The Quest for Stability of Perovskite Solar Cells: Understanding Degradation, Improving Lifetimes and Towards Experimental Standards

Perovskite solar cells (PSCs) have attracted a substantial interest owing to a very fast achievement of efficiencies >20 % within only several years of development. However, for any solar cell to become technologically viable, two additional milestones have to be achieved alongside high efficiency: means of industrial production and good operational stability. The former being mostly the focus of the private sector and industrially-oriented research institutes, understanding degradation and improving the stability of PSCs has become one of the major research topics in the field of emerging photovoltaics. This is also the focus of this thesis, where I investigate different degradation mechanisms in PSCs with the aim of extending their long-term stability. This dissertation can be divided into four parts: in the first one, I show how, through a series of prototypes, I designed and built a dedicated setup to investigate stability of PSCs. I also show how I developed its variation to improve by 700 % the efficiency of measuring current-voltage characteristics of our solar cells. Subsequently, I describe the intrinsic instability of, at the time, state-of-the-art PSCs. I show how, along with my colleagues, we managed to achieve breakthrough room temperature stability coupled with record efficiency through incorporation of Cs into perovskite. Next, I describe how and why these solar cells suffer from irreversible degradation if left at elevated temperatures however. This is due to a vulnerability to Au diffusion from the electrode, through Spiro-MeOTAD hole transporting layer into the perovskite. I show how, by incorporation of Cr diffusion barrier I managed to circumvent this problem (albeit at considerable efficiency loss). Subsequently, I describe an alterna-tive solution to the problem by substituting Spiro-MeOTAD with PTAA - a polymeric hole transporting layer. This approach effectively stops Au diffusion without compromising device efficiency, which was at the same time improved by incorporating Rb into the perovskite. Finally, a third approach is presented: replacing the Au electrode with one based on carbon nanotubes. This gives away with using Au and PTAA - both prohibitively expensive materials - and hence paves the way towards facile and inexpensive fabrication of stable PSCs. In the third part, I describe the effects of mobile ions in the perovskite on the behaviour of PSCs. First, I show how they lead to a partial reversibility of losses in aged devices. This has potentially far-reaching consequences for the way stability measurements of PSCs are conducted and how their lifetime is reported. Next, I show how the ionic movement in the perovskite can lead to PSCs with certain architecture to work as high-gain photodetectors. This is enabled by piling up of ions at the interfaces within the devices, which modifies the energy levels within. Finally, in the last chapter I describe systematically, how different factors such as temperature, illumination, atmosphere, load on the device and cycling of the environmental conditions affect the stability of PSCs. Based on this, I discuss the important parameters to control when ageing PSCs, as the first attempt to bring the community to a consensus on how to measure stability of PSCs. This is urgently needed to streamline the efforts to create stable PSCs and to commercialize the technology

Migration of cations induces reversible performance losses over day/night cycling in perovskite solar cells

Perovskites have been demonstrated in solar cells with a power conversion efficiency of well above 20​%, which makes them one of the strongest contenders for next generation photovoltaics. While there are no concerns about their efficiency, very little is known about their stability under illumination and load. Ionic defects and their migration in the perovskite crystal lattice are some of the most alarming sources of degrdn., which can potentially prevent the commercialization of perovskite solar cells (PSCs)​. In this work, we provide direct evidence of elec. field-​induced ionic defect migration and we isolate their effect on the long-​term performance of state-​of-​the-​art devices. Supported by modeling, we demonstrate that ionic defects, migrating on timescales significantly longer (above 103 s) than what has so far been explored (from 10-​1 to 102 s)​, abate the initial efficiency by 10-​15​% after several hours of operation at the max. power point. Though these losses are not negligible, we prove that the initial efficiency is fully recovered when leaving the device in the dark for a comparable amt. of time. We verified this behavior over several cycles resembling day​/night phases, thus probing the stability of PSCs under native working conditions. This unusual behavior reveals that research and industrial stds. currently in use to assess the performance and the stability of solar cells need to be adjusted for PSCs. Our work paves the way for much needed new testing protocols and figures of merit specifically designed for PSCs

Incorporation of rubidium cations into perovskite solar cells improves photovoltaic performance

