M.Sc. / Thin film solar cell devices based on amorphous silicon absorber films are promising candidates for the efficient conversion of sunlight into useable, cheap electrical energy. However, typical device structures are rather complex and consist of semiconductor/metal contacts as well as a complicated p-i-n junction. Against this background, the present study focussed on the optimization of certain key components of the device, including the transparent conductive oxide, amorphous silicon absorber layers and substrate/metal structures. These thin films were deposited by direct current (DC) magnetron sputtering and radio frequency (RF) capacitativecoupled gas discharge. In each case, a systematic study was conducted in which all the relevant processing parameters were varied over a broad range. The material quality of the respective films was subsequently correlated against the growth parameters. In the case of DC magnetron sputtered ZnO, w hich is generally used as a transparent conductive oxide in the device structure, the material quality were critically influenced by geometric orientation of the sample with respect to the target, the substrate-target distance, deposition power, working pressure and substrate temperature. Optimum structural, optical and electrical properties were obtained in the case of samples deposited at an angle of 80° with respect to the surface of the target. Bombardment damage was to a large extent prevented when the samples were placed at a vertical substrate-to-target distance of 70 mm, 75 mm away from the center zone of the plasma. The optimum substrate temperature, deposition power and working pressure was experimentally found to be 100°C; 600 mW/cm2 and 5.25 ´ 10-3 Torr, respectively. The structural features of the substrates influenced the morphology and optical properties of the DC sputtered metallic films. In general, the surface roughness increased when the glass substrates were replaced by kapton. The glass/silver structures were characterized by relatively smooth surface morphologies, while glass/aluminium films exhibited spike-like growth features. The material properties of intrinsic amorphous silicon were influenced by the RF power, substrate temperature and deposition pressure. A systematic study revealed optimum structural, optical and electrical properties at depositions powers around 43 mW/cm2, substrate temperatures close to 200°C and deposition pressures in the order of 500 mT. / Professor V. Alberts

abstract: Perovskite solar cells are the next generation organic-inorganic hybrid technology and have achieved remarkable efficiencies comparable to Si-based conventional solar cells. Since their inception in 2009 with an efficiency of 3.9%, they have improved tremendously over the past decade and recently demonstrated 25.2% efficiency for single-junction devices. There are a few hurdles, however, that prevent this technology from realizing their full potential, such as stability and toxicity of the perovskites. Apart from solution processing in the fabrication of perovskites, precursor composition plays a major role in determining the quality of the thin film and its general properties. This work studies novel approaches for improving the efficiency and stability of the perovskite solar cells with minimized toxicity. The effect of excess Pb on photo-degradation in MAPbI3 perovskites in an inverted device architecture was studied with a focus on improving stability and efficiency. Precursor concentration with 5% excess Pb was found to be optimal for better efficiency and stability against photo-degradation. Further improvements in efficiency were made possible through the addition of Zirconium Acetylacetonate as a secondary electron buffer layer. A concentration of 1.5mg/ml was found to be optimal for demonstrating better efficiency and stability. Partial substitution of Pb with non-toxic Sr was also studied for improving the stability of inverted devices. Using acetate-derived precursors, 10% Sr was introduced into perovskites for improvements to the stability of the device. In another study, triple-cation perovskites with FAMACs cations were studied with doping different amounts of Phenyl Ethyl Ammonium (PEA) to induce a quasi 2D-3D structure for improved moisture stability. Doping the perovskite with 1.67% PEA was found to be best for improved morphology with fewer pinholes, which further resulted in better VOC and stability. A passivation effect for triple-cation perovskites was further proposed with the addition of a Guanidinium Iodide layer on the perovskite. Concentrations of 1mg/ml and 2mg/ml were demonstrated to be best for reducing defects and trap states and increasing the overall stability of the device. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2020

