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Here, we show a new diketopyrrole based polymeric hole-transport material (PBDTP-DTDPP, (poly[[2,5-bis(2-hexyldecyl)-2,3,5,6-tetrahydro-3,6-dioxopyrrolo[3,4-c]pyrrole-1,4-diyl]-alt-[[2,2′-(4,8-bis(4-ethylhexyl-1-phenyl)-benzo[1,2-b:4,5-b′]dithiophene)bis-thieno[3,2-b]thiophen]-5,5′-diyl]])) for application in perovskite solar cells. The material performance was tested in a solar cell with an optimized configuration, FTO/SnO₂/perovskite/PBDTP-DTDPP/Au, and the device showed a power conversion efficiency of 14.78%. The device charge carrier dynamics were investigated using transient absorption spectroscopy. The charge separation and recombination kinetics were determined in a device with PBDTP-DTDPP and the obtained results were compared to a reference device. We find that PBDTP-DTDPP enables similar charge separation time (<∼4.8 ps) to the spiro-OMeTAD but the amount of nongeminate recombination is different. Specifically, we find that the polymeric PBDTP-DTDPP hole-transport layer (HTL) slows-down the second-order recombination much less than spiro-OMeTAD. This effect is of particular importance in studying the charge transportation in optimized solar cell devices with diketopyrrole based HTL materials.

Electron-electron interactions are the fastest processes in materials, occurring on femtosecond to attosecond timescales, depending on the electronic band structure of the material and the excitation energy. Such interactions can play a dominant role in light-induced processes such as nano-enhanced plasmonics and catalysis, light harvesting, or phase transitions. However, to date it has not been possible to experimentally distinguish fundamental electron interactions such as scattering and screening. Here, we use sequences of attosecond pulses to directly measure electron-electron interactions in different bands of different materials with both simple and complex Fermi surfaces. By extracting the time delays associated with photoemission we show that the lifetime of photoelectrons from the d band of Cu are longer by similar to 100 as compared with those from the same band of Ni. We attribute this to the enhanced electron-electron scattering in the unfilled d band of Ni. Using theoretical modeling, we can extract the contributions of electron-electron scattering and screening in different bands of different materials with both simple and complex Fermi surfaces. Our results also show that screening influences high-energy photoelectrons (approximate to 20 eV) significantly less than low-energy photoelectrons. As a result, high-energy photoelectrons can serve as a direct probe of spin-dependent electron-electron scattering by neglecting screening. This can then be applied to quantifying the contribution of electron interactions and screening to low-energy excitations near the Fermi level. The information derived here provides valuable and unique information for a host of quantum materials.

    The current implementation of conjugated polymers (“conducting plastics”) in a wide range of devices promises to bring the vision of a new generation of flexible, efficient and low-cost applications to reality. Plastic lightemitting devices in the form of polymer light-emitting diodes (PLEDs) are projected to be particularly close to the market in applications such as large area and conformable illumination panels and high-performance thin displays. However, two notable drawbacks of PLEDs are that they depend on vacuum deposition of a reactive metal for the negative electrode and that the active material must be extremely thin and uniform in thickness. As a consequence, PLEDs cannot be expected to allow for a low-cost continuous production using a roll-to-roll coating and/or printing process.

This thesis focuses on an alternative to the PLED: A light-emitting electrochemical cell (LEC). LECs comprise a mixture of a conjugated polymer and a solid-state electrolyte as the active material positioned between two electrodes. The existence of mobile ions in the active material allows for a number of interesting attributes, both from a fundamental science and an application perspective. Importantly, the ions and the related unique operation of LECs make these devices apt for the utilization of low-cost roll-to-roll fabrication of the entire device as the electrode materials can be air stable and solution-processible and the requirement on the thickness of the active material is much less stringent than in PLEDs.

   The herein presented “basic science” studies primarily focus on the operation of LECs. It is for instance firmly established that a light-emitting p-n junction can form in-situ in a LEC device during the application of a voltage. This dynamic p-n junction exhibits some similarities, but also distinct differences, in comparison to the static p-n junctions that are exploited in crystalline inorganic semiconductor devices. We have also systematically explored the role that the constituent materials (ions, conjugated polymer, ionic solvent, and electrode material) can have on the performance of LECs, and two of the more important findings are that the concentration of ions can influence the doping structure in a motivated fashion and that it is critically important to consider the electrochemical stability window of the constituent materials in order to attain stable device operation.

   With this knowledge at hand, we have executed a number of more “applied science” studies, where we have used the acquired information from the basic-science studies for the rational design of improved devices. We have demonstrated LEC devices with significantly improved device performance, as exemplified by an orange-red device that emitted significant light (> 100 cd/m²) for more than one month of uninterrupted operation, and a yellow-green device that emitted significant light for 25 days at a low voltage of 4 V and at relatively high efficiency (6 lm/W). Finally, we have conceptualized and realized a solely solution-processed and metal-free LEC comprising graphene as the negative electrode and the conducting polymer PEDOT-PSS as the positive electrode. This type of devices represents a paradigm shift in the field of solid-state lighting as they demonstrate that it is possible to fabricate an entire light-emitting device from solution-processible and “green” carbon-based materials in a process that is akin to printing.

Incorporation of ions in the active layer of organic semiconductor devices may lead to attractive device properties like enhanced injection and improved carrier transport. In this paper, we investigate the effect of the salt concentration on the operation of light-emitting electrochemical cells, using experiments and numerical calculations. The current density and light emission are shown to increase linearly with increasing ion concentration over a wide range of concentrations. The increasing current is accompanied by an ion redistribution, leading to a narrowing of the recombination zone. Hence, in absence of detrimental side reactions and doping-related luminescence quenching, the ion concentration should be as high as possible.

The dynamics of doping transformation fronts in organic semiconductor plasma is studied for application in light-emitting electrochemical cells. We show that new fundamental effects of the plasma dynamics can significantly improve the device performance. We obtain an electrodynamic instability, which distorts the doping fronts and increases the transformation rate considerably. We explain the physical mechanism of the instability, develop theory, provide experimental evidence, perform numerical simulations, and demonstrate how the instability strength may be amplified technologically. The electrodynamic plasma instability obtained also shows interesting similarity to the hydrodynamic Darrieus-Landau instability in combustion, laser ablation, and astrophysics.

The application of doping in semiconductors plays a major role in the high performances achieved to date in inorganic devices. In contrast, doping has yet to make such an impact in organic electronics. One organic device that does make extensive use of doping is the light-emitting electrochemical cell (LEC), where the presence of mobile ions enables dynamic doping, which enhances carrier injection and facilitates relatively large current densities. The mechanism and effects of doping in LECs are, however, still far from being fully understood, as evidenced by the existence of two competing models that seem physically distinct: the electrochemical doping model and the electrodynamic model. Both models are supported by experimental data and numerical modeling. Here, we show that these models are essentially limits of one master model, separated by different rates of carrier injection. For ohmic nonlimited injection, a dynamic p−n junction is formed, which is absent in injection-limited devices. This unification is demonstrated by both numerical calculations and measured surface potentials as well as light emission and doping profiles in operational devices. An analytical analysis yields an upper limit for the ratio of drift and diffusion currents, having major consequences on the maximum current density through this type of device.

Organic electronic circuits based on a combination of n- and p-type transistors (so-called CMOS circuits) are attractive, since they promise the realization of a manifold of versatile and low-cost electronic devices. Here, we report a novel photoinduced transformation method, which allows for a particularly straightforward fabrication of highly functional organic CMOS circuits. A solution-deposited single-layer film, comprising a mixture of the n-type semiconductor [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and the p-type semiconductor poly-3-hexylthiophene (P3HT) in a 3:1 mass ratio, was utilized as the common active material in an array of transistors. Selected film areas were exposed to laser light, with the result that the irradiated PCBM monomers were photochemically transformed into a low-solubility and high-mobility dimeric state. Thereafter, the entire film was developed via immersion into a developer solution, which selectively removed the nonexposed, and monomeric, PCBM component. The end result was that the transistors in the exposed film areas are n-type, as dimeric PCBM is the majority component in the active material, while the transistors in the nonexposed film areas are p-type, as P3HT is the sole remaining material. We demonstrate the merit of the method by utilizing the resulting combination of n-type and p-type transistors for the realization of CMOS inverters with a high gain of ∼35.

The emerging field of “organic” or “plastic” electronics has brought low-voltage, ultrathin, and energy-efficient lighting and displays to market as organic light-emitting diode (OLED) televisions and displays in cameras and mobile phones. Despite using carbon-based materials as the light-emitting layer, previous efficient organic electronic light-emitting devices have required at least one metal electrode. Here, we utilize chemically derived graphene for the transparent cathode in an all-plastic sandwich-structure device, similar to an OLED, called a light-emitting electrochemical cell (LEC). Using a screen-printable conducting polymer as a partially transparent anode and a micrometer-thick active layer solution-deposited from a blend of a light-emitting polymer and a polymer electrolyte, we demonstrate a light-emitting device based solely on solution-processable carbon-based materials. Our results demonstrate that low-voltage, inexpensive, and efficient light-emitting devices can be made without using metals. In other words, electronics can truly be “organic”.

We develop a model describing the electrochemical conversion of an organic semiconductor (specifically, the active material in a light-emitting electrochemical cell) from the undoped nonconducting state to the doped conducting state. The model, an extended Nernst-Planck-Poisson model, takes into account both strongly concentration-dependent mobility and diffusion for the electronic charge carriers and the Nernst equation in the doped conducting regions. The standard Nernst-Planck-Poisson model is shown to fail in its description of the properties of the doping front. Solving our extended model numerically, we demonstrate that doping front progression in light-emitting electrochemical cells can be accurately described.