Photo-induced charge transfer which occurs between molecules or different parts of a large molecule is the pivotal process related to performances of organic electronics. In particular, injection of charge carriers into conjugated polymers and dissociation of photo-generated excitons at the heterojunction between a donor and acceptor system are of great importance in determining the luminescence efficiency of organic light emitting diodes (OLEDs) and solar energy conversion efficiency of organic solar cells, respectively. However, the complex nature of organic semiconductors as well as complicated primary processes involved in the functioning of these devices have prevented us from understanding unique characteristics of these processes and thereby engineering better materials for higher performances. In this dissertation, two different types of photo-induced (or -related) charge transfer processes occurring in organic semiconductors were investigated by using single molecule spectroscopy (SMS) techniques to unravel the complexities of these processes. The carefully designed functioning capacitor-like model devices similar to OLEDs and photovoltaic cells were fabricated where isolated single nanoparticles were introduced as an active medium to mitigate the complexities of these materials. We observed that injection of positively charged carriers (holes) into poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) single nanoparticles from the carbazole hole transport layer does not occur in the absence of light. We denoted the observed hole injection in aid of light as the light-induced hole transfer mechanism (LIHT). It was revealed that the charging dynamics are highly consistent with a cooperative charging effect. In addition, the LIHT was proposed as the possible source for the formation of deep trapped hole in organic devices. Local exciton dissociation yields across a nanostructured domain between poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) single nanoparticles and either poly(9,9- dioctylfluorene - co - bis-N,N- (4 -butylphenyl)-bis-N,N-phenyl-1,4-phenylene diamine) (PFB) or poly(9,9-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine) (TFB) film in model photovoltaic devices was also investigated. A wide distribution of exciton dissociation yields was observed from each nanodomain due to the device geometry. The observed hysteresis in fluorescence voltage curve was ascribed to accumulated charges following charge separations. The dynamics of charge separation under the applied electric field was described in more detail. / text

Maleimide based highly luminescent material Cbz-MI with donor acceptor donor (D-A-D) backbone has been synthesized and characterized. An organic light emitting diode fabricated using this material as emitting layer exhibited EQE of 2.5% in the yellow region of visible spectrum. Due to the small energy gap of materials emitting in this region of spectrum, EQE of OLED is usually limited by various non-radiative decays and high EQE of OLED using this material proves that most of the nonradiative decay pathways have been avoided by the careful design of molecule and device structure. Although Cbz-MI did not show TADF properties, but if tailored with right electron donor along with maleimide as an acceptor, such derivatives may exhibit TADF properties

