Hybrid organic-inorganic perovskites has attracted much attention for its diverse optoelectronic applications. Many studies point out that hybrid organic-inorganic perovskites compounds have superior physical properties that can enable these materials to fabricate good performance solar cells. However, there is a lack of repeatable recipe for the fabrication of perovskite transistors with high mobilities. In this work, a detailed investigation has been conducted on the fabrication of Methylammonium-based perovskite compounds transistors on various polymer substrates. A group of methacrylate-based polymers has been chosen as the materials for gate dielectric layers. Generally, we found that the growth of perovskite crystals highly depends on the hydrophobicity of the substrates. More hydrophobic polymer layers yield larger crystal growth, but suppress the adhesion of perovskites crystals. Aromatic groups in methacrylate-based polymers have hydrophobic properties but it still gives better compact perovskite films with larger crystals. Poly(phenyl methacrylate) (PPhMA) enables the growth of the best perovskite films. The best performance of MAPbI3-xClx perovskite transistors was fabricated on PPhMA with an electron mobility µsat = 4.30 cm2 V−1 s−1 at 150 K. Photothermal deflection spectroscopy was used to investigate the subgap optical absorptions of the perovskite films.

As the power conversion efficiency (PCE) of single-junction solar cells approaching its theoretical limit, tandem solar cells have attracted great attention due to their ability to break this limitation. For example, the PCE of crystalline silicon-based solar cells (c-Si) reached 26.81% with an area of 274.4 cm2, approaching the theoretical limit of 29.4%. By combining the c-Si with perovskites, the theoretical PCE limitation of 29.4% can be further increased to 45%. The wide-bandgap (1.68 eV) inverted (p-i-n) perovskite solar cells (PSCs) are ideal candidates to integrate on top of narrow-bandgap solar cells to fabricate tandem solar cells, owing to the simple fabrication process and tunable bandgap. However, the PCE of wide-bandgap perovskite solar cells is limited by the severe open-circuit voltage loss due to non-radiative recombination arising from trap-assisted recombination and interfacial recombination. In this thesis, Poly[(9,9-bis[3-(trimethylammonium)propyl-2,7-fluorene)]-alt-2,7- (9,9-dioctylfluorene) diiodide (PFN-I), as modification layer between hole transport layer (HTL) and perovskite, was applied to efficiently passivate the interfacial defects, moderate the growth of perovskite crystal and modify the interfacial energy level alignment to enhance hole extraction. Through comprehensive characterization, it has been observed that the introduction of PFN-I into the system effectively reduces non-radiative recombination. Therefore, a PCE of 21.9% with an open-circuit voltage of 1.24 V and a fill factor of 80% was obtained for 1.68 eV-bandgap inverted PSCs.

Organo-metallic halide perovskite solar cells (PSCs) are considered as a promising alternative photovoltaic technology due to the advantages of low-cost solution fabrication capability and high power conversion efficiency (PCE). PSCs can be made using a conventional (n-i-p) structure and an inverted (p-i-n) configuration. PCE of the conventional p-i-n type PSCs is slightly higher than that of the inverted n-i-p type PSCs. However, the TiO2 electron transporting layer adopted in the conventional PSCs is formed at a high sintering temperature of >450 °C. The TiO2 electron transporting layer limits the application of conventional PSCs using flexible substrates that are not compatible with the high processing temperature. The hole extraction layer (HEL) in the inverted p-i-n type PSCs can be prepared by low-temperature solution fabrication processes, which can be adopted for achieving high performance large area flexible solar cells at a low cost. Inverted PSCs with a PCE range from 10 to 20% have been reported over the past few years. In comparison with the progresses of other photovoltaic technologies, the rapid enhancement in PCE of the PSCs offers an attractive option for commercial viability. The aim of this PhD project is to study the origin of the improvement in the performance of solution-processable inverted PSCs. The surface morphological and electronic properties of the HEL are crucial for the growth of the perovskite active layer and hence the performance of the inverted PSCs. Enhancement in short circuit current density (Jsc), reduced loss in open circuit voltage (Voc), improvement in cha Organo-metallic halide perovskite solar cells (PSCs) are considered as a promising alternative photovoltaic technology due to the advantages of low-cost solution fabrication capability and high power conversion efficiency (PCE). PSCs can be made using a conventional (n-i-p) structure and an inverted (p-i-n) configuration. PCE of the conventional p-i-n type PSCs is slightly higher than that of the inverted n-i-p type PSCs. However, the TiO2 electron transporting layer adopted in the conventional PSCs is formed at a high sintering temperature of >450 °C. The TiO2 electron transporting layer limits the application of conventional PSCs using flexible substrates that are not compatible with the high processing temperature. The hole extraction layer (HEL) in the inverted p-i-n type PSCs can be prepared by low-temperature solution fabrication processes, which can be adopted for achieving high performance large area flexible solar cells at a low cost. Inverted PSCs with a PCE range from 10 to 20% have been reported over the past few years. In comparison with the progresses of other photovoltaic technologies, the rapid enhancement in PCE of the PSCs offers an attractive option for commercial viability. The aim of this PhD project is to study the origin of the improvement in the performance of solution-processable inverted PSCs. The surface morphological and electronic properties of the HEL are crucial for the growth of the perovskite active layer and hence the performance of the inverted PSCs. Enhancement in short circuit current density (Jsc), reduced loss in open circuit voltage (Voc), improvement in charge collection efficiency (ηcc) through suppression of charge recombination were investigated systematically via controlled growth of the perovskite active layer in solution-processed inverted PSCs. Poly (3,4-ethylenedioxythiophene): poly (4-styrenesulfonate) (PEDOT:PSS) is one of the widely used solution processable conductive materials for hole transporting in different optoelectronic devices. PEDOT:PSS HEL also is a perfect electron blocking layer due to its high LUMO level. However, it has been reported that PEDOT:PSS HEL is related to the deterioration in the stability of PSCs due to its acidic and hygroscopic nature. Modification of PEDOT:PSS using solvent additives or incorporating metallic oxide nanoparticles for improving the processability and the performance of the inverted PSCs were reported. This work has been focused primary on realizing the controlled growth of perovskite active layer via HEL/perovskite interfacial modification using sodium citrate-treated PEDOT:PSS HEL and WO3-PEDOT:PSS composite HEL. Apart from investigating the properties of the modified PEDOT:PSS HELs, the purpose of the work is to improve the understanding of the effect of modified HEL on the growth of the perovskite layer, revealing the charge recombination processes under different operation conditions, analyzing change extraction probability, and thereby improving the overall performance of the PSCs. PCE of >11.30% was achieved for PSCs with a sodium citrate-modified PEDOT:PSS HEL, which is >20% higher than that of a structurally identical control device having a pristine PEDOT:PSS HEL (9.16%). The incident photon to current efficiency (IPCE) and light intensity-dependent J-V measurements reveal that the use of the sodium citrate-modified PEDOT:PSS HEL helps to boost the performance of the inverted PSCs in two ways: (1) it improves the processability of perovskite active layer on HEL, and (2) it enables to enhance the charge extraction efficiency at the HEL/perovskite interface. The suppression of charge recombination in the PSCs with a modified HEL also was examined using photocurrent-effective voltage (Jph-Veff) and transient photocurrent (TPC) measurements. Morphological and structural properties of the perovskite layers were investigated using the scanning electron microscope (SEM) and X-ray diffraction (XRD) measurements. The results reveal that high quality perovskite active layer on the modified HEL was attained forming complete perovskite phase. The surface electronic properties of the modified PEDOT:PSS and pristine PEDOT:PSS layers were studied using X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) measurements. XPS results reveal that treatment of sodium citrate partially removes the PSS unit in the PEDOT:PSS, resulting in an increase in the ratio of PEDOT to PSS from 0.197 for a treated PEDOT:PSS HEL to that of 0.108 for the pristine PEDOT:PSS HEL. UPS measurements also show that