Only recently organic light-emitting diode (OLED) technology has successfully managed the transition from research labs into the consumer market, taking a 60% share of the global mobile display market in 2018. The latest discovery of thermally activated delayed fluorescence attracted a lot of attention in research and industry due to the potential to fabricate fluorescence-based OLEDs with high efficiencies comparable to the currently used phosphorescence-based OLEDs, but with the advantage of possibly cheaper and more sustainable emitter materials (no Ir-, Pt-complexes). For achieving high efficiencies in OLEDs, a substantial number of layers and interfaces of the multilayer stack have to be optimized. A particularly important role is assigned to the emission layer within which light is generated by charge recombination and subsequent energy transfer and radiative decay of excitons. The understanding of charge recombination and exciton dynamics and the determination of the position of light generation are essential for the fabrication of modern OLEDs and are the goal of this thesis. Therefore two different OLED types, phosphorescence-based OLEDs and state-of-the-art TADF exciplex host OLEDs incorporating a fluorescent emitter, are studied by electro-optical characterization and device modelling. In a first step the emission zones are determined and analyzed by angle-dependent steady-state measurements at different biases and optical simulations. In both OLED types split emission zones are obtained with densities of emissive excitons that decay way from both emission layer interfaces toward the center. For the phosphorescence-based OLEDs an additional bias-dependence of the split emission zone is observed, meaning that at low bias the main emission is located at the cathode side and shifts to the anode side for increasing bias. In a second step, with transient EL decay measurements and electro-optical simulations the split emission zones are correlated to an EL peak appearing after OLED turn-off. To study the influence of the emission zone and the exciton dynamics on the OLED efficiency an electro-optical device model is established to reproduce the experimentally obtained measurement data. As the model includes charge carrier dynamics, light outcoupling and time- and position-dependent exciton processes, such as the formation, diffusion, transfer, decay and quenching, the physical mechanisms in the OLEDs are elucidated. For the phosphorescence-based OLED a surprising current efficiency increase of up to 60% for increasing bias as well as a subsequent decrease is explained with the shift of the emission zone and its influence on exciton quenching and light outcoupling. Similarly, for the TADF exciplex host OLEDs a model parameter study illustrates promising EQE enhancement routes, which could lead to EQEs as high as 42%. This thesis emphasizes the need of accurate knowledge of the emission zone and its bias-dependence due to its potentially strong influence on the OLED efficiency and its importance for the optimization of the OLED layer stack. In addition, this thesis shows that full electro-optical device modelling (including electrons, excitons and photons) combined with advanced electro-optical characterization techniques is crucial for elucidating the physical mechanisms in state-of-the-art OLEDs as well as for the prediction of promising routes for future efficiency enhancements.