Indium tin oxide (ITO) is the most widely used transparent electrode in flexible solar cells because of its high transparency and conductivity. But still, cracking of ITO on PET substrates due to tensile loading is not fully understood and it affects the functionality of the solar cell tremendously as ITO loses its conductivity. Here, we investigate the cracking evolution in ITO/PET exposed to two categories of tests. Monotonous tensile testing is done in order to trace the crack propagation in ITO coating as well as determining a loading range to focus on during our study. Five cycles test is also conducted to check the crack closure effect on the resistance variation of ITO. Analytical model for the damage in ITO layer is implemented using the homogenization concept as in laminated composites for transverse cracking. The homogenization technique is done twice on COMSOL to determine the mechanical and electrical degradation of ITO due to applied loading. Finally, this damage evolution is used for a simulation to predict the degradation of ITO as function in the applied load and correlate this degradation with the resistance variation. Experimental results showed that during unloading, crack closure results in recovery of conductivity and decrease in the overall resistance of the cracked ITO. Also, statistics about the crack spacing showed that the cracking pattern is not perfectly periodical however it has a positively skewed distribution. The higher the applied load, the less the discrepancy in the crack spacing data. It was found that the cracking mechanism of ITO starts with transverse cracking with local delamination at the crack tip unlike the mechanism proposed in the literature of having only cracking pattern without any local delamination. This is the actual mechanism that leads to the high increase in ITO resistance. The analytical code simulates the damage evolution in the ITO layer as function in the applied strain. This will be extended further to correlate the damage to the resistance variation in following studies.

As one of the most promising solar cell technologies, organic solar cells have unique superiorities distinct from inorganic counterparts, such as semitransparency, flexibility and solution-processability, as well as tunable photophysical properties, which originate from the structural verstailities of organic semiconductors. A major breakthrough in OSCs was the exploration of novel non-fullerene electron acceptor (NFAs): In comparison with traditional fullerene derivative acceptors, NFA possesses several advantages, such as low synthesis cost, tunable absorption range and adjustable energetic level, which effectively provides a wide light-harvesting window with low energetic loss. In recent decades, fused-ring electron acceptors (FREAs) have obtained an irreplaceable status in the development of OSCs. However, there are still initial drawbacks to FREA-based devices including: 1: the degree of molecular packing and the corresponding impact on device performance, which has not been studied in depth; 2: the feasibility of approaches for controlling the bulk heterojunction morphology of the film, which also has not been systemic researched; 3: the presence of bulk (geminate and non-geminate) and surface recombination which significantly affects the efficiency and stability of working devices. In this thesis, I took the above three issues as my main doctoral research subjects. In the first part of the thesis, I shine light onto the strength of π-conjugated backbones in FREA molecular structures, which strongly affect the intramolecular interaction. Herein, two FREA with different conjugated framework (IDT core vs IDTT core) are synthesized and employed as electron acceptors in OSCs. A significantly enhanced power conversion efficiency of 11.2% is obtained from IDTTIC-based devices in comparison with that of IDTIC-based devices (5.6%). After considering the electron-donating part in FREA molecules, I also study the effect of the terminal unit, which has a strong relationship with the intramolecular charge transfer effect and intermolecular interactions. Solvent additives are another powerful strategy to further improve the photovoltaic efficiency. 1-chloronaphthalene (CN) was found to be useful in the PTB7-Th:IEICO-4F system, which show a PCE improvement from 9.5% to 12.8%. Furthermore, by utilizing a small molecule donor, BIT-4F-T, as a third component, an optimum PCE of 14.0% is achieved in the devices based on PTB7-Th:IEICO-4F.

Inkjet printing promises to be an invaluable technique for processing organic solar cells with key advantages such as low material consumption, freedom of design and compatibility with different types of flexible substrates making it suitable for large-area production. However, one concern about inkjet printed organic solar cells is the common use of chlorinated solvents during the ink formulation process. While chlorinated solvents suit the inkjet printing process due to their high boiling points, suitable viscosity, and excellent solubility of organic donor and acceptor compounds, they still pose some risks for both human health and the environment, excluding them from being the ultimate choice for large-area production. As a step towards commercialization of OPV, we demonstrated the possibility to close the laboratory to fabrication gap, through the engineering of environmentally friendly inks, using a blend of non-halogenated benzene derivatives solvents optimized to meet the viscosity and surface tension requirements for the inkjet printing process. Starting from using the non-fullerene acceptor O-IDTBR combined with the commercially available donor polymer P3HT we obtained solar cell device with efficiency up to 4.73% - the best efficiency achieved by the P3HT:O-IDTBR system processed with all non-halogenated solvents via inkjet printing. We also delivered highly transparent active layer with device power conversion efficiency of up to 10% with a highly efficient blend of polymer donor PTB7-Th in combination with the ultranarrow band gap NFA IEICO-4F, using hydrocarbons solvent. Lastly, we demonstrated both high efficiency, transparency, and stability by presenting a novel approach based on NFAs consisting of lowering the donor:acceptor ratio in the photoactive layer ink formulations, resulting in more stable devices with comparable power conversion efficiencies to those achieved by lab methods. This breakthrough in ink engineering paves the way in closing the lab-to-fab gap in organic photovoltaic using the low-cost, high throughput inkjet printing technology while considering both environmental and health-conscious mass production and device stability of organic photovoltaics.