there is an observable reduction in the work function of the modified HEL, implying that sodium citrate-modified PEDOT:PSS HEL possesses an improved electron blocking capability, which is beneficial for efficient operation of the inverted PSCs.;The performance enhancement in MAPbI3-based PSCs with a tungsten oxide (WO3)-PEDOT:PSS composite HEL also was analyzed. The uniform composite WO3-PEDOT:PSS HEL was formed on indium tin oxide (ITO) surface by solution fabrication process. The morphological and surface electronic properties of WO3-PEDOT:PSS composite film were examined using AFM, XPS, UPS and Raman Spectroscopy. SEM images reveal that the perovskite films grown on the composite HEL had a full coverage without observable pin holes. XRD results show clearly that no residual of lead iodide phase was observed, suggesting a complete perovskite phase was obtained for the perovskite active layer grown on the composite HEL. The volume ratio of WO3 to PEDOT:PSS of 1:0.25 was optimized for achieving enhanced current density and Voc in the PSCs. It is demonstrated clearly that the use of the WO3-PEDOT:PSS composite HEL helps to improve the charge collection probability through suppression of the charge recombination at the MAPbI3/composite HEL interface. The charge extraction efficiency at the perovskite/PEDOT:PSS and perovskite/composite HEL interfaces were investigated by analyzing the PL quenching efficiency of the MAPbI3 active layer. It is shown that the PL efficiency quenching at the MAPbI3/composite HEL samples is one order of magnitude higher than that measured for the perovskite/pristine PEDOT:PSS sample, suggesting an enhanced hole extraction probability at the MAPbI3/composite HEL interface. The combined effects of improved perovskite crystal growth and enhanced charge extraction capabilities result in the inverted PSCs with a PCE of 12.65%, which is 22% higher than that of a structurally identical control device (10.39%). The use of the WO3-PEDOT:PSS composite HEL also benefits the efficient operation of the PSCs, demonstrated in the stability test, as compared to that of the control cell under the same aging conditions. With the progresses made in improving the performance of MAPbI3-based PSCs, the research was extended to study the performance of efficient PSCs with mixed halide of MA0.7FA0.3Pb (I0.9Br0.1)3. The effect of the annealing temperature on the growth of the mixed MA0.7FA0.3Pb (I0.9Br0.1)3 perovskite active layer was analyzed. It was found that the optimal growth of the mixed perovskite active layer occurred at an annealing temperature of 100°C. UPS results reveal that the ionization potential of 5.76 eV measured for the mixed cation perovskite is lower than that of MAPbI3-based single cation perovskite layer (5.85 eV), while the corresponding electron affinity of the mixed perovskite was 4.28 eV and that for the MAPbI3 layer was 4.18 eV, respectively. The changes in the bandgap and the energy levels of the MA0.7FA0.3Pb (I0.9Br0.1)3 and MAPbI3 active layers were examined using UV-vis absorption spectroscopy and UPS measurements. Compared to the MAPbI3-based control cell, a 23% increase in Jsc, a 15% increase in Voc and an overall 25% increase in PCE for the MA0.7FA0.3Pb (I0.9Br0.1)3 were achieved as compared to that of the MAPbI3-based PSCs. An obvious improvement in charge collection efficiency in MA0.7FA0.3Pb (I0.9Br0.1)3-based PSCs operated at different Veff was clearly manifested by the light intensity dependent J-V characteristic measurements. PL quenching efficiency also shows the charge transfer between MA0.7FA0.3Pb (I0.9Br0.1)3 and PEDOT:PSS HEL is one order of magnitude higher as compare to that in the MAPbI3-based PSCs, suggesting the formation of improved interfacial properties at the MA0.7FA0.3Pb (I0.9Br0.1)3/HEL interface. The impact of incorporating mixed MA0.7FA0.3Pb (I0.9Br0.1)3 perovskite active layer on PCE and the stability of the PSCs was further studied using a combination of TPC measurement and aging test. The stability of MA0.7FA0.3Pb (I0.9Br0.1)3- and MAPbI3-based PSCs with respect to the aging time was monitored for a period of >2 months. The MA0.7FA0.3Pb (I0.9Br0.1)3-based PSCs are more stable compared to the MAPbI3-based PSCs aged under the same conditions. The aging test supports the findings made with the TPC and light intensity dependent J-V measurements. It shows that the improved interfacial quality at the perovskite/HEL and the enhanced charge extraction capability are favorable for efficient and stable operation of MA0.7FA0.3Pb (I0.9Br0.1)3-based PSCs.

Historically, the interfaces and charge transportation layers dictate the performance in heterojunction solar cells. This thesis addresses the interface behaviours and the interfacial layers within perovskite solar cells (PSCs), and provides insights and practicable solutions to facilitate the realisation of efficient PSCs. To achieve efficient charge collection with interlayer fabricated with low-temperature processes, a graphene-TiO₂ nanocomposite is demonstrated; By investigating the carrier transport, we found the insertion of graphene improved the electron collection efficiency with its high surface area and ballistic carrier conduction properties, and in conjunction with pre-synthesised TiO₂, we have successfully circumvented the need for high-temperature annealing, enabling the whole device to be fabricated at under 150 °C. While the anomalous hysteresis behaviour which is widely observed in regular PSCs structure is a significant problem, the quest of stable PSCs seems to be answered by the use of inverted PSCs structures. We show a detailed development of inverted PSCs which are deconstructed layer by layer. Numerous approaches have been tailored to improve interfaces, and energy levels between layers, leading to an efficient and hysteresis-free perovskite solar cells. Lastly, an in-depth study of impurity doping is investigated using Al³⁺. The doping with small metal ions in the perovskite precursor has been found to influenced the crystallisation and optoelectronic properties of the perovskite crystals. Here, for the first time, the correlation between reduced structural crystal defects is clearly linked to enhanced photovoltaic properties, with the best performance for the lowest electronic disorder in the CH₃NH₃PbI₃ crystal.

Over the last 4 years, perovskite solar cells emerged as an attractive, highly efficient, and low-cost alternative to established, conventional photovoltaic technologies. The power conversion efficiency of these devices recorded an unprecedented rise, currently exceeding certified values of 20%. This thesis covers a number of technological advancements which lead to improved photovoltaic performance, as well as vital insight into some more fundamental aspects of the perovskite device operation. The focus of this body of work is primarily directed towards the electric contact in the PV stack which is responsible for electron collection. The motivation of the study presented here is given in Chapter 1, and includes a brief summary of the current energy landscape. Chapter 2 introduces the theoretical background of photovoltaic technology, starting from the basics of semiconductor physics, through to the principles of solar cell operation, as well as some characteristic properties of the perovskite materials. Details of the experimental methods used in this study are reported in Chapter 3. Chapter 4 reports the development of a low temperature process (sub-150 °C) for the manufacture of perovskite solar cells. Dispersions of pre-synthesised, highly crystalline TiO2 nanoparticles were used as an electron selective contact, which eliminated the high temperature sintering step. Chapters 5, 6 and 7, report the interface modification of an n-type contact, resulting in a substantially improved device operation and suppression of hysteresis phenomenon which is characteristic of perovskite photovoltaics. Fullerene-based materials have been found to make excellent electronic contact with halide perovskite materials, and are shown to be far superior to commonly used metal oxides. The facilitated electron collection allows enhancements in the photovoltaic performance of these devices. Furthermore, the organic layers used in this study can be processed at low temperatures. Finally, the development of transparent conductive electrodes based on silver nanowires is presented in Chapter 8. The fabricated electrodes exhibit low sheet resistance, high degree of transparency, and can be processed at low temperatures, allowing them to be compatible with processing on flexible substrates and multi-junction architectures. The application of silver nanowires in different perovskite solar cell architectures is also reported.

Over the last five years hybrid organic-inorganic metal halide perovskites have attracted strong interest in the solar cell community as a result of their high power conversion efficiency and the solid opportunity to realise a low-cost as well as industry-scalable technology. Nevertheless, several aspects of this novel class of materials still need to be explored and the level of our understanding is rapidly and constantly evolving, from month to month. This dissertation reports investigations of perovskite solar cells with a particular focus on their local chemical composition. The analytical characterisation of such devices is very challenging due to the intrinsic instability of the organic component in the nanostructured compounds building up the cell. STEM-EDX (Scanning Transmission Electron Microscopy - Energy Dispersive X-ray spectroscopy) was employed to resolve at the nanoscale the morphology and the elemental composition of the devices. Firstly, a powerful procedure, involving FIB (Focus Ion Beam) sample preparation, the acquisition of STEM-EDX maps and the application of cutting edge post-processing data techniques based on multivariate analysis was developed and tested. The application of this method has drastically improved the quality of the signal that can be extracted from perovskite thin films before the onset of beam-induced transformations. Morphology, composition and interfaces in devices deposited by using different methodologies and external conditions were then explored in detail by combining multiple complementary advanced characterisation tools. The observed variations in the nanostructure of the cells were related to different photovoltaic performance, providing instructive indications for the synthesis and fabrication routes of the devices. Finally, the main degradation processes that affect perovskite solar cells were probed. STEM-EDX was used in conjunction with the application of in situ heating, leading to the direct observation of elemental species migration within the device, reported here for the first time with nanometric spatial resolution. Further analyses, involving a set of experiments aimed to study the effects of air exposure and light soaking on the cells, were designed and performed, providing evidence of the main pathways leading to the drastic drop in the 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.

>Magister Scientiae - MSc / Perovskite solar cells have attracted a tremendous amount of research interest in the scientific community recently, owing to their remarkable performance reaching up to 22% power conversion efficiency (PCE) in merely 6 to 7 years of development. Numerous advantages such as reduced price of raw materials, ease of fabrication and so on, have contributed to their increased popularity.

Metal halide perovskites have emerged as photoactive materials in solution-processed devices thanks to their unique properties such as high absorption coefficient, sharp absorption edge, long carrier diffusion lengths, and tunable bandgap, together with ease of fabrication. The single-junction perovskite solar cells have reached power conversion efficiencies of more than 25%. Although the efficiency of perovskite devices has increased tremendously in a very short time, the efficiency is still limited by carrier recombination at defects and interfaces. Thus, understanding these losses and how to reduce them is the way forward towards the Shockley-Queisser limit. This thesis aims to apply ultrafast optical spectroscopy techniques to investigate the recombination pathways in halide perovskites, and understand the charge extraction from perovskite to transport layers and nonradiative losses at the interface. The first part focuses on perovskite solar cells with planar n–i–p device architecture which offers significant advantages in terms of large scale processing, the potential use of flexible substrates, and applicability to tandems. In addition to the optimization of MAPbI3 solar cell fabrication using a modified sequential interdiffusion protocol, the photophysics of perovskites exposed to humid air and illumination are discussed. The MAPbI3 film processed with the addition of glycol ethers to the methylammonium iodide solution results in the control of PbI2 to perovskite conversion dynamics, thus enhanced morphology and crystallinity. For samples exposed to humid air and illumination, the formation of sub-bandgap states and increased trap-assisted recombination are observed, using highly-sensitive absorption and time-resolved photoluminescence measurements, respectively. It appears that such exposure primarily affects the perovskite surface. The second part discusses the hole extraction from Cs0.07Rb0.03FA0.765MA0.135PbI2.55Br0.45 to the polymeric hole transport layer and interfacial recombination using ultrafast transient absorption spectroscopy technique. To illustrate this, PDPP-3T was used as HTL, since its ground state absorption is red-shifted compared to the perovskite’s photobleach, thereby allowing direct probing of the interfacial hole extraction and recombination. Moreover, carrier diffusion is investigated by varying the perovskite film thickness, and carrier mobility is found to be 39 cm2V-1s-1. Finally, hole extraction is found to be one order of magnitude faster than the recombination at the interface.

No description available.