Submitted by Geandra Rodrigues (geandrar@gmail.com) on 2018-10-24T15:44:07Z No. of bitstreams: 1 leisabrandrios.pdf: 3333252 bytes, checksum: eb46615b96454ef8cb84c80277532dff (MD5) / Approved for entry into archive by Renata Lopes (renatasil82@gmail.com) on 2018-11-06T13:27:31Z (GMT) No. of bitstreams: 1 leisabrandrios.pdf: 3333252 bytes, checksum: eb46615b96454ef8cb84c80277532dff (MD5) / Made available in DSpace on 2018-11-06T13:27:31Z (GMT). No. of bitstreams: 1 leisabrandrios.pdf: 3333252 bytes, checksum: eb46615b96454ef8cb84c80277532dff (MD5) Previous issue date: 2017-02-17 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho, filmes finos de Óxido de Índio-Estanho (ITO) foram crescidos sobre substratos de vidro e de quartzo, pela técnica de deposição por pulverização catódica com radiofrequência assistida por um campo magnético constante do inglês “RF Magnetron Sputtering” à temperatura ambiente. O objetivo do trabalho foi estudar a influência dos parâmetros de deposição nas propriedades elétricas, ópticas e estruturais desses filmes. Caracterizações elétricas, ópticas e estruturais foram realizadas, respectivamente, por medidas de Efeito Hall, absorção óptica no UV-VIS e difração de Raios-X. Observou-se que os parâmetros de deposição - potência de pulverização e pressão de trabalho - têm forte influência sobre as propriedades elétricas e estruturais dos filmes finos ITO, mas a transmitância óptica na região visível (400 ˂ λ ˂ 700) nm sempre esteve acima de 80% para todos os filmes a 550 nm. Por meio das medidas de difração de Raios-X verificamos que os filmes apresentaram pequena orientação na direção [111] e a cristalinidade dos filmes aumentou com o acréscimo da potência de pulverização. A otimização dos parâmetros de crescimento reduziu a resistividade elétrica dos filmes, principalmente devido ao aumento da concentração e da mobilidade dos portadores de carga. Os melhores filmes finos foram obtidos com a potência de pulverização de 140 W, pressão de trabalho de 0,08 mbar e fluxo de argônio de 300 sccm, com baixa resistividade elétrica, e mobilidade e concentração de portadores elevadas de, respectivamente, 8,81 x 10⁻⁴ Ωcm, 9,98 cm²/Vs e 6,30 x 10²⁰ cm⁻³, aliados a uma alta transmitância óptica de 97,7% em 550nm e gap óptico de 3,78 eV. O filme otimizado foi utilizado como cátodo em um diodo emissor de luz orgânico (OLEDs) que apresentou uma eficiência satisfatória quando comparado a um dispositivo similar feito com ITO comercial. O próximo passo foi produzir um diodo emissor de luz orgânico transparente (TOLED), que emite luz para ambos os lados usando filmes transparentes de ITO para ânodo e cátodo. Para isso, as películas de ITO foram depositadas sobre camadas orgânicas, que são sensíveis a potências de pulverização elevadas. Assim, uma nova série de deposições com diferentes pressões de trabalho foram realizadas mantendo-se a potência fixa em 40 W. O melhor filme com esta potência menor foi obtido com pressão de trabalho de 0,08 mbar e fluxo de argônio de 300 sccm. Estes filmes apresentaram, como resistividade elétrica, mobilidade e concentração de portadores, 3,99 x 10⁻³ Ωcm, 2,07 cm²/Vs e 7,55 x 10²⁰ cm⁻³, respectivamente. Eles também mostraram uma transmitância acima de 92% para 400 < λ < 700 nm e gap óptico de 3,50 eV. Através das medidas de XRD, verificamos que todos os filmes depositados com baixa potência de pulverização apresentaram uma banda amorfa com picos de difração referentes a direção [111] com baixa intensidade, indicando que as películas são praticamente amorfas. Finalmente, serão apresentados os resultados da caracterização de TOLEDs, utilizando os filmes de ITO otimizados fabricados com uma potência de 40 W. / In this work, thin films of Indium-Tin Oxide (ITO) were grown onto glass and quartz substrates by R.F. Magnetron Sputtering deposition technique at room temperature. The objective of this work was to study the influence of deposition parameters on the electrical, optical and structural properties of these films. Electrical, optical and structural characterizations were performed, by Hall Effect measurements, UV-VIS optical absorption and X-ray diffraction, respectively. It was observed that the deposition parameters – sputtering power and working pressure– have a strong influence on the electrical and structural properties of ITO thin films, but the optical transmittance in the visible region (400 ˂ λ ˂ 700) nm was always above 80 % for all films at 550 nm. By means of the XRD measurements, we verified that the films showed small orientation in the direction [111] and the crystallinity of the films increased with the increase of the sputtering power. The optimization of growth parameters reduced the electrical resistivity of the films mainly because of the increase of carrier concentration and carrier mobility. Thin films with the best electrical properties were obtained with sputtering power of 140 W, working pressure of 0.08 mbar and argon flow of 300 sccm. The best ITO thin films had electrical resistivity of 8.81 x 10⁻⁴ Ωcm, mobility of 9.98 cm²/Vs, and carrier concentration of 6.30 x 10²⁰ cm⁻³ together with a high optical transmittance of 97.7 % at 550 nm and a band gap of 3.78 eV. The optimized film was used as cathode in an organic light-emitting diode (OLEDs) that presented a satisfactory efficiency when compared to a similar device made with commercial ITO. The next step was to produce a Transparent Organic Light Emitting Diode (TOLED), which emits light from both sides by using ITO transparent films for both anode and cathode. To do so, ITO films were deposited on top of organic active layers, which are sensitive to high sputtering powers. So a new series of depositions with different working pressures were performed with a fixed power of 40 W. The best film with this smaller power was obtained with working pressure of 0.08 mbar and argon flow of 300sccm. These films presented, as electrical resistivity, mobility and carrier concentration, 3.99 x 10⁻³ Ωcm, 2.07 cm2 / Vs and 7.55 x 10²⁰ cm⁻³, respectively. They also showed a transmittance above 92 % for 400 < λ < 700 nm and band gap of 3.50 eV. Through X rays difraction measurements, we verified that all films deposited with low sputtering power presented an amorphous band with diffraction peaks referring to the [111] direction with low intensity, indicating that the films are practically amorphous. Finally, the results of the characterization of TOLEDs presented, using the optimized ITO films made with a sputtering power of 40 W.