Defect passivation and surface modification of perovskite semiconductors play a key role in achieving highly efficient and stable perovskite solar cells (PSCs) and light-emitting diodes (LEDs). This dissertation describes three novel strategies for such defect passivation and surface modification. In the first strategy, we demonstrate a facile approach using inorganic perovskite quantum dots (QDs) to supply bulk- and surface-passivation agents to combine high power conversion efficiency (PCE) with high stability in CH3NH3PbI3 (MAPbI3) inverted PSCs. This strategy utilizes inorganic perovskite QDs to distribute elemental dopants uniformly across the MAPbI3 film and attach ligands to the film’s surface. Compared with pristine MAPbI3 films, MAPbI3 films processed with QDs show a reduction in tail states, smaller trap-state density, and an increase in carrier recombination lifetime. The strategy results in reduced voltage losses and an improvement in PCE from 18.3% to 21.5%, which is among the highest efficiencies for MAPbI3 devices. The devices maintain 80% of their initial PCE under 1-sun continuous illumination for 500 h and show improved thermal stability. In the second strategy, we reduce the efficiency gap between the inverted PSCs and regular PSCs using a trace amount of surface-anchoring, long-chain alkylamine ligands (AALs) as grain and interface modifiers. We show that long-chain AALs suppress nonradiative carrier recombination and improve the optoelectronic properties of mixed-cation mixed-halide perovskite films. These translate into a certified stabilized PCE of 22.3% (23.0% PCE for lab-measured champion devices). The devices operate for over 1000 hours at the maximum power point (MPP), under simulated AM1.5 illumination, without loss of efficiency. Finally, we report a strategy to passivate Cl vacancies in mixed halide perovskite (MHP) QDs using non-polar-solvent-soluble organic pseudohalide (n-dodecylammonium thiocyanate (DAT)), enabling blue MHP LEDs with enhanced efficiency. Density-function-theory calculations reveal that the thiocyanate (SCN-) groups fill in the Cl vacancies and remove deep electron traps within the bandgap. DAT-treated CsPb(BrxCl1-x)3 QDs exhibit near unity (~100%) photoluminescence quantum yields; and their blue (~470 nm) LEDs are spectrally stable with an external quantum efficiency (EQE) of 6.3% – a record for perovskite LEDs emitting at the 460-480 nm range relevant to Rec. 2020 display standards.

Abstract: Even though improvements in the efficiency of organic solar cells encouraged the commercialization of this technology in the past two decades, the stability of organic solar cells is still an active area of research. The effect of photo-oxidative degradation on the performance of organic solar cell devices is significant. One way to lower the rate of photooxidation degradation is by preventing oxygen molecules from reaching the active layer of organic solar cells. This could be achieved by fabricating the devices in an inert environment in the absence of oxygen. Once the devices are fabricated, they would be encapsulated in a transparent material.1, 2 Even though this is a viable solution, there are two main issues. First, it was shown that oxygen molecules could diffuse through the encapsulating material and degrade the devices.3 Second, implementing this solution would increase the fabrication cost of these devices, which would make this solution commercially unfeasible compared to other solar cell technologies.3 Speller and his colleges reported a possible mechanism of the photo-oxidative degradation and showed a relationship between the rate of degradation and LUMO energy levels of electron acceptor molecule4. In this thesis, we report the photo-oxidative degradation rate of O-IDTBR and O-IDTBR-(C3N2)2. The later electron acceptor is analogous to O-IDTBR with deeper LUMO by 0.1 eV. After four hours of constant irradiation from a 1-sun intensity xenon solar simulator, the maximum UV-Vis absorbance of O-IDTBR is reduced by 12% relative to O-IDTBR-(C3N2)2. Lower absolute degradation rates were observed when 1-sun LED solar simulator was used compare to xenon solar simulator.

With the soaring advancement of organolead halide perovskite solar cells rising from a power conversion efficiency of merely 3% to more than 22% shortly in five years, researchers’ interests on this big material family have been greatly spurred. So far, both in-depth studies on the fundamental properties of organolead halide perovskites and their extended applications such as photodetectors, light emitting diodes, and lasing have been intensively reported. The great successes have been ascribed to various superior properties of organolead halide hybrid perovskites such as long carrier lifetimes, high carrier mobility, and solution-processable high quality thin films, as will be discussed in Chapter 1. Notably, most of these studies have been limited to their polycrystalline thin films. Single crystals, as a counter form of polycrystals, have no grain boundaries and higher crystallinity, and thus less defects. These characteristics gift single crystals with superior optical, electrical, and mechanical properties, which will be discussed in Chapter 2. For example, organolead halide perovskite single crystals have been reported with much longer carrier lifetimes and higher carrier mobilities, which are especially intriguing for optoelectronic applications. Besides their superior optoelectronic properties, organolead halide perovskites have shown large composition versatility, especially their organic components, which can be controlled to effectively adjust their crystal structures and further fundamental properties. Single crystals are an ideal platform for such composition-structure-property study since a uniform structure with homogeneous compositions and without distraction from grain boundaries as well as excess defects can provide unambiguously information of material properties. As a major part of work of this dissertation, explorative work on the composition-structure-property study of organic-cation-alloyed organolead halide perovskites using their single crystals will be discussed in Chapter 3 and 4. Despite their outstanding charge transport characteristics, organolead halide perovskite single crystals grown by hitherto reported crystallization methods are not suitable for most optoelectronic devices due to their small aspect ratios and free standing growth. As the other major part of work of this dissertation, explorative work on growing organolead halide perovskite monocrystalline films and further their application in solar cells will be discussed in Chapter 5.

The successful realization of highly efficient bulk heterojunction OPV devices requires the development of organic donor and acceptor materials with tailored properties. Recently, non-fullerene acceptors (NFAs) have emerged as an alternative to the ubiquitously used fullerene derivatives. NFAs showed a rapid increase in efficiencies, now exceeding a PCE of 13%. In my thesis research, I used two small molecule IDT-based acceptors, namely O-IDTBR and O-IDTBCN, in combination with a wide bandgap donor polymer, GeNIDT-BT, as active material in BHJ solar cells and investigated their photophysical characteristics. The polymer combined with O-IDTBR as acceptor achieved a power conversion efficiency of only 2%, which is significantly lower than that obtained for the system of GeNIDT-BT: O-IDTBCN (5.3%). Using nano- to microsecond transient absorption spectroscopy, I investigated both systems and demonstrated that GeNIDT-BT:O-IDTBR exhibits more geminate recombination of interfacial charge-transfer states, leading to lower short circuit currents. Using time-delayed collection field experiments, I studied the field dependence of charge generation and its impact on the device fill factor. Overall, my results provide a qualitative understanding of the efficiency-limiting processes in both systems and their impact on device performance.

>Magister Scientiae - MSc / Perovskite solar cells have gained tremendous attention within the past decade, due to its rapid improvement in power conversion e ciency (PCE), with the current record cell at 25%. The aim of this study is to create a repeatable and scalable chemical vapour deposition technique that can be used to construct perovskite solar cells with a high PCE while maintaining long-term stability. The technique requires the formation of a uniform and compact lead halide layer, either PbI2 or PbCl2 that is sequentially converted into the perovskite structure with the exposure of Methylammonium iodide (MAI) vapour. The use of CVD with a 5 cm diameter quartz tube was successfully used to deposit uniform thin lms of both PbI2 and PbCl2 over an area of 6 cm2 with a thickness deviation of 5%. Thickness control was obtained by varying the amount of source material which allows for repeatable control within 5% error, without the need for a crystal thickness monitor.