2CO3) and without special gases application. All materials prepared with H3BO3 flux exhibit LuBO3 impurities that were quantified by Rietveld refinement. The flux and dopants does not considerably affect the crystalline structure of the C-Lu2O3 host matrix. Scanning electron micrographs suggest that Na2CO3 flux and nitrates precursors produce Lu2O3 particles of small size due to the gases evolution from the decomposition of these compounds. On the other hand, the materials prepared from oxides precursors have particles of large size and H3BO3 flux induces particle xi aggregation. The carbon used as the susceptor generates CO gas, leading to complete reduction of TbIV to Tb3+ and partial conversion of PrIV to Pr3+ present in the Tb4O7 and Pr6O11 precursors, as indicated by XANES. Persistent luminescence spectra of the materials show emission in the red/NIR, reddish orange and green ranges assigned to the 4fN &#8594 4fN transitions characteristics of Pr3+, Eu3+ and Tb3+ ions, respectively. Differences between the spectra recorded under UV excitation and after ceased the irradiation can be explained by the predominant persistent luminescence emission of TR3+ ion in the S6 site rather than TR3+ in the C2 site. In addition, inclusion of HfIV and Ca2+ codopants in the Lu2O3 host increases the emission intensity and duration of persistent luminescence due to generation of traps caused by charge compensation in the lattice as well as these metal ions in the Lu3+ sites. The photonic materials prepared by MASS method with H3BO3 flux show higher persistent luminescence performance than those prepared by the ceramic method or MASS without flux. The persistent luminescence mechanisms were developed through similar principles based on experimental data of band gap energy, energy level positions of TR3+/2+ ions in the host and traps energy. This similarity confirms the consistency of the interpretation of experimental data for the Lu2O3:TR3+,M materials and encourages the expansion of similar models for other persistent luminescence materials. Color tuning of persistent luminescence in Lu2O3:TR3+,M (TR,M: Pr,HfIV; Eu,Ca2+ or Tb,Ca2+) provides potential applications in bioimaging as well as in solar cell sensitizers.