Not All That Glitters Is Gold: Metal-Migration-Induced Degradation in Perovskite Solar Cells

Perovskite solar cells (PSCs) have now achieved efficiencies in excess of 22%, but very little is known about their long-term stability under thermal stress. So far, stability reports have hinted at the importance of substituting the organic components, but little attention has been given to the metal contact. We investigated the stability of state-of-the-art PSCs with efficiencies exceeding 20%. Remarkably, we found that exposing PSCs to a temperature of 70 degrees C is enough to induce gold migration through the hole-transporting layer (HTL), Spiro-MeOTAD, and into the perovskite material, which in turn severely affects the device performance metrics under working conditions. Importantly, we found that the main cause of irreversible degradation is not due to decomposition of the organic and hybrid perovskite layers. By introducing a Cr metal interlayer between the HTL and gold electrode, high-temperature-induced irreversible long-term losses are avoided. This key finding is essential in the quest for achieving high efficiency, long-term stable PSCs which, in order to be commercially viable, need to withstand hard thermal stress tests.

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

Konrad Domanski

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.

EPFL2018

A chain is as strong as its weakest link - Stability study of MAPbI(3) under light and temperature

Michael Graetzel, Ulf Anders Hagfeldt, Philippe Jürgen Holzhey, Michael Saliba, Silver Hamill Turren Cruz, Amita Ummadisingu, Pankaj Kumar Yadav

The stability of perovskite solar cells is a key issue for industrial development. One reason for this is the volatile organic methylammonium (MA) cation, which is prone to degas under elevated temperatures from the perovskite. At the same time, small amounts of MA are used for practically all highest performing solar cells. These compositions have also shown relatively promising stabilities. This raises the question of MA stability with respect to different, application-dependent stability requirements. Interestingly, MA stability was mainly studied on thin films that differ from full devices or with architectures which are also prone to degrade. Therefore, the degradation behavior on complete MA containing devices with a relatively stable architecture is required to quantify the long-term stability of MA. This enables to determine at which timescales MA is unstable and which role it can play in future compositions. If MA is indeed unstable at much longer timescales than previously recorded, it also indicates that more severe degradation pathways are currently underappreciated. Here, "weakest link" MAPbI(3) solar cells show stability where devices retained 100% of their initial efficiency over 1000 h of aging under constant illumination and maximum power point tracking at 20 degrees C. At elevated temperatures of 50 and 65 degrees C, the devices retained 100% and 90% of their initial efficiency after 500 h of illumination, respectively. Impressively, at 95 degrees C the MAPbI(3) device retained 85% of its initial efficiency after 500 h under constant illumination, which is some of the best stability data reported to date for MA. Thus, MA-containing devices require further studying. Nevertheless to achieve the necessary industrial lifetimes of more than 25 years, the complete removal of MA is a sensible precaution to systematically avoid any long-term risk factors.

2019

Organic Ammonium Halide Modulators as Effective Strategy for Enhanced Perovskite Photovoltaic Performance

Seckin Akin, Bitao Dong, Michael Graetzel, Ulf Anders Hagfeldt, Yuhang Liu, Lukas Pfeifer

Despite rapid improvements in efficiency, long-term stability remains a challenge limiting the future up-scaling of perovskite solar cells (PSCs). Although several approaches have been developed to improve the stability of PSCs, applying ammonium passivation materials in bilayer configuration PSCs has drawn intensive research interest due to the potential of simultaneously improving long-term stability and boosting power conversion efficiency (PCE). This review focuses on the recent advances of improving n-i-p PSCs photovoltaic performance by employing ammonium halide-based molecular modulators. The first section briefly summarizes the challenges of perovskite materials by introducing the degradation mechanisms associated with the hygroscopic nature and ion migration issues. Then, recent reports regarding the roles of overlayers formed from ammonium-based passivation agents are discussed on the basis of ligand and halide effects. This includes both the formation of 2D perovskite films as well as purely organic passivating layers. Finally, the last section provides future perspectives on the use of organic ammonium halides within bilayer-architecture PSCs to improve the photovoltaic performances. Overall, this review provides a roadmap on current demands and future research directions of molecular modulators to address the critical limitations of PSCs, to mitigate the major barriers on the pathway toward future up-scaling applications.