Over the last decades organic light-emitting diodes (OLEDs) and organic solar cells (OSCs) have gained considerable attention as efficient, flexible, lightweight, and potentially low-cost technology for lighting and display applications or as a renewable energy source, respectively. However, achieving long-term stability remains challenging. Revealing and understanding aging processes is therefore of great interest. This work presents fundamental investigations to understand and circumvent organic device degradation. In the first part, single materials used in organic devices were investigated. By tailoring an attenuated total reflection infrared (ATR-IR) spectrometer to the specific needs and subsequent measurements, it is shown that the tris(8-hydroxyquinoline)aluminum (Alq3) molecule, a well known fluorescent green emitter, degrades during air exposure by the formation of carbonyl groups. By using a laser desorption/ionization time of flight mass spectrometer (LDI-TOF-MS) it was shown that a,w-bis-(dicyanovinylen)-sexithiophen (DCV6T-Bu4), a well known small-molecule material which is used as part of the active layer, reacts with oxygen during ultraviolet (UV) irradiation. By using climate boxes and a sun simulator the impact of dry and humid air as well as sunlight on C60, a widely-used acceptor molecule in organic solar cells, was investigated. The breaking of the C60 cage to C58 and C56 and the further reaction of these components with oxygen as well as the dimerization of C58 and C56 molecules were found. The degradation products such as C58O increase with air exposure time but they are independent of the humidity level of the ambient air as well as sunlight irradiation. Subsequent annealing leads to a decrease of the C58O concentration. Many efficient n-dopants are prone to degradation in air, due to the low ionization potentials, thereby limiting the processing conditions. It was found that the air exposure of the highly efficient n-dopant tetrakis(1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinato)ditungsten(II) (W2(hpp)4) leads to oxidation reactions of the molecule to [W(hpp)2 + O] and other degradation products. The decay constant of W2(hpp)4 and the matching mean growth time of the [W(hpp)2 + O] degradation as well as a second very quick degradation of the dopant could be determined. The two decay constants can be explained by the assumption that W2(hpp)4 molecules, which are involved in the charge transfer, do degrade slower due to the fact that the charge transfer leads to a downshift of the energy levels of the W2(hpp)4 molecule. Apart from the properties of the organic materials, other effects such as the impact of different purification systems on the material purity as well as the dependence of material purity on the OLED lifetime has been investigated. No correlations between the purification grade and the amount of impurities were found. OLEDs which contain N,N\'-di(naphthalen-1-yl)-N,N\'-diphenyl-benzidine (alpha-NPD) purified in a vertically interlaced stainless steel sublimation systems shows slightly higher external quantum efficiencies compared to tube-based vacuum sublimation systems. The devices which contain alpha-NPD purified by a sublimation system have an extended lifetime. Finally, the impact of residual gases during device fabrication on OLED lifetime and electrical characteristics was investigated. It was found that water vapor introduces an additional series resistance to the OLED, while the other gases do not influence the electric characteristics. The presence of nitrogen or oxygen impacts the lifetime of the OLEDs by the same amount. Nitrogen is non-reactive, this leads to the conclusion that the influence of nitrogen and oxygen on the OLED lifetime is of non-chemical nature, such as changes in the morphology of the organic layers. Water vapor introduces an additional, even faster degradation process within the first hours of OLED operation. As major sources of device degradation, the dimerization of 4,7-diphenyl-1,10-phenanthroline (BPhen) as well as the complexation reaction of alpha-NPD with a bis(1-phenylisoquinoline)iridium(III) (Ir(piq)2) fragment was identified.

[pt] Diversos trabalhos de pesquisa constatam as evidentes correlações entre a exposição excessiva à radiação solar e a incidência de câncer de pele, de catarata e de envelhecimento precoce da pele. O mercado de cosméticos destinados à proteção solar encontra-se em franca expansão; diversos países adotam legislações específicas para esses produtos. No Brasil eles são regulados pela Agência Nacional de Vigilância Sanitária (ANVISA). Porém, não existem métodos oficiais de análise química para determinar filtros solares em cosméticos. No presente trabalho foi desenvolvido um procedimento de análise qualitativa de cosméticos comerciais com filtros solares por espectrometria de massa LDI-TOF (Laser Desorption Ionization - Time-of-Flight). A técnica LDI utiliza um feixe de luz laser monocromático, Lambda = 337nm, como sonda para excitar, dessorver e ionizar o analito. Embora o espectro da radiação solar seja contínuo, o comprimento de onda utilizado em LDI se situa bem próximo do valor médio da faixa de radiação que compreende UVA e UVB, o que torna a técnica LDI potencialmente apropriada para excitar moléculas das substâncias ativas similarmente aos raios solares. Por tais características, é razoável esperar que LDI seja seletiva para detectar filtros solar presentes nas composições dos cosméticos. Paralelamente, foi utilizada também a espectrometria de massa (252)Cf-PDMS (Plasma Desorption Mass Spectrometry), que utiliza os fragmentos de fissão do nuclídeo radioativo califórnio 252 no lugar do laser. Foram obtidos espectros de massa de íons positivos e negativos de 8 cosméticos comerciais por ambas as técnicas, bem como espectros PDMS das substâncias ativas permitidas pela ANVISA. As massas observadas nos espectros de massa LDI dos produtos selecionados foram comparadas com: i) as massas moleculares de todas as substâncias ativas permitidas; ii) as massas observadas nos espectros PDMS das substâncias padrões permitidas e dos cosméticos comerciais; iii) as massas moleculares dos filtros solares indicados nos rótulos. A seletividade da técnica LDI para identificar filtros solares em cosméticos foi demonstrada pelos espectros de massa de íons positivos e negativos das oito amostras analisadas. / [en] Several studies of research note the obvious correlation between excessive exposure to sunlight, and the incidence of skin cancer, cataracts and premature aging of the skin. The market for cosmetics for sun protection is in the booming; various countries adopt laws specific to these products. In Brazil they are regulated by the National Sanitary Surveillance Agency (ANVISA). However, there are no official methods of chemical analysis to determine solar filters in cosmetics. In this work was developed a procedure for qualitative analysis of commercial cosmetics with solar filters by mass spectrometry LDI-TOF (Laser Desorption Ionization - Time-of-Flight). LDI technique uses a beam of monochromatic laser light, Lambda = 337 nm, as a probe to excite, desorbs and ionize the analyte. Although the spectrum of solar radiation is continuous, the wavelength used in LDI is well on the average range of radiation that includes UVA and UVB, which makes technical LDI potentially suitable to excite molecules of active substances similarly to lightning Sun. For such characteristics, it is reasonable to expect that LDI be selective to detect solar filters presents on cosmetics products. In parallel, was also used mass spectrometry (252)Cf-PDMS (Plasma Desorption Mass Spectrometry), which uses fragments of the fission of radioactive nuclide californium 252 instead of laser. Mass spectra were obtained from positive and negative ions, eight commercial cosmetics by both techniques, and PDMS spectra of active substances allowed by ANVISA. Masses observed on LDI mass spectra from selected products were compared with: i) molecular masses of all active substances allowed; ii) masses observed on PDMS mass spectra from standards allowed and commercial cosmetics; iii) molecular masses of sunscreens in its labels. The selectivity of the LDI technique to identify solar filters in cosmetics was demonstrated by mass spectra of positive and negative ions of the eight samples.

Over the last decades organic light-emitting diodes (OLEDs) and organic solar cells (OSCs) have gained considerable attention as efficient, flexible, lightweight, and potentially low-cost technology for lighting and display applications or as a renewable energy source, respectively. However, achieving long-term stability remains challenging. Revealing and understanding aging processes is therefore of great interest. This work presents fundamental investigations to understand and circumvent organic device degradation. In the first part, single materials used in organic devices were investigated. By tailoring an attenuated total reflection infrared (ATR-IR) spectrometer to the specific needs and subsequent measurements, it is shown that the tris(8-hydroxyquinoline)aluminum (Alq3) molecule, a well known fluorescent green emitter, degrades during air exposure by the formation of carbonyl groups. By using a laser desorption/ionization time of flight mass spectrometer (LDI-TOF-MS) it was shown that a,w-bis-(dicyanovinylen)-sexithiophen (DCV6T-Bu4), a well known small-molecule material which is used as part of the active layer, reacts with oxygen during ultraviolet (UV) irradiation. By using climate boxes and a sun simulator the impact of dry and humid air as well as sunlight on C60, a widely-used acceptor molecule in organic solar cells, was investigated. The breaking of the C60 cage to C58 and C56 and the further reaction of these components with oxygen as well as the dimerization of C58 and C56 molecules were found. The degradation products such as C58O increase with air exposure time but they are independent of the humidity level of the ambient air as well as sunlight irradiation. Subsequent annealing leads to a decrease of the C58O concentration. Many efficient n-dopants are prone to degradation in air, due to the low ionization potentials, thereby limiting the processing conditions. It was found that the air exposure of the highly efficient n-dopant tetrakis(1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinato)ditungsten(II) (W2(hpp)4) leads to oxidation reactions of the molecule to [W(hpp)2 + O] and other degradation products. The decay constant of W2(hpp)4 and the matching mean growth time of the [W(hpp)2 + O] degradation as well as a second very quick degradation of the dopant could be determined. The two decay constants can be explained by the assumption that W2(hpp)4 molecules, which are involved in the charge transfer, do degrade slower due to the fact that the charge transfer leads to a downshift of the energy levels of the W2(hpp)4 molecule. Apart from the properties of the organic materials, other effects such as the impact of different purification systems on the material purity as well as the dependence of material purity on the OLED lifetime has been investigated. No correlations between the purification grade and the amount of impurities were found. OLEDs which contain N,N\'-di(naphthalen-1-yl)-N,N\'-diphenyl-benzidine (alpha-NPD) purified in a vertically interlaced stainless steel sublimation systems shows slightly higher external quantum efficiencies compared to tube-based vacuum sublimation systems. The devices which contain alpha-NPD purified by a sublimation system have an extended lifetime. Finally, the impact of residual gases during device fabrication on OLED lifetime and electrical characteristics was investigated. It was found that water vapor introduces an additional series resistance to the OLED, while the other gases do not influence the electric characteristics. The presence of nitrogen or oxygen impacts the lifetime of the OLEDs by the same amount. Nitrogen is non-reactive, this leads to the conclusion that the influence of nitrogen and oxygen on the OLED lifetime is of non-chemical nature, such as changes in the morphology of the organic layers. Water vapor introduces an additional, even faster degradation process within the first hours of OLED operation. As major sources of device degradation, the dimerization of 4,7-diphenyl-1,10-phenanthroline (BPhen) as well as the complexation reaction of alpha-NPD with a bis(1-phenylisoquinoline)iridium(III) (Ir(piq)2) fragment was identified.