The present thesis deals with a theoretical study of electronic structures in -conjugated molecular materials with focus on their application in organic elec-tronics. We also discuss a modified and efficient symmetrized DMRG algorithm for studying excited states in these systems. In recent times, organic conjugated systems have emerged as potential candidates in a wide range of fascinating fields by virtue of their tunable electronic properties, easy processability and low cost. Tunability in the electronic and optical properties primarily are centered on the or-dering and nature of the low-lying excited states. Probing these important excited states also demands development of efficient and adaptable techniques. Chapter 1 provides a basic overview of conjugated organic polymers which have been utilized over decades in diverse fields as in organic light emitting diodes (OLED), organic solar cells (OSC) and non-linear optical (NLO) devices. These systems also contribute significantly to theoretical understanding as they pro vide important insights of one and quasi-one dimensional systems. In this chapter, we have given basic description of the electronic processes in OLED and OSC along with a brief theoretical description of -conjugated organic systems. Chapter 2 gives an account of the numerical techniques which are necessary for the study of low-dimensional strongly correlated systems like -conjugated sys-tems. For this purpose, effective low-energy model Hamiltonians viz. Huckel,¨ Hubbard and Pariser-Parr-Pople Hamiltonians are discussed. Exact diagonalization technique within the diagrammatic valence bond (DVB) basis and density matrix renormalization group (DMRG) technique are discussed in details. We have also given brief accounts of the methods employed to study real-time dynamics. A short description of different computational techniques for the study of NLO properties in -conjugated systems is also provided. Engineering the position of the lowest triplet state (T1) relative to the first excited singlet state (S1) is of great importance in improving the efficiencies of organic light emitting diodes and organic photovoltaic cells. In chapter 3, we have carried out model exact calculations of substituted polyene chains to understand the fac-tors that affect the energy gap between S1 and T1. The factors studied are backbone dimerization, different donor-acceptor substitutions and twisted backbone geome-try. The largest system studied is an eighteen carbon polyene which spans a Hilbert space of about 991 million in the triplet subspace. We show that for reverse inter-system crossing (RISC) process, the best choice involves substituting all carbon sites on one half of the polyene with donors and the other half with acceptors. Singlet fission (SF) is a potential pathway for significant enhancement of efficiency in OSC. In chapter 4, we study singlet fission in a pair of polyene molecules in two different stacking arrangements employing exact many-body wave packet dy-namics. In the non-interacting model, SF is absent. The individual molecules are treated within Hubbard and Pariser-Parr-Pople (PPP) models and the interac-tion between them involves transfer terms, intersite electron repulsions and site-charge—bond-charge repulsion terms. Initial wave packet is construc ted from ex-cited singlet state of one molecule and ground state of the other. Time develop-ment of this wave packet under the influence of intermolecular interactions is fol-lowed within the Schrodinger¨ picture by an efficient predictor-corrector scheme. In unsubstituted Hubbard and PPP chains, 21A state leads to significant SF yield while the 11B state gives negligible fission yield. On substitution by donor-acceptor groups of moderate strength, the lowest excited state will have sufficient 2 1A char-acter and hence gives significant SF yield. Because of rapid internal c onversion, the nature of the lowest excited singlet will determine the SF contribution to OSC effi - ciency. Furthermore, we find the fission yield depends considerably on th e stacking arrangement of the polyene molecules. In chapter 5, we have given an account of a new modified algorithm for symmetry adaptation within symmetrized density matrix renormalization group (SDMRG) technique. SDMRG technique has been an efficient method for studying low-lying eigenstates in one and quasi-one dimensional electronic systems. However, SDMRG method until now, had bottlenecks involving construction of linearly in-dependent symmetry adapted basis states as the symmetry matrices in the DMRG basis were not sparse. Our modified algorithm overcomes this bottleneck. T he new method incorporates end-to-end interchange symmetry (C2), electron-hole symmetry (J) and parity or spin-flip symmetry (P) in these calculations. The one-to-one correspondence between direct-product basis states in the DMRG Hilbert space for these symmetry operations renders the symmetry matrices in the new ba-sis with maximum sparseness, just one non-zero matrix element per row. Using methods similar to those employed in exact diagonalization technique for Pariser-Parr-Pople (PPP) models, developed in the eighties, it is possible to construct or-thogonal SDMRG basis states while bypassing the slow step of Gram-Schmidt orthonormalization procedure. The method together with the PPP model which incorporates long-range electronic correlations is employed to study the correlated excited states of 1,12-benzoperylene. In chapter 6, we have studied the correlated excited states of coronene and ova-lene within Pariser-Parr-Pople (PPP) model employing symmetry adapted density matrix renormalization group technique. These polynuclear aromatic hydrocar-bons can be considered as graphene nanoflakes and study of their ele ctronic struc-tures will shed light on the electron correlation effects in these finite-size gr aphene analogues. The electron correlation effect usually diminishes on going from one-dimensional to higher-dimensional systems, yet, it is significant within these fin ite-size graphene derivatives where it depends on the molecular topology. We have characterized these low-lying energy states by calculating bond orders, spin den-sities in the lowest triplet state and two-photon absorption cross-sections for low-lying two-photon states. vi

White organic light-emitting diodes (OLEDs) are promising candidates for future solid-state lighting applications and backplane illumination in large-area displays. One very specific feature of OLEDs, which is currently gaining momentum, is that they can enable tunable white light emission. This feature is conventionally realized either through the vertical stacking of independent OLEDs emitting different colors or in lateral arrangement of OLEDs. The vertical design is optically difficult to optimize and often results in efficiency compromises between the units. In contrast, the lateral concept introduces severe area losses to dark regions between the subunits, which requires a significantly larger overall device area to achieve equal brightness. Here we demonstrate a color-tunable, two-color OLED device realized by side-by-side alignment of yellow and blue p-i-n OLEDs structured down to 20 μm by a simple and up-scalable orthogonal photolithography technique. This layout eliminates the problems of conventional lateral approaches by utilizing all area for light emission. The corresponding emission of the photo-patterned two-unit OLED can be tuned over a wide range from yellow to white to blue colors. The independent control of the different units allows the desired overall spectrum to be set at any given brightness level. Operated as a white light source, the microstructured OLED reaches a luminous efficacy of 13 lm W−1 at 1000 cd m−2 without an additional light outcoupling enhancement and reaches a color rendering index of 68 when operated near the color point E. Finally, we demonstrate an improved device lifetime by means of size variation of the subunits.

White organic light-emitting diodes (OLEDs) are promising candidates for future solid-state lighting applications and backplane illumination in large-area displays. One very specific feature of OLEDs, which is currently gaining momentum, is that they can enable tunable white light emission. This feature is conventionally realized either through the vertical stacking of independent OLEDs emitting different colors or in lateral arrangement of OLEDs. The vertical design is optically difficult to optimize and often results in efficiency compromises between the units. In contrast, the lateral concept introduces severe area losses to dark regions between the subunits, which requires a significantly larger overall device area to achieve equal brightness. Here we demonstrate a color-tunable, two-color OLED device realized by side-by-side alignment of yellow and blue p-i-n OLEDs structured down to 20 μm by a simple and up-scalable orthogonal photolithography technique. This layout eliminates the problems of conventional lateral approaches by utilizing all area for light emission. The corresponding emission of the photo-patterned two-unit OLED can be tuned over a wide range from yellow to white to blue colors. The independent control of the different units allows the desired overall spectrum to be set at any given brightness level. Operated as a white light source, the microstructured OLED reaches a luminous efficacy of 13 lm W−1 at 1000 cd m−2 without an additional light outcoupling enhancement and reaches a color rendering index of 68 when operated near the color point E. Finally, we demonstrate an improved device lifetime by means of size variation of the subunits.

A new dual-boron-cored luminogen ligated with a nitrogen-containing multidentate ligand and four bulky phenyl rings was readily synthesized. The unique molecular structure endows this BN-containing luminogen with rich photophysical properties in either solution or in the solid state, including a large Stokes shift, aggregation induced emission activity and reversible piezochromism. Furthermore, this BN-containing luminogen exhibits good capabilities for imaging living cells and sensing of fluoride anions.

We discuss approaches to increase the light outcoupling efficiency in organic microcavity (MC) lasers and organic light-emitting diodes (OLEDs). We find that the introduction of metals into the cavities leads to additional Tamm-plasmon polariton modes, while the corrugation of metal contacts, such as perforated m-size holes or a periodic array of metal stripes, leads to 2D confinement of the cavity modes, which in turn reduces the lasing threshold in MCs. Furthermore, we elucidate light loss mechanisms in OLEDs and reveal how external dielectric layers and periodic gratings can be used to enhance outcoupling from the OLED cavity.

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.

We present a novel top-electrode spray-coating process for the solution-based deposition of silver nanowires (AgNWs) onto vacuum-processed small molecule organic electronic solar cells. The process is compatible with organic light emitting diodes (OLEDs) and organic light emitting thin film transistors (OLETs) as well. By modifying commonly synthesized AgNWs with a perfluorinated methacrylate, we are able to disperse these wires in a highly fluorinated solvent. This solvent does not dissolve most organic materials, enabling a top spray-coating process for sensitive small molecule and polymer-based devices. The optimized preparation of the novel AgNW dispersion and spray-coating at only 30 °C leads to high performance electrodes directly after the deposition, exhibiting a sheet resistance of 10.0 Ω □−1 at 87.4% transparency (80.0% with substrate). By spraying our novel AgNW dispersion in air onto the vacuum-processed organic p-i-n type solar cells, we obtain working solar cells with a power conversion efficiency (PCE) of 1.23%, compared to the air exposed reference devices employing thermally evaporated thin metal layers as the top-electrode.