All of the cations currently used in perovskite solar cells abide by the tolerance factor for incorporation into the lattice. We show that the small and oxidation-stable rubidium cation (Rb+) can be embedded into a "cation cascade" to create perovskite materials with excellent material properties. We achieved stabilized efficiencies of up to 21.6% (average value, 20.2%) on small areas (and a stabilized 19.0% on a cell 0.5 square centimeters in area) as well as an electroluminescence of 3.8%. The open-circuit voltage of 1.24 volts at a band gap of 1.63 electron volts leads to a loss in potential of 0.39 volts, versus 0.4 volts for commercial silicon cells. Polymer-coated cells maintained 95% of their initial performance at 85 degrees C for 500 hours under full illumination and maximum power point tracking

Incorporation of rubidium cations into perovskite solar cells improves photovoltaic performance

All of the cations currently used in perovskite solar cells abide by the tolerance factor for incorporation into the lattice. We show that the small and oxidation-stable rubidium cation (Rb+) can be embedded into a "cation cascade" to create perovskite materials with excellent material properties. We achieved stabilized efficiencies of up to 21.6% (average value, 20.2%) on small areas (and a stabilized 19.0% on a cell 0.5 square centimeters in area) as well as an electroluminescence of 3.8%. The open-circuit voltage of 1.24 volts at a band gap of 1.63 electron volts leads to a loss in potential of 0.39 volts, versus 0.4 volts for commercial silicon cells. Polymer-coated cells maintained 95% of their initial performance at 85 degrees C for 500 hours under full illumination and maximum power point tracking

Ionic Liquid Control Crystal Growth to Enhance Planar Perovskite Solar Cells Efficiency

Ionic liquids can retard the perovskite crystallization with the aim to form compact films with larger and more uniformly distributed grain size. The ionic liquid driven crystallization is exploited to prepared a record planar perovskite solar cell with stabilized power output of 19.5%

Molecular Engineering of Functional Materials for Energy and Opto-Electronic Applications

This review presents an overview of the dedicated research directions of the Group for Molecular Engineering of Functional Materials (GMF). This includes molecular engineering aspects of sensitizers constructed from ruthenium complexes, organic molecules, porphyrins and phthalocyanines. Manipulation of organometal trihalide perovskites, and charge transporting materials for high performance perovskite solar cells and photo-detectors are also described. Controlling phosphorescence color, and quantum yields in iridium complexes by tailoring ligands for organic light emitting diodes are demonstrated. Efficient reduction of CO2 to CO using molecular catalyst on a protected Cu2O photocathode, and cost-effective water-splitting cell using a high efficiency perovskite solar cell are presented

Working Principles of Perovskite Photodetectors: Analyzing the Interplay Between Photoconductivity and Voltage-Driven Energy-Level Alignment

Organic-inorganic lead halide perovskites have recently received significant attention as active materials for high-performance photovoltaics and photo-detectors. However, the understanding of their operation mechanism remains limited. High-gain, low-voltage CH3NH3PbI3 photodetectors in various architectures are demonstrated herein. Photomultiplication in all structures with direct contact of fluorine-doped tin oxide (FTO) and perovskite with the highest responsivity 208 A W-1 corresponding to an incident photon-to-current efficiency of 47 000% is observed. Studying the dynamics and temperature dependence, a slow process with an activation energy of 420 +/- 90 meV in the time scale of seconds is found, which is essential to photocurrent multiplication. A model based on ion migration to explain the observed transients and the photomultiplication is developed. The accumulation of negative ionic charge at the FTO/perovskite interface under reverse bias lowers the FTO work function allowing for direct hole injection into the perovskite valence band. Under illumination, the conductivity of perovskite is increased and the device behaves similar to a photoconductor

Photodetector

The present invention concerns a device for room temperature reverse-bias operation photo-detection. The device comprising: - a planar first electrode extending in a planar direction; - a second electrode positioned above the first electrode in a direction substantially perpendicular to said planar direction; and - an active region sandwiched between the first and second electrode. The active region consists of a light absorbing perovskite and wherein the light absorbing perovskite is in direct contact with at least one of the first and second electrodes