Improvement of the performance of organic disordered semiconductors (OSC) is driven by the understanding   of the underlying charge transport mechanisms and systematic exploitation thereof. There exists a multitude of materials and material systems based on polymers and small molecules with promising performance for use in organic light emitting diodes, photovoltaics, organic field-effect transistors and thermoelectrics. However, universal understanding of many classes of these materials has eluded researchers, due to their broad   spectrum of morphologies, molecular structures and electrical properties. Building on the large body of existing models, this thesis deals with charge transport phenomena from the perspective of transport energetics, by studying the interplay between a few but important concepts commonly accepted to play a crucial role in all  OSC materials; energetic disorder, charge carrier hopping and Coulomb interactions. The influence of these concepts on the energetic landscape through which charge carriers move and how this translates to experimentally observed transport phenomena are studied by a combination of experimental work, kinetic Monte Carlo (MC) simulations and empirical and analytical models.

The universal scaling and collapse of the temperature and electric field dependence of the conductivity of PEDOT:PSS to a single curve is shown to be functionally equivalent to the scaling of the effective temperature, which describes the effect of field heating as a broadening of the charge carrier distribution. From numerical investigation of the energy relaxation, an empirical model is developed that relates the physical meaning   behind both concepts to the heat balance between Joule heating of the carrier distribution via the effective temperature and energy loss to the lattice. For this universal description to be applicable a strongly energy- dependent density of states (DOS) as well as Coulomb interactions and large carrier concentrations are needed.

Chemical doping is a common way of improving charge transport in OSC and is also beneficial for energy transport, which combined leads to an increased thermoelectric power factor. The ensuing thermoelectric investigations not only showed the potential of these materials for use in thermoelectric generators, but are  also helpful in unraveling charge transport mechanism as they give direct insight into the energetics of a material. Interestingly, doped OSC exhibit the same universal power-law relationship between thermopower and conductivity, independent of material system or doping method, pointing towards a common energy and charge transport mechanism. In this thesis an analytical model is presented, which reproduces said universal power-law behavior and is able to attribute it to Variable Range Hopping (VRH) or a transition between Nearest Neighbour Hopping (NNH) and VRH at higher concentrations. This model builds on an existing three- dimensional hopping formalism that includes the effect of the attractive Coulomb potential of ionized dopants that leads to a broadening of the DOS. Here, this model is extended by including the energy offset between   host and dopant material and is positively tested against MC simulations and a set of thermoelectric measurements covering different material groups and doping mechanisms.

Organic field effect transistors (OFETs) have become increasingly comparable in electrical mobility to their inorganic (silicon) counterparts. The spatial extent of charge transport in OFETs has been subject to debate since their inception with many experimental, numerical and analytical studies having been undertaken. Here it is shown that the common way of analyzing the dimensionality of charge transport in OFETs may be prone to misinterpretations. Instead, the results in this thesis suggest that charge transport in OFETs is, in fact, quasi- two-dimensional (2D) due to the confinement of the gate field in addition to a morphology-induced preferred in-plane direction of the transport. The inherently large charge carrier concentrations in OFETs in addition to   the quasi-2D confinement leads to increased Coulomb interaction between charge carriers as compared to bulk material, leading to a thermoelectric behavior that deviates from doped organic systems. At very large concentrations interesting charge transport phenomena are observed, including an unexpected simultaneous increase of the concentration dependence and the magnitude of the mobility, the appearance of a negative transconductance, indicating a transition to an insulating Mott-Hubbard phase. The experimental and   numerical results in this thesis relate these phenomena the intricacies of the interplay between Coulomb interactions, energetic disorder and charge carrier hopping.

Thermoelectric materials can turn temperature differences directly into electricity. To use this to harvest e.g. waste heat with an efficiency that approaches the Carnot efficiency requires a figure of merit ZT larger than 1. Compared with their inorganic counterparts, organic thermoelectrics (OTE) have numerous advantages, such as low cost, large-area compatibility, flexibility, material abundance and an inherently low thermal conductivity. Therefore, organic thermoelectrics are considered by many to be a promising candidate material system to be used in lower cost and higher efficiency thermoelectric energy conversion, despite record ZT values for OTE currently lying around 0.25.

A complete organic thermoelectric generator (TEG) normally needs both p-type and n-type materials to form its electric circuit. Molecular doping is an effective way to achieve p- and ntype materials using different dopants, and it is necessary to fundamentally understand the doping mechanism. We developed a simple yet quantitative analytical model and compare it with numerical kinetic Monte Carlo simulations to reveal the nature of the doping effect. The results show the formation of a deep tail in the Gaussian density of states (DOS) resulting from the Coulomb potentials of ionized dopants. It is this deep trap tail that negatively influences the charge carrier mobility with increasing doping concentration. The trends in mobilities and conductivities observed from experiments are in good agreement with the modeling results, for a large range of materials and doping concentrations.

Having a high power factor PF is necessary for efficient TEG. We demonstrate that the doping method can heavily impact the thermoelectric properties of OTE. In comparison to conventional bulk doping, sequential doping can achieve higher conductivity by preserving the morphology, such that the power factor can improve over 100 times. To achieve TEG with high output power, not only a high PF is needed, but also having a significant active layer thickness is very important. We demonstrate a simple way to fabricate multi-layer devices by sequential doping without significantly sacrificing PF.

In addition to the application discussed above, harvesting large amounts of heat at maximum efficiency, organic thermoelectrics may also find use in low-power applications like autonomous sensors where voltage is more important than power. A large output voltage requires a high Seebeck coefficient. We demonstrate that density of states (DOS) engineering is an effective tool to increase the Seebeck coefficient by tailoring the positions of the Fermi energy and the transport energy in n- and p-type doped blends of conjugated polymers and small molecules.

In general, morphology heavily impacts the performance of organic electronic devices based on mixtures of two (or more) materials, and organic thermoelectrics are no exception. We experimentally find that the charge and energy transport is distinctly different in well-mixed and phase separated morphologies, which we interpreted in terms of a variable range hopping model. The experimentally observed trends in conductivity and Seebeck coefficient are reproduced by kinetic Monte Carlo simulations in which the morphology is accounted for.