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.

Ever since the first experimental investigations of organic field effect transistors (OFETs) the dimensionality of charge transport has alternately been described as two dimensional (2D) and three dimensional (3D). More recently, researchers have turned to an analytical analysis of the temperature-dependent transfer characteristics to classify the dimensionality as either 2D or 3D as well as to determine the disorder of the system, thereby greatly simplifying dimensionality investigations. We applied said analytical analysis to the experimental results of our OFETs comprising molecularly well-defined polymeric layers as the active material as well as to results obtained from kinetic Monte Carlo simulations and found that it was not able to correctly distinguish between 2D and 3D transports or give meaningful values for the disorder and should only be used for quasiquantitative and comparative analysis. We conclude to show that the dimensionality of charge transport in OFETs is a function of the interplay between transistor physics and morphology of the organic material.

We investigate the scalability of the temperature-and electric field-dependence of the conductivity of disordered organic semiconductors to universal curves by two different but commonly employed methods; by so-called universal scaling and by using the effective temperature concept. Experimentally both scaling methods were found to be equally applicable to the out-of-plane charge transport in PEDOT: PSS thin films of various compositions. Both methods are shown to be equivalent in terms of functional dependence and to have identical limiting behavior. The experimentally observed scaling behavior can be reproduced by a numerical nearest-neighbor hopping model, accounting for the Coulomb interaction, the high charge carrier concentration and the energetic disorder. The underlying physics can be captured in a simple empirical model, describing the effective temperature of the charge carrier distribution as the outcome of a heat balance between Joule heating and (effective) temperature-dependent energy loss to the lattice.

The recent upswing in attention for the thermoelectric properties of organic semiconductors (OSCs) adds urgency to the need for a quantitative description of the range and energetics of hopping transport in organic semiconductors under relevant circumstances, i.e., around room temperature (RT). In particular, the degree to which hops beyond the nearest neighbor must be accounted for at RT is still largely unknown. Here, measurements of charge and energy transport in doped OSCs are combined with analytical modeling to reach the univocal conclusion that variable-range hopping is the proper description in a large class of disordered OSC at RT. To obtain quantitative agreement with experiment, one needs to account for the modification of the density of states by ionized dopants. These Coulomb interactions give rise to a deep tail of trap states that is independent of the materials initial energetic disorder. Insertion of this effect into a classical Mott-type variable-range hopping model allows one to give a quantitative description of temperature-dependent conductivity and thermopower measurements on a wide range of disordered OSCs. In particular, the model explains the commonly observed quasiuniversal power-law relation between the Seebeck coefficient and the conductivity.

Electronic ratchets use a periodic potential with broken inversion symmetry to rectify undirected (electromagnetic, EM) forces and can in principle be a complement to conventional diode-based designs. Unfortunately, ratchet devices reported to date have low or undetermined power conversion efficiencies, hampering applicability. Combining experiments and numerical modeling, field-effect transistor-based ratchets are investigated in which the driving signal is coupled into the accumulation layer via interdigitated finger electrodes that are capacitively coupled to the field effect transistor channel region. The output current-voltage curves of these ratchets can have a fill factor amp;gt;amp;gt; 0.25 which is highly favorable for the power output. Experimentally, a maximum power conversion efficiency well over 10% at 5 MHz, which is the highest reported value for an electronic ratchet, is determined. Device simulations indicate this number can be increased further by increasing the device asymmetry. A scaling analysis shows that the frequency range of optimal performance can be scaled to the THz regime, and possibly beyond, while adhering to technologically realistic parameters. Concomitantly, the power output density increases from approximate to 4 W m(-2) to approximate to 1 MW m(-2). Hence, this type of ratchet device can rectify high-frequency EM fields at reasonable efficiencies, potentially paving the way for actual use as energy harvester.

Scalable production methods and low-cost materials with low embodied energy are key to success for organic solar cells. PEDOT(PSS) electrodes meet these criteria and allow for low-cost and all solution-processed solar cells. However, such devices are prone to shunting. In this work we introduce a roll-to-roll lamination method to construct semitransparent solar cells with a PEDOT(PSS) anode and an polyethyleneimine (PEI) modified PEDOT(PSS) cathode. We use the polymer:PCBM active layer coated on the electrodes as the lamination adhesive. Our lamination method efficiently eliminates any shunting. Extended exposure to ambient degrades the laminated devices, which manifests in a significantly reduced photocurrent extraction when the device is illuminated through the anode, despite the fact that the PEDOT(PSS) electrodes are optically equivalent. We show that degradation-induced electron traps lead to increased trap-assisted recombination at the anode side of the device. By limiting the exposure time to ambient during production, degradation is significantly reduced. We show that lamination using the active layer as the adhesive can result in device performance equal to that of conventional sequential coating.

Organic ferroelectric diodes attract increasing interest as they combine non-destructive data read-out and low cost fabrication, two requirements in the development of novel non-volatile memory elements. The macroscopic electrical characteristics and performances of such devices strongly depend on their structural properties. Various studies of their global microscopic morphology have already been reported. Here, a multi-technique approach including different scanning force and X-ray microscopies permitted to reveal and locally study nanometer-scale unexpected sub-structures within a P(VDF-TrFE):F8BT ferroelectric diode. The strong impact of these structures on the local polarizability of the ferroelectric is shown. Two alternative fabrication methods are proposed that prevent the formation of these structures and demonstrate improved macroscopic device performances such as endurance and ON/OFF ratio.

The deep levels ON1 and ON2a/b introduced by oxidation into 4H-SiC are characterized via standard DLTS and via filling pulse dependent DLTS measurements. Separation of the closely spaced ON2a/b defect is achieved by using a higher resolution correlation function (Gaver-Stehfest 4) and apparent energy level, apparent electron capture cross section and filling pulse measurement derived capture cross sections are given.

The combination of switchable dipolar side groups and the semiconducting core of the newly synthetized C-3-symmetric benzotrithiophene molecule (BTTTA) leads to an ordered columnar material showing continuous tunability from injection- to bulk-limited conductivity modulation.

Ferroelectrics find broad applications, e.g. in non-volatile memories, but the switching kinetics in real, disordered, materials is still incompletely understood. Here, we develop an electrostatic model to study ferroelectric switching using 3D Monte Carlo simulations. We apply this model to the prototypical small molecular ferroelectric trialkylbenzene-1,3,5-tricarboxamide (BTA) and find good agreement between the Monte Carlo simulations, experiments, and molecular dynamics studies. Since the model lacks any explicit steric effects, we conclude that these are of minor importance. While the material is shown to have a frustrated antiferroelectric ground state, it behaves as a normal ferroelectric under practical conditions due to the large energy barrier for switching that prevents the material from reaching its ground state after poling. We find that field-driven polarization reversal and spontaneous depolarization have orders of magnitude different switching kinetics. For the former, which determines the coercive field and is relevant for data writing, nucleation occurs at the electrodes, whereas for the latter, which governs data retention, nucleation occurs at disorder-induced defects. As a result, by reducing the disorder in the system, the polarization retention time can be increased dramatically while the coercive field remains unchanged.

Nanometer-thick Langmuir-Schafer monolayers of an electron transporting polymer display charge transport, optical and electro-optical properties that do not depend on the number of layers deposited one above the other. This phenomenon can be rationalized with the micro-structure of the specific multi-layers, which introduces an interlayer hopping penalty confining transport to a neat 2D regime, with a channel not extending beyond a single similar to 3 nm thick polymer strand, as confirmed by kinetic Monte Carlo simulations. Such findings are critical to establish a quantitative structure-property nexus in high mobility polymer semiconductors and in the control of charge transport at a molecular scale.

Organic photovoltaics (OPVs) is a promising low-cost and environmental-friendly technology currently achieving 12-14% power conversion efficiency. Despite the extensive focus of the research community over the last years, critical mechanisms defining the performance of OPVs are still topics of debate. While energetic disorder is known to be characteristic of organic semiconductors in general, its potential role in OPV has received surprisingly little attention. In this thesis we investigate some aspects of the relation between energetic disorder and several optoelectronic properties of OPV.

Charge carrier mobility is a key parameter in characterizing the performance of organic semiconductors. Analyzing the temperature dependence of the mobility is also an oftenused method to obtain (estimates for) the energetic disorder in the HOMO and LUMO levels of an organic semiconductor material. Different formalisms to extract and analyze mobilities from space charge limited conductivity (SCLC) experiments are reviewed. Surprisingly, the Murgatroyd-Gill analytical model in combination with the Gaussian disorder model in the Boltzmann limit yields similar mobilities and energetic disorders as a more elaborate drift-diffusion model with parametrized mobility functionals. Common analysis and measurement errors are discussed. All the models are incorporated in an automated analysis freeware tool.

The open circuit voltage (Voc) has attracted considerable interest as the large difference between Voc and the bandgap is the main loss mechanism in bulk heterojunction OPVs. Surprisingly, in ternary devices composed of two donors and one acceptor, the Voc is not pinned to the shallowest HOMO but demonstrates a continuous tunability between the binary extremities. We show that this phenomenon can be explained with an equilibrium model where Voc is defined as the splitting of the quasi-Fermi levels of the photo-created holes and electrons in a common density of states accounting for the stoichiometry, i.e. the ratio of the donor materials and the broadening by Gaussian disorder. Evaluating the PCE, it is found that ternary devices do not offer advantages over binary unless the fill factor (FF) is increased at intermediate compositions, as a result of improved transport/recombination upon material blending.

Stressing the importance of material intermixing to improve the performance, we found that the presence of an acceptor may drastically alter the mobility and energetic disorder of the donor and vice versa. The effect of different acceptors was studied in a ternary onedonor- two-acceptors system, where the unpredictable variability with composition of the energetic disorder in the HOMO and the LUMO explained the almost linear tunability of Voc. Designing binary OPVs based on the design rule that the energetic disorder can be reduced upon material blending, as we observed, can yield a relative PCE improvement of at least 20%.

CT states currently play a key role in evaluating the performance of OPVs and CTelectroluminescence (CT-EL) is assumed to stem from the recombination of thermalized electron-hole pairs. The varying width of the CT-EL peak for different material combinations is intuitively expected to reflect the energetic disorder of the effective HOMO and LUMO. We employ kinetic Monte Carlo (kMC) CT-EL simulations, using independently measured disorder parameters as input, to calculate the ground-to-ground state (0-0) transition spectrum. Including the vibronic broadening according to the Franck Condon principle, we reproduce the width and current dependence of the measured CT-EL peak for a large number of donor-acceptor combinations. The fitted dominant phonon modes compare well with the values measured using the spectral line narrowing technique. Importantly, the calculations show that CT-EL originates from a narrow, non-thermalized subset of all available CT states, which can be understood by considering the kinetic microscopic process with which electron-hole pairs meet and recombine.

Despite electron-hole pairs being strongly bound in organic materials, the charge separation process following photo-excitation is found to be extremely efficient and independent of the excitation energy. However, at low photon energies where the charges are excited deep in the tail of the DOS, it is intuitively expected for the extraction yield to be quenched. Internal Quantum Efficiency (IQE) experiments for different material systems show both inefficient and efficient charge dissociation for excitation close to the CT energy. This finding is explained by kinetic Monte Carlo simulations accounting for a varying degree of e-h delocalization, where strongly bound localized CT pairs (< 2nm distance) are doomed to recombine at low excitation energies while extended delocalization over 3-5nm yields an increased and energy-independent IQE. Using a single material parameter set, the experimental CT electroluminescence and absorption spectra are reproduced by the same kMC model by accounting for the vibronic progression of the calculated 0-0 transition. In contrast to CT-EL, CT-absorption probes the complete CT manifold.

Charge transport in organic solar cells is currently modelled as either an equilibrium or a non-equilibrium process. The former is described by drift-diffusion (DD) equations, which can be calculated quickly but assume local thermal equilibrium of the charge carriers with the lattice. The latter is described by kMC models, that are time-consuming but treat the charge carriers individually and can probe all relevant time and energy scales. A hybrid model that makes use of the multiple trap and release (MTR) concept in combination with the DD equations is shown to describe both steady-state space charge limited conductivity experiments and non-equilibrium time-resolved transport experiments using a single parameter set. For the investigated simulations, the DD-MTR model is in good agreement with kMC and ~10 times faster.

Steady-state mobilities from DD equations have been argued to be exclusively relevant for operating OPVs while charge carrier thermalization and non-equilibrium time-dependent mobilities (although acknowledged) can be disregarded. This conclusion, based on transient photocurrent experiments with μs time resolution, is not complete. We show that non-equilibrium kMC simulations can describe the extraction of charge carriers from subps to 100 μs timescales with a single parameter set. The majority of the fast charge carriers, mostly non-thermalized electrons, are extracted at time scales below the resolution of the experiment. In other words, the experiment resolves only the slower fraction of the charges, predominantly holes.

The photon energy dependence of long-range charge separation is studied for two prototypical polymer:fullerene systems. The internal quantum efficiency (IQE) of PCDTBT:PC61BM is experimentally shown to be independent of the excitation energy. In contrast, for TQ1:PC71BM the IQE is strongly energy-dependent for excitation energies close to charge transfer (CT) electroluminescence peak maximum while it becomes energy-independent at higher excitation energies. Kinetic Monte Carlo simulations reproduce the experimental IQE and reveal that the photon energy-dependence of the IQE is governed by charge delocalization. Efficient long-range separation at excitation energies corresponding to the CT electroluminescence peak maximum or lower requires an initial separation of the hole- electron pair by similar to 4-5 nm, whereas delocalization is less important for charge separation at higher photon energies. Our modeling results suggest that a phenomenological reciprocity between CT electroluminescence and external quantum efficiency does not necessarily prove that commonly employed reciprocity relations between these spectra are valid from a fundamental perspective.

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Organic electronics is an emerging technology with numerous applications in which the active layer is composed of an organic semiconductor (OSC) or blends of multiple OSC. One of the key performance parameters for such devices is the charge carrier mobility which can be evaluated by different measurement techniques. Here, we review different formalisms for extraction and analysis of hole mobilities from temperature-dependent space-charge limited conductivity (SCLC) measurements for pristine OSC as well as for binary and ternary blends as used in e.g. photovoltaic applications. The model is also applicable to n-type materials. Possible sources of measurement errors, such as the presence of traps and series resistance, are discussed. We show that by a simple method of selecting a proper experimental data range these errors can be avoided. The Murgatroyd-Gill analytical model in combination with the Gaussian Disorder Model is used to extract zero-field hole mobilities as well as estimates of the Gaussian energetic disorder in the HOMO level from experimental data. The resulting mobilities are in excellent agreement with those found from more elaborate fits to a full drift-diffusion model that includes a temperature, field and density dependent charge carrier mobility; the same holds for the Gaussian disorder of pure materials and blends with low fullerene concentration. The zero-field mobilities are also analyzed according to an Arrhenius model that was previously argued to reveal a universal mobility law; for most -but not all- material systems in the present work this framework gave an equally good fit to the experimental data as the other models. An automated fitting freeware, incorporating the different models, is made openly available for download and minimizes error, user input and SCLC data analysis time; e.g. SCLC current-voltage curves at several different temperatures can be globally fitted in a few seconds.

Mixing different compounds to improve functionality is one of the pillars of the organic electronics field. Here, the degree to which the charge transport properties of the constituent materials are simply additive when materials are mixed is quantified. It is demonstrated that in bulk heterojunction organic solar cells, hole mobility in the donor phase depends critically on the choice of the acceptor material, which may alter the energetic disorder of the donor. The same holds for electron mobility and disorder in the acceptor. The associated mobility differences can exceed an order of magnitude compared to pristine materials. Quantifying these effects by a state-filling model for the open-circuit voltage (V-oc) of ternary Donor:Acceptor(l):Acceptor(2) (D:A(1):A(2)) organic solar cells leads to a physically transparent description of the surprising, nearly linear tunability of the Voc with the A(1):A(2) weight ratio. It is predicted that in binary OPV systems, suitably chosen donor and acceptor materials can improve the device power conversion efficiency (PCE) by several percentage points, for example from 11 to 13.5% for a hypothetical state-ofthe-art organic solar cell, highlighting the importance of this design rule.

Two prevailing formalisms are currently used to model charge transport in organic semiconductor devices. Drift-diffusion calculations, on the one hand, are time effective but assume local thermodynamic equilibrium, which is not always realistic. Kinetic Monte Carlo models, on the other hand, do not require this assumption but are computationally expensive. Here, we present a nonequilibrium drift-diffusion model that bridges this gap by fusing the established multiple trap and release formalism with the drift-diffusion transport equation. For a prototypical photovoltaic system the model is shown to quantitatively describe, with a single set of parameters, experiments probing (1) temperature-dependent steady-state charge transport-space-charge limited currents, and (2) time-resolved charge transport and relaxation of nonequilibrated photocreated charges. Moreover, the outputs of the developed kinetic drift-diffusion model are an order of magnitude, or more, faster to compute and in good agreement with kinetic Monte Carlo calculations.

Organic bulk heterojunction solar cells based on ternary blends of two donor absorbers and one acceptor are investigated by experiments and modeling. The commonly observed continuous tunability of the open circuit voltage V-OC with the donor1 : donor2 ratio can quantitatively be explained as quasi-Fermi level splitting due to photocreated charges filling a joint density of states that is broadened by Gaussian disorder. On this basis, a predictive model for the power conversion efficiency that accounts for the composition-dependent absorption and the shape of the current-voltage characteristic curve is developed. When all other parameters, most notably the fill factor, are constant, we find that for state-of-the-art absorbers, having a broad and strong absorption spectrum, ternary blends offer no advantage over binary ones. For absorbers with a more narrow absorption spectrum ternary blends of donors with complementary absorption spectra, offer modest improvements over binary ones. In contrast, when, upon blending, transport and/or recombination kinetics are improved, leading to an increased fill factor, ternaries may offer significant advantages over binaries.

A synthetic method for the end-functionalization of vinylidene fluoride oligomers (OVDF) via a radical reaction between terminal olefins and I-OVDF is described. The method shows a wide substrate scope and excellent conversions, and permits the preparation of different disc-shaped cores such as benzene-1,3,5-tricarboxamides (BTAs), perylenes bisimide and phthalocyanines (Pc) bearing three to eight ferroelectric oligomers at their periphery. The formation, purity, OVDF conformation, and morphology of the final adducts has been assessed by a combination of techniques, such as NMR, size exclusion chromatography, differential scanning calorimetry, polarized optical microscopy, and atomic force microscopy. Finally, PBI-OVDF and Pc-OVDF materials show ferroelectric hysteresis behavior together with high remnant polarizations, with values as high as P-r approximate to 37 mC/m(2) for Pc-OVDF. This work demonstrates the potential of preparing a new set of ferroelectric materials simply by attaching OVDF oligomers to different small molecules. The use of carefully chosen small molecules paves the way to new functional materials in which ferroelectricity and electrical conductivity or light-harvesting properties coexist in a single compound.

We have investigated the ferroelectric polarization switching properties of trialkylbenzene-1,3,5-tricarboxamide (BTA), which is a model system for a large class of novel organic ferroelectric materials. In the solid state BTAs form a liquid crystalline columnar hexagonal phase that provides long range order that was previously shown to give rise to hysteretic dipolar switching. In this work the nature of the polar switching process is investigated by a combination of dielectric relaxation spectroscopy, depth-resolved pyroelectric response measurements, and classical frequency- and time-dependent electrical switching. We show that BTAs, when brought in a homeotropically aligned hexagonal liquid crystalline phase, are truly ferroelectric. Analysis of the transient switching behavior suggests that the ferroelectric switching is limited by a highly dispersive nucleation process, giving rise to a wide distribution of switching times.

We disclose a supramolecular material that combines semiconducting and dipolar functionalities. The material consists of a discotic semiconducting carbonyl-bridged triarylamine core, which is surrounded by three dipolar amide groups. In thin films, the material self-organizes in a hexagonal columnar fashion through Jr-stacking of the molecular core and hydrogen bonding between the amide groups. Alignment by an electrical field in a simple metal/semiconductor/metal geometry induces a polar order in the interface layers near the metal contacts that can be reversibly switched, while the bulk material remains nonpolarized. On suitably chosen electrodes, the presence of an interfacial polarization field leads to a modulation of the barrier for charge injection into the semiconductor. Consequently, a reversible switching is possible between a high-resistance, injection-limited off-state and a low-resistance, space-charge-limited on-state. The resulting memory diode shows switchable rectification with on/off ratios of up to two orders of magnitude. This demonstrated multifunctionality of a single material is a promising concept toward possible application in lowcost, large-area, nonvolatile organic memories.

Advanced molecular materials that combine two or more physical properties are typically constructed by combining different molecules, each being responsible for one of the properties required. Ideally, single molecules could take care of this combined functionality, provided they are self-assembled correctly and endowed with different functional subunits whose strong electronic coupling may lead to the emergence of unprecedented and exciting properties. We present a class of disc-like semiconducting organic molecules that are functionalized with strong dipolar side groups. Supramolecular organization of these materials provides long-range polar order that supports collective ferroelectric behavior of the side groups as well as charge transport through the stacked semiconducting cores. The ferroelectric polarization in these supramolecular polymers is found to couple to the charge transport and leads to a bulk conductivity that is both switchable and rectifying. An intuitive model is developed and found to quantitatively reproduce the experimental observations. In a larger perspective, these results highlight the possibility of modulating material properties using the large electric fields associated with ferroelectric polarization.

We investigate the polarization loss in the archetypical molecular organic ferroelectric trialkylbenzene-1,3,5-tricarboxamide (BTA). We prove that the polarization loss is due to thermally activated R-relaxation,which is a collective reversal of the amide dipole moments in ferroelectric domains. By applying a weakelectrostatic field both the polarization loss and the R-relaxation are suppressed, leading to anenhancement of the retention time by at least several orders of magnitude. Alternative loss mechanismsare discussed and ruled out. By operating the thin-film devices slightly above the crystalline to liquidcrystalline phase transition temperature the retention time of one compound becomes more than12 hours even in absence of supportive bias, which is among the longest reported so far for organicferroelectric materials.

The dynamics of charge carriers after their creation at, or near, an interface play a critical role in determining the efficiency of organic solar cells as they dictate, via mechanisms that are not yet fully understood, the pathways for charge separation and recombination. Here, a combination of ultrafast transient spectroscopy and kinetic Monte Carlo simulations based on a minimalistic model are used to examine various aspects of these charge dynamics in a typical donor-acceptor copolymer:methanofullerene blend. The observed rates of charge carrier energetic relaxation and recombination for a sequence of charge densities can be all consistently described in terms of the extended Gaussian disorder model. The physical picture that arises is a) that initial charge motion is highly diffusive and boosted by energetic relaxation in the disordered density of states and b) that mobile charge carriers dissociate from and re-associate into Coulombically associated pairs faster than they recombine, especially at early times. A simple analytical calculation confirms this picture and can be used to identify sub-Langevin recombination as the cause for quantitative deviations between the Monte Carlo calculations and the measured concentration dependence of the charge recombination.

The thermoelectric power factor of a broad range of organic semiconductors scales with their electrical conductivity according to a widely obeyed power law, and therefore, strategies that permit this empirical trend to be surpassed are highly sought after. Here, tensile drawing of the conjugated polymer poly(3-hexylthiophene) (P3HT) is employed to create free-standing films with a high degree of uniaxial alignment. Along the direction of orientation, sequential doping with a molybdenum tris(dithiolene) complex leads to a 5-fold enhancement of the power factor beyond the predicted value, reaching up to 16 mu W m(-1) K-2 for a conductivity of about 13 S cm(-1). Neither stretching nor doping affect the glass transition temperature of P3HT, giving rise to robust free-standing materials that are of interest for the design of flexible thermoelectric devices.

Molecular p-doping of the conjugated polymer poly(3-hexylthiophene) (P3HT) with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-quinodimethane (F4TCNQ) is a widely studied model system. Underlying structure property relationships are poorly understood because processing and doping are often carried out simultaneously. Here, we exploit doping from the vapor phase, which allows us to disentangle the influence of processing and doping. Through this approach, we are able to establish how the electrical conductivity varies with regard to a series of predefined structural parameters. We demonstrate that improving the degree of solid-state order, which we control through the choice of processing solvent and regioregularity, strongly increases the electrical conductivity. As a result, we achieve a value of up to 12.7 S cm(-2) for P3HT:F4TCNQ, We determine the F4TCNQ anion concentration and find that the number of (bound + mobile) charge carriers of about 10(-4) mol cm(-3) is not influenced by the degree of solid-state order. Thus, the observed increase in electrical conductivity by almost 2 orders of magnitude can be attributed to an increase in charge-carrier mobility to more than 10(-1) cm(2) V-1 s(-1). Surprisingly, in contrast to charge transport in undoped P3HT, we find that the molecular weight of the polymer does not strongly influence the electrical conductivity, which highlights the need for studies that elucidate structure property relationships of strongly doped conjugated polymers.

Extraction of photocreated charge carriers from a prototypical all-polymer organic solar cell is investigated by combining transient photocurrent and time-delayed collection field experiments with numerical simulations. It is found that extraction is significantly hampered by charges getting trapped in spatial traps that are tentatively attributed to dead ends in the intermixed polymer networkin photovoltaic devices based on the same donor polymer and a fullerene acceptor this effect is much weaker. The slow-down in charge extraction leads to enhanced recombination and associated performance losses. These effects are observed in addition to the dispersive behavior that is characteristic of charge motion in energetically disordered media. Upon annealing the effects of spatial traps diminish, rationalizing the doubling in device power conversion efficiency after annealing.

combination of steady-state and time-resolved spectroscopic measurements is used to investigate the photophysics of the all-polymer bulk heterojunction system TQ1:N2200. Upon thermal annealing a doubling of the external quantum efficiency and an improved fill factor (FF) is observed, resulting in an increase in the power conversion efficiency. Carrier extraction is similar for both blends, as demonstrated by time-resolved electric-field-induced second harmonic generation experiments in conjunction with transient photocurrent studies, spanning the ps-mu s time range. Complementary transient absorption spectroscopy measurements reveal that the different quantum efficiencies originate from differences in charge carrier separation and recombination at the polymer-polymer interface: in as-spun samples similar to 35% of the charges are bound in interfacial charge-transfer states and recombine geminately, while this pool is reduced to similar to 7% in thermally-annealed samples, resulting in higher short-circuit currents. Time-delayed collection field experiments demonstrate a field-dependent charge generation process in as-spun samples, which reduces the FF. In contrast, field-dependence of charge generation is weak in annealed films. While both devices exhibit significant non-geminate recombination competing with charge extraction, causing low FFs, our results demonstrate that the donor/acceptor interface in all-polymer solar cells can be favourably altered to enhance charge separation, without compromising charge transport and extraction.

Solution-processed organic ferroelectric resistive switches could become the long-missing non-volatile memory elements in organic electronic devices. To this end, data retention in these devices should be characterized, understood and controlled. First, it is shown that the measurement protocol can strongly affect the apparent retention time and a suitable protocol is identified. Second, it is shown by experimental and theoretical methods that partial depolarization of the ferroelectric is the major mechanism responsible for imperfect data retention. This depolarization occurs in close vicinity to the semiconductor-ferroelectric interface, is driven by energy minimization and is inherently present in this type of phase-separated polymer blends. Third, a direct relation between data retention and the charge injection barrier height of the resistive switch is demonstrated experimentally and numerically. Tuning the injection barrier height allows to improve retention by many orders of magnitude in time, albeit at the cost of a reduced on/off ratio. (c) 2016 Elsevier B.V. All rights reserved.

In many organic electronic devices functionality is achieved by blending two or more materials, typically polymers or molecules, with distinctly different optical or electrical properties in a single film. The local scale morphology of such blends is vital for the device performance. Here, a simple approach to study the full 3D morphology of phase-separated blends, taking advantage of the possibility to selectively dissolve the different components is introduced. This method is applied in combination with AFM to investigate a blend of a semiconducting and ferroelectric polymer typically used as active layer in organic ferroelectric resistive switches. It is found that the blend consists of a ferroelectric matrix with three types of embedded semiconductor domains and a thin wetting layer at the bottom electrode. Statistical analysis of the obtained images excludes the presence of a fourth type of domains. The criteria for the applicability of the presented technique are discussed. (c) 2015 Wiley Periodicals, Inc.

Molecular doping is a crucial tool for controlling the charge-carrier concentration in organic semiconductors. Each dopant molecule is commonly thought to give rise to only one polaron, leading to a maximum of one donor: acceptor charge-transfer complex and hence an ionization efficiency of 100%. However, this theoretical limit is rarely achieved because of incomplete charge transfer and the presence of unreacted dopant. Here, we establish that common p-dopants can in fact accept two electrons per molecule from conjugated polymers with a low ionization energy. Each dopant molecule participates in two charge-transfer events, leading to the formation of dopant dianions and an ionization efficiency of up to 200%. Furthermore, we show that the resulting integer charge-transfer complex can dissociate with an efficiency of up to 170%. The concept of double doping introduced here may allow the dopant fraction required to optimize charge conduction to be halved.

We demonstrate multilevel data storage in organic ferroelectric resistive memory diodes consisting of a phase-separated blend of P(VDF-TrFE) and a semiconducting polymer. The dynamic behaviour of the organic ferroelectric memory diode can be described in terms of the inhomogeneous field mechanism (IFM) model where the ferroelectric components are regarded as an assembly of randomly distributed regions with independent polarisation kinetics governed by a time-dependent local field. This allows us to write and non-destructively read stable multilevel polarisation states in the organic memory diode using controlled programming pulses. The resulting 2-bit data storage per memory element doubles the storage density of the organic ferroelectric resistive memory diode without increasing its technological complexity, thus reducing the cost per bit.

Ferroelectric nanostructures offer a promising route for novel integrated electronic devices such as non-volatile memories. Here we present a facile fabrication route for ferroelectric capacitors comprising a linear array of the ferroelectric random copolymer of vinylidenefluoride and trifluoroethylene (P(VDF-TrFE)) interdigitated with the electrically insulating polymer polyvinyl alcohol (PVA). Micrometer size line gratings of both polymers were fabricated over large area by solution micromolding, a soft lithography method. The binary linear arrays were realized by backfilling with the second polymer. We investigated in detail the device physics of the patterned capacitors. The electrical equivalent circuit is a linear capacitor of PVA in parallel with a ferroelectric capacitor of P(VDF-TrFE). The binary arrays are electrically characterized by both conventional Sawyer-Tower and shunt measurements. The dependence of the remanent polarization on the array topography is explained by numerical simulation of the electric field distribution.

In photovoltaic devices, the photo-generated charge carriers are typically assumed to be in thermal equilibrium with the lattice. In conventional materials, this assumption is experimentally justified as carrier thermalization completes before any significant carrier transport has occurred. Here, we demonstrate by unifying time-resolved optical and electrical experiments and Monte Carlo simulations over an exceptionally wide dynamic range that in the case of organic photovoltaic devices, this assumption is invalid. As the photo-generated carriers are transported to the electrodes, a substantial amount of their energy is lost by continuous thermalization in the disorder broadened density of states. Since thermalization occurs downward in energy, carrier motion is boosted by this process, leading to a time-dependent carrier mobility as confirmed by direct experiments. We identify the time and distance scales relevant for carrier extraction and show that the photo-generated carriers are extracted from the operating device before reaching thermal equilibrium.

The performance of organic optoelectronic devices, such as organic photovoltaic (OPV) cells, is to a large extent dictated by their ability to transport the photogenerated charge, with relevant processes spanning a wide temporal (fs-mu s) and spatial (1-100 nm) range. However, time-resolved techniques can access only a limited temporal window, and often contradict steady-state measurements. Here, commonly employed steady-state and time-resolved techniques are unified over an exceptionally wide temporal range (fs-mu s) in a consistent physical picture. Experimental evidence confirmed by numerical simulations shows that, although various techniques probe different time scales, they are mutually consistent as they probe the same physical mechanisms governing charge motion in disordered media-carrier hopping and thermalization in a disorder-broadened density of states (DOS). The generality of this framework is highlighted by time-resolved experimental data obtained on polymer:fullerene, polymer:polymer, and small-molecule blends with varying morphology, including recent experiments revealing that low donor content OPV devices operate by long-range hole tunneling between non-nearest-neighbor molecules. The importance of nonequilibrium processes in organic electronic materials is reviewed, with a particular focus on experimental data and understanding charge transport physics in terms of material DOS.

Organic bulk heterojunction solar cells are often regarded as near-equilibrium devices, whose kinetics are set by well-defined charge carrier mobilities, and relaxation in the density of states is commonly ignored or included purely phenomenologically. Here, the motion of photocreated charges is studied experimentally with picosecond time resolution by a combination of time-resolved optical probing of electric field and photocurrent measurements, and the data are used to define parameters for kinetic Monte Carlo modelling. The results show that charge carrier motion in a prototypical polymer:fullerene solar cell under operational conditions is orders of magnitude faster than would be expected on the basis of corresponding near-equilibrium mobilities, and is extremely dispersive. There is no unique mobility. The distribution of extraction times of photocreated charges in operating organic solar cells can be experimentally determined from the charge collection transients measured under pulsed excitation. Finally, a remarkable distribution of the photocurrent over energy is found, in which the most relaxed charge carriers in fact counteract the net photocurrent.

In organic solar cells continuous donor and acceptor networks are considered necessary for charge extraction, whereas discontinuous neat phases and molecularly mixed donor–acceptor phases are generally regarded as detrimental. However, the impact of different levels of domain continuity, purity, and donor–acceptor mixing on charge transport remains only semiquantitatively described. Here, cosublimed donor–acceptor mixtures, where the distance between the donor sites is varied in a controlled manner from homogeneously diluted donor sites to a continuous donor network are studied. Using transient measurements, spanning from sub-picoseconds to microseconds photogenerated charge motion is measured in complete photovoltaic devices, to show that even highly diluted donor sites (5.7%–10% molar) in a buckminsterfullerene matrix enable hole transport. Hopping between isolated donor sites can occur by long-range hole tunneling through several buckminsterfullerene molecules, over distances of up to ≈4 nm. Hence, these results question the relevance of “pristine” phases and whether a continuous interpenetrating donor–acceptor network is the ideal morphology for charge transport.

Charge transport in organic photovoltaic (OPV) devices is often characterized by space-charge limited currents (SCLC). However, this technique only probes the transport of charges residing at quasi-equilibrium energies in the disorder-broadened density of states (DOS). In contrast, in an operating OPV device the photogenerated carriers are typically created at higher energies in the DOS, followed by slow thermalization. Here, by ultrafast time-resolved experiments and simulations it is shown that in disordered polymer/fullerene and polymer/polymer OPVs, the mobility of photogenerated carriers significantly exceeds that of injected carriers probed by SCLC. Time-resolved charge transport in a polymer/polymer OPV device is measured with exceptionally high (picosecond) time resolution. The essential physics that SCLC fails to capture is that of photo­generated carrier thermalization, which boosts carrier mobility. It is predicted that only for materials with a sufficiently low energetic disorder, thermalization effects on carrier transport can be neglected. For a typical device thickness of 100 nm, the limiting energetic disorder is σ ≈71 (56) meV for maximum-power point (short-circuit) conditions, depending on the error one is willing to accept. As in typical OPV materials the disorder is usually larger, the results question the validity of the SCLC method to describe operating OPVs.

We explore a new approach to organic ferroelectric diodes using a benzene-tricarboxamide (BTA) core connected with C10 alkyl chains to pyrrole groups, which can be polymerized to provide a semiconducting ferroelectric material. The compound possesses a columnar hexagonal liquid crystalline (LC) phase and exhibits ferroelectric switching. At low switching frequencies, an additional process occurs, which leads to a high hysteretic charge density of up to similar to 1000 mC/m(2). Based on its slow rate, the formation of gas bubbles, and the emergence of characteristic polypyrrole absorption bands in the UV-Vis-NIR, the additional process is identified as the oxidative polymerization of pyrrole groups, enabled by the presence of amide groups. Polymerization of the pyrrole groups, which is essential to obtain semiconductivity, is limited to thin layers at the electrodes, amounting to similar to 17 nm after cycling for 21 h. (C) 2017 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc.

Organic electronics is becoming more and more important because the low level of fabrication and deposition complexity even at large scale makes it a good candidate for future low cost technological product development. P(VDF-TrFE) is a co-polymer of special interest due its ferroelectric property enabling usage in re-programmable non-volatile organic memory and magnetoelectric sensors. Piezo force microscopy (PFM) provides access to the technologically relevant ferroelectric polarisability and its remanent polarization via imaging of the piezoelectric property. Here we use PFM to show that piezoelectric response of a P(VDF-TrFE) film can be enhanced by up to 260 % after soft X-ray irradiation. This enhancement correlates with morphological change of part of the film, from amorphous to crystalline. An optimal irradiation dose is found above which the film gets eroded and the piezoelectric response gets lowered. (C) 2016 Elsevier B.V. All rights reserved.

We report pulsed terahertz (THz) emission from solution-processed metal halide perovskite films with electric field 1 order of magnitude lower than p-InAs, an efficient THz emitter. Such emission is enabled by a unique combination of efficient charge separation, high carrier mobilities, and more importantly surface defects. The mechanism of generation was identified by investigating the dependence of the THz electric field amplitude on surface defect densities, excess charge carriers, excitation intensity and energy, temperature, and external electric field. We also show for the first time THz emission from a curved surface, which is not possible for any crystalline semiconductor and paves the way to focus high-intensity sources. These results represent a possible new direction for perovskite optoelectronics and for THz emission spectroscopy as a complementary tool in investigating surface defects on metal halide perovskites, of fundamental importance in the optimization of solar cells and light-emitting diodes.

We investigated the impact of singly occupied molecular orbital (SOMO) energy on the n-doping efficiency of benzimidazole derivatives. By designing and synthesizing a series of new air-stable benzimidazole-based dopants with different SOMO energy levels, we demonstrated that an increase of the dopant SOMO energy by only similar to 0.3 eV enhances the electrical conductivity of a benchmark electron-transporting naphthalenediimide-bithiophene polymer by more than 1 order of magnitude. By combining electrical, X-ray diffraction, and electron paramagnetic resonance measurements with density functional theory calculations and analytical transport simulations, we quantitatively characterized the conductivity, Seebeck coefficient, spin density, and crystallinity of the doped polymer as a function of the dopant SOMO energy. Our findings strongly indicate that charge and energy transport are dominated by the (relative) position of the SOMO level, whereas morphological differences appear to play a lesser role. These results set molecular-design guidelines for next-generation n-type dopants.

With the increasing performance of organic semiconductors, contact resistances become an almost fundamental problem, obstructing the accurate measurement of charge carrier mobilities. Here, a generally applicable method is presented to determine the true charge carrier mobility in an organic field-effect transistor (OFET). The method uses two additional finger-shaped gates that capacitively generate and probe an alternating current in the OFET channel. The time lag between drive and probe can directly be related to the mobility, as is shown experimentally and numerically. As the scheme does not require the injection or uptake of charges it is fundamentally insensitive to contact resistances. Particularly for ambipolar materials the true mobilities are found to be substantially larger than determined by conventional (direct current) schemes.

The full potential of scanning tunnelling microscopy (STM) and scanning tunnelling spectroscopy for in-situ characterization of organic semiconductors has so far not been accessible. Here, we demonstrate that the underlying problem, the low intrinsic conductivity, can be overcome by working in a field-effect geometry. We present high resolution surface topographies obtained by STM on pentacene organic field-effect transistors (OFETs). By virtue of the OFET geometry, the hole accumulation layer that is present at sufficiently negative gate bias acts as back contact, collecting the tunnelling current. The presence of a true tunnelling gap is established, as is the need for the presence of an accumulation layer. The tunnelling current vs. tip bias showed rectifying behaviour, which is rationalized in terms of the tip acting as a second gate on the unipolar semiconductor. An explanatory band diagram is presented. The measurements shown indicate that intrinsic organic semiconductors can be in-situ characterized with high spatial and energetic resolution in functional devices.

We employed bias-assisted charge extraction techniques to investigate the transient and steady-state recombination of photogenerated charge carriers in complete devices of a disordered polymer-fullerene blend. Charge recombination is shown to be dispersive, with a significant slowdown of the recombination rate over time, consistent with the results from kinetic Monte Carlo simulations. Surprisingly, our experiments reveal little to no contributions from early time recombination of nonequilibrated charge carriers to the steady-state recombination properties. We conclude that energetic relaxation of photogenerated carriers outpaces any significant nongeminate recombination under application-relevant illumination conditions. With equilibrated charges dominating the steady-state recombination, quasi-equilibrium concepts appear suited for describing the open-circuit voltage of organic solar cells despite pronounced energetic disorder.

The light-emitting electrochemical cell promises cost-efficient, large-area emissive applications, as its characteristic in-situ doping enables use of air-stabile electrodes and a solution-processed single-layer active material. However, mutual exclusion of high efficiency and high brightness has proven a seemingly fundamental problem. Here we present a generic approach that overcomes this critical issue, and report on devices equipped with air-stabile electrodes and outcoupling structure that deliver a record-high efficiency of 99.2 cd A(-1) at a bright luminance of 1910 cd m(-2). This device significantly outperforms the corresponding optimized organic light-emitting diode despite the latter employing calcium as the cathode. The key to this achievement is the design of the host-guest active material, in which tailored traps suppress exciton diffusion and quenching in the central recombination zone, allowing efficient triplet emission. Simultaneously, the traps do not significantly hamper electron and hole transport, as essentially all traps in the transport regions are filled by doping.

Ferroelectric materials are known and valued for their multifunctionality arising from the possibility to perturb the remnant ferroelectric polarization by electric field, temperature and/or mechanical stimuli. While inorganic ferroelectrics dominate the current market, their organic counterparts may provide highly desired properties like eco-friendliness, easy processability and flexibility, concomitantly opening unique opportunities to combine multiple functionalities into a single compound that facilitates unprecedented device concepts and designs. Supramolecular organic ferroelectrics of columnar discotic type, that are the topic of this thesis, offer additional advantages related to their strong hierarchical self-assembly and easy tunability by molecular structure modifications, allowing optimization of ferroelectric characteristics and their hybridization with, e.g., semiconductivity. This not only leads to textbook ferroelectric materials that can be used as model systems to understand the general behaviour of ferroics, but also gives rise to previously unobserved effects stemming from the interplay of different functionalities.

The core-shell structure of the molecules under the scope enables multiple pathways forrational design by molecular structure modification. This was firstly pursued via peripheral tail engineering on an archetypal self-assembling ferroelectric trialkylbenzene-1,3,5-tricarboxamide (BTA). We found that by shortening the alkyl chain length all the ferroelectric properties can be continuously tuned. In particular, changing the tail from C18H37 to C6H13causes an increase in depolarization activation energy (~0.8 eV to ~1.55 eV), coercive field(~25 V/μm to ~50 V/μm) and remnant polarization (~20 mC/m2 to ~60 mC/m2). The combination of the mentioned characteristics resulted in a record polarization retention time of close to 3 months at room temperature for capacitor devices of the material having the shortest alkyl chain – BTA-C6, which at the time of writing was one of the best results for liquid-crystalline ferroelectrics.

Taking one step further, we experimentally demonstrated how introduction of branched-tailsubstituents results in materials with a wide operating temperature range and a data retention time of more than 10 years in thin-film solution-processed capacitor devices already atelevated temperatures with no measurable depolarization at room temperature. The observed differences between linear- and branched-tail compounds were analysed using density functional theory (DFT) and molecular dynamics (MD) simulations. We concluded that morphological factors like improved packing quality and reduced disorder, rather than electrostatic interactions or intra/inter-columnar steric hindrance, underlay the superior properties of the branched-tailed BTAs. Synergistic effects upon blending of compounds with branched and linear sidechains were shown to further improve the materials’ characteristics.

Exploiting the excellent ferroelectric performance and the well-defined nanostructure of BTAs, we experimentally determined the Preisach (hysteron) distribution of BTA and confronted it to the one obtained for the semi-crystalline P(VDF:TrFE). This allowed to elucidate how the broadening of the Preisach distribution relates to the materials’ morphology. We further connected the experimental Preisach distribution to the corresponding microscopic switching kinetics. We argue that the combination of the two underlays the macroscopic dispersive switching kinetics as commonly observed for practical ferroelectrics. These insights lead to guidelines for further advancement of ferroelectric materials both for conventional and multi-bit data storage applications.

Although having strong differences in the Preisach distribution, BTA and P(VDF:TrFE) both demonstrate negative piezoelectricity – a rare anomalous phenomenon which is characteristic to two-phased materials and has never been observed in small-molecular ferroelectrics. We measured a pronounced negative piezoelectric effect in a whole family of BTAs and revealed its tunability by mesogenic tail substitution and structural disorder. While the large- and small-signal strain in highly ordered thin-film BTA capacitor devices are dominated by intrinsic contributions and originates from piezostriction, rising disorder introduces additional extrinsic factors that boost the large-signal d33 up to −20 pm/V in short-tailed molecules. Interestingly, homologues with longer mesogenic tails show a large-signal electromechanical response that is dominated by the quadratic Maxwell strain with significant mechanical softening upon polarization switching, whereas the small-signal strain remains piezostrictive. Molecular dynamics and DFT calculations both predict a positive d33 for defect-free BTA stacks. Hence, the measured negative macroscopic d33 is attributed to the presence of structural defects that enable the dimensional effect to dominate the piezoelectric response of BTA thin films.

The true multifunctionality of supramolecular discotics manifests when large semiconducting cores surrounded by field-switchable strongly polar moieties are introduced in the structure. We showed how the combination of switchable dipolar side groups and the semiconducting core of the newly synthetized C3-symmetric benzotristhiophene molecule (BTTTA) leads to an ordered columnar material showing continuous tunability from injection- to bulk-limited conductivity modulation. Both these resistive switching mechanisms may lead to the next-generation high-density non-volatile rewritable memory devices with high on/off ratios and non-destructive data readout – the element that has been desperately sought after to enablefully organic flexible electronics.