2023, Bautista-Quijano, Jose Roberto, Telschow, Oscar, Paulus, Fabian, Vaynzof, Yana

The fabrication of metal halide perovskite films using the solvent-engineering method is increasingly common. In this method, the crystallisation of the perovskite layer is triggered by the application of an antisolvent during the spin-coating of a perovskite precursor solution. Herein, we introduce the current state of understanding of the processes involved in the crystallisation of perovskite layers formed by solvent engineering, focusing in particular on the role of antisolvent properties and solvent-antisolvent interactions. By considering the impact of the Hansen solubility parameters, we propose guidelines for selecting the appropriate antisolvent and outline open questions and future research directions for the fabrication of perovskite films by this method.

2022, Ji, Ran, Zhang, Zongbao, Hofstetter, Yvonne J., Buschbeck, Robin, Hänisch, Christian, Paulus, Fabian, Vaynzof, Yana

Modern photovoltaic devices are often based on a heterojunction structure where two components with different optoelectronic properties are interfaced. The properties of each side of the junction can be tuned by either utilizing different materials (for example, donor/acceptor) or doping (for example, p–n junction) or even varying their dimensionality (for example, 3D/2D). Here we demonstrate the concept of phase heterojunction (PHJ) solar cells by utilizing two polymorphs of the same material. We demonstrate the approach by forming γ-CsPbI3/β-CsPbI3 perovskite PHJ solar cells. We find that all of the photovoltaic parameters of the PHJ device significantly surpass those of each of the single-phase devices, resulting in a maximum power conversion efficiency of 20.1%. These improvements originate from the efficient passivation of the β-CsPbI3 by the larger bandgap γ-CsPbI3, the increase in the built-in potential of the PHJ devices enabled by the energetic alignment between the two phases and the enhanced absorption of light by the PHJ structure. The approach demonstrated here offers new possibilities for the development of photovoltaic devices based on polymorphic materials.

2020, Hernandez, J.-A., Morard, G., Guarguaglini, M., Alonso-Mori, R., Benuzzi-Mounaix, A., Bolis, R., Fiquet, G., Galtier, E., Gleason, A.E., Glenzer, S., Guyot, F., Ko, B., Lee, H.J., Mao, W.L., Nagler, B., Ozaki, N., Schuster, A.K., Shim, S.H., Vinci, T., Ravasio, A.

We report in situ structural measurements of shock-compressed single crystal orthoenstatite up to 337 ± 55 GPa on the Hugoniot, obtained by coupling ultrafast X-ray diffraction to laser-driven shock compression. Shock compression induces a disordering of the crystalline structure evidenced by the appearance of a diffuse X-ray diffraction signal at nanosecond timescales at 80 ± 13 GPa on the Hugoniot, well below the equilibrium melting pressure (>170 GPa). The formation of bridgmanite and post-perovskite have been indirectly reported in microsecond-scale plate-impact experiments. Therefore, we interpret the high-pressure disordered state we observed at nanosecond scale as an intermediate structure from which bridgmanite and post-perovskite crystallize at longer timescales. This evidence of a disordered structure of MgSiO3 on the Hugoniot indicates that the degree of polymerization of silicates is a key parameter to constrain the actual thermodynamics of shocks in natural environments. © 2020. The Authors.

2023, Zhang, Zongbao, Ji, Ran, Hofstetter, Yvonne J., Deconinck, Marielle, Brunner, Julius, Li, Yanxiu, An, Qingzhi, Vaynzof, Yana

Inorganic cesium lead iodide (CsPbI3) perovskite solar cells (PSCs) have attracted enormous attention due to their excellent thermal stability and optical bandgap (∼1.73 eV), well-suited for tandem device applications. However, achieving high-performance photovoltaic devices processed at low temperatures is still challenging. Here we reported a new method for the fabrication of high-efficiency and stable γ-CsPbI3 PSCs at lower temperatures than was previously possible by introducing the long-chain organic cation salt ethane-1,2-diammonium iodide (EDAI2) and regulating the content of lead acetate (Pb(OAc)2) in the perovskite precursor solution. We find that EDAI2 acts as an intermediate that can promote the formation of γ-CsPbI3, while excess Pb(OAc)2 can further stabilize the γ-phase of CsPbI3 perovskite. Consequently, improved crystallinity and morphology and reduced carrier recombination are observed in the CsPbI3 films fabricated by the new method. By optimizing the hole transport layer of CsPbI3 inverted architecture solar cells, we demonstrate efficiencies of up to 16.6%, surpassing previous reports examining γ-CsPbI3 in inverted PSCs. Notably, the encapsulated solar cells maintain 97% of their initial efficiency at room temperature and under dim light for 25 days, demonstrating the synergistic effect of EDAI2 and Pb(OAc)2 in stabilizing γ-CsPbI3 PSCs.

2023, Gallop, Nathaniel. P., Maslennikov, Dmitry R., Mondal, Navendu, Goetz, Katelyn P., Dai, Zhenbang, Schankler, Aaron M., Sung, Woongmo, Nihonyanagi, Satoshi, Tahara, Tahei, Bodnarchuk, Maryna I., Kovalenko, Maksym V., Vaynzof, Yana, Rappe, Andrew M., Bakulin, Artem A.

Vibrational control (VC) of photochemistry through the optical stimulation of structural dynamics is a nascent concept only recently demonstrated for model molecules in solution. Extending VC to state-of-the-art materials may lead to new applications and improved performance for optoelectronic devices. Metal halide perovskites are promising targets for VC due to their mechanical softness and the rich array of vibrational motions of both their inorganic and organic sublattices. Here, we demonstrate the ultrafast VC of FAPbBr3 perovskite solar cells via intramolecular vibrations of the formamidinium cation using spectroscopic techniques based on vibrationally promoted electronic resonance. The observed short (~300 fs) time window of VC highlights the fast dynamics of coupling between the cation and inorganic sublattice. First-principles modelling reveals that this coupling is mediated by hydrogen bonds that modulate both lead halide lattice and electronic states. Cation dynamics modulating this coupling may suppress non-radiative recombination in perovskites, leading to photovoltaics with reduced voltage losses.

2020, Singh, Birender, Vogl, M., Wurmehl, S., Aswartham, S., Büchner, B., Kumar, Pradeep

The quest for Kitaev spin liquids in particular three-dimensional solids is a long sought goal in condensed matter physics, as these states may give rise to exotic new types of quasiparticle excitations carrying fractional quantum numbers, namely Majorana fermionic excitations. Here we report the experimental signature of this characteristic feature of the Kitaev spin liquid via Raman measurements. Sm2ZnIrO6 is a strongly spin-orbit-coupled Mott insulator where Jeff=1/2 controls the physics, which provides striking evidence for this characteristic feature of the Kitaev spin liquid. As the temperature is lowered, we find that the spin excitations form a continuum in contrast to the conventional sharp modes expected in ordered antiferromagnets. Our observation of a broad magnetic continuum and anomalous renormalization of the phonon self-energy parameters shows the existence of fractionalization excitations in the double-perovskite structure, as theoretically conjectured in a Kitaev-Heisenberg geometrically frustrated double-perovskite system.

2023, Lapalikar, Vaidehi, Dacha, Preetam, Hambsch, Mike, Hofstetter, Yvonne J., Vaynzof, Yana, