| 1. |
- Wang, Chuanfei, 1986-
(författare)
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Electronic Structure of π-Conjugated Materials and Their Effect on Organic Photovoltaics
- 2017
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The great tunability of structure and electronic properties of π-conjugated organic molecules/polymers combined with other advantages such as light weight and flexibility etc., have made organic-based electronics the focus of an exciting still-growing field of physics and chemistry for more than half a century. The application of organic electronics has led to the appearance of wide range of organic electronic devices mainly including organic light emitting diodes (OLED), organic field effect transistors (OFET) and organic solar cells (OSC). The application of the organic electronic devices mainly is limited by two dominant parameters, i.e., their performance and stability. Up to date, OLED has been successfully commercialized in the market while the OSC are still on the way to commercialization hindered by low efficiency and inferior stability. Understanding the energy levels of organic materials and energy level alignment of the devices is crucial to control the efficiency and stability of the OSC. In this thesis, energy levels measured by different methods are studied to explore their relationship with device properties, and the strategies on how to design efficient and stable OSC based on energy level diagrams are provided.Cyclic Voltammetry (CV) is a traditional and widely used method to probe the energy levels of organic materials, although there is little consensus on how to relate the oxidation/reduction potential ((Eox/Ered) to the vacuum level. Ultraviolet Photoelectron Spectroscopy (UPS) can be used to directly detect vertical ionization potential (IP) of organic materials. In this thesis, a linear relationship of IP and Eox was found, with a slope equal to unity. The relationship provides for easy conversion of values obtained by the two techniques, enabling complementarily use in designing and fabricating efficient and stable OSC. A popular rule of thumb is that the offset between the LUMO levels of donor and acceptor should be 0.3 eV, according to which a binary solar cell with the minimum voltage losses around 0.49 V was designed here.Introduction of the ternary blend as active layer is an efficient way to improve both efficiency and stability of the OSC. Based on our studied energy-level diagram within the integer charge transfer (ICT) model, we designed ternary solar cells with enhanced open circuit voltage for the first time and improved thermal stability compared to reference binary ones. The ternary solar cell with minimum voltage losses was developed by combining two donor materials with same ionization potential and positive ICT energy while featuring complementary optical absorption. Furthermore, the fullerene acceptor was chosen so that the energy of the positive ICT state of the two donor polymers is equal to the energy of negative ICT state of the fullerene, which can enhance dissociation of all polymer donor and fullerene acceptor excitons and suppress bimolecular and trap-assistant recombination.Rapid development of non-fullerene acceptors in the last two years affords more recipes of designing both efficient and stabile OSC. We show in this thesis how non-fullerene acceptors successfully can be used to design ternary solar cells with both enhanced efficiency and thermal stability. Besides improving the efficiency of the devices, understanding of the stability and degradation mechanism is another key issue. The degradation of conjugated molecules/polymers often follow many complicated pathways and at the same time many factors for degradation are coupled with each other. Therefore, the degradation of non-fullerene acceptors was investigated in darkness by photoelectron spectroscopy in this thesis with the in-situ method of controlling exposure of O2 and water vapor separately.
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| 2. |
- Zuo, Guangzheng, 1985-
(författare)
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Doping and Density of States Engineering for Organic Thermoelectrics
- 2018
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- 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.
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| 3. |
- Bian, Qingzhen, 1988-
(författare)
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Excitonic and charge carrier transport in organic materials and device applications
- 2020
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- With the potential for future commercial use, organic electronics have been intensively studied for the last few decades. To exploit the next generation of high-performance devices, detailed study of the underlying physics is essential. Excitonic and charge carrier transport plays a critical role in device performance and related studies have attracted a lot of attention in recent decades. This thesis particularly focused on excitonic and charge carrier transport in organic materials and related device applications.In natural light harvesting systems, such as the reaction centers of purple bacteria, quantum coherence has been proposed to be present as a contributor to the related charge and energy transport processes, and almost 100% charge conversion is present in these efficient biological systems. This high energy conversion efficiency inspires the idea that if a similar strategy was used in artificial energy conversion devices such as organic photovoltaics, etc., this could significantly enhance the device’s performance. In the first study, the charge separation process in some donor/acceptor blends was investigated. The contribution of quantum coherence to device performance was studied in detail using several steady state and ultrafast transient techniques. In one efficient donor/acceptor blend, a pronounced coherence of charge separation was identified, which contributed to the enhancement of the photocurrent generation, which finally resulted in efficient device performance.For the light emitting diodes, triplet excitons harvesting plays a critical role in device performance. In the thermally activated delayed fluorescence (TADF) materials, due to an efficient reverse intersystem process from triplet excitons to singlet excitons, the losses due to triplet excitons were suppressed. As a result, a desired high quantum yield has been achieved. To enhance device efficiency, the detailed study of the upconversion physics between triplet and singlet is needed. Previous studies have proposed some physical models to explain this efficient upconversion process, while the nature of this physical process is still under debate and unclear. In my second work, we studied the exciton kinetics in two different TADF materials. These TADF materials were inserted in a protein fibril host, and the resulting protein scaffold was able to modify the geometric configuration of the related TADF molecule. As a result, an enhancement of the photoluminescence quantum yield was achieved.To achieve efficient device performance in organic electronics, the physical processes at the metal/material interface and charge carrier injection/extraction, also play a critical role. Efficient charge injection can be achieved by Ohmic contact, and charge injection/extraction of metal/organic materials has been intensively studied in the last few decades. In my third study, an efficient hole transport material based on the biopolymer DNA was introduced. A hole doping process was found in the hybrid materials and contributes to the Ohmic contacts. The hybrid material can be used in different organic electronics devices, such as field effect transistors, light emitting diodes and solar cells, and thus demonstrates a general application capability.In organic photovoltaics, the loss from the open circuit photovoltages has been an Achilles’ heel for further enhancement of device performance. The voltage loss includes the radiative and non-radiative value, and intensive studies have focused on how to suppress losses from the non-radiative channel. In my fourth study, the non-radiative voltage loss was studied in a series of terpolymer blends and ternary blends. Compared to the ternary blends, a decreased nonradiative loss was found in the terpolymer blends.
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| 4. |
- Wang, Fei, 1988-
(författare)
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Properties of multilayered and multicomponent nitride alloys from first principles
- 2018
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis is a theoretical exploration of properties of multilayered and multicomponent nitride alloys, in particular their mixing thermodynamics and elastic behaviors. Systematic investigation of properties of a large class of materials, such as the multicomponent nitride solid solutions, is in line with the modern approach of high-throughput search of novel materials. In this thesis we benchmark and utilize simple but efficient methodological frameworks in predicting mixing thermodynamics, Young’s moduli distribution of multilayer alloys and the linear thermal expansion of quaternary nitride solid solutions.We demonstrate by accurate ab-initio calculations that Ti1−xAlxN solid solution is stabilized by interfacial effects if it is coherently sandwiched between TiN layers along (001). For TiN/AlN and ZrN/AlN multilayers we show higher thermodynamic stability with semicoherent interfaces than with isostructural coherent ones.Accurate 0 Kelvin elastic constants of cubic TixXyAl1−x−yN (X=Zr, Hf, Nb, V, Ta) solid solutions and their multilayers are derived and an analytic comparison of strengths and ductility are presented to reveal the potential of these materials in hard coating applications. The Young’s moduli variation of the bulk materials has provided a reliable descriptor to screen the Young’s moduli of coherent multilayers.The Debye model is used to reveal the high-temperature thermodynamics and spinodal decomposition of TixNbyAl1−x−yN. We show that though the effect of vibration is large on the mixing Gibbs free energy the local spinoal decomposition tendencies are not altered. A quasi-harmonic Debye model is benchmarked against results of molecular dynamics simulations in predicting the thermal expansion coefficients of TixXyAl1−x−yN (X=Zr, Hf, Nb, V, Ta).
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| 5. |
- Wang, Yan, 1978-
(författare)
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A domain-specific language for protocol stack implementation in embedded systems
- 2011
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Embedded network software has become increasingly interesting for both research and business as more and more networked embedded systems emerge. Well-known infrastructure protocol stacks are reimplemented on new embedded hardware and software architectures. New requirements of modern applications and devices require to implement newly designed or revised protocols. However, implementing protocol stacks for embedded systems remains a time-consuming and error-prone task due to the complexity and performancecritical nature of network software. It is even more so when targeting resource constrained embedded systems: implementations have to minimize energy consumption, memory usage etc., while programming efficiency is needed to improve on time-to-market, scalability, maintainability and product evolution. Therefore, it is worth researching on how to make protocol stack implementations for embedded systems both easier and more likely to be correct within the resource limits. In the work presented in this thesis, we take a language-based approach and aim to facilitate the implementation of protocol stacks while realizing performance demands and being aware of energy consumption and memory usage within the constraints imposed by embedded systems. We give background on DSL implementation techniques, investigate common practices in network protocol development to determine the potential of domain-specifi languages (DSLs) for embedded network software, and propose a domain-specifi embedded language (DSEL), Protege (Protocol Implementation Generator), for declaratively describing overlaid protocol stacks. In Protege, a high-level packet specification is dually compiled into an internal data representation for protocol logic implementation, and packet processing methods which are then integrated into the dataflow framework of a protocol overlay specification. Constructs for finite state machines allow to specify protocol logic in a concise manner, close to the protocol specification style. Protege specifications are compiled to highly portable C code for various architectures. Four attached scientific papers report our main results in more detail: an embedded implementation of the data description calculus in Haskell, a compilation framework for generating packet processing code with overlays, the domain-specific language Protege in overview (including embedding techniques and runtime system features), and a real-world case study implementing an industrial application protocol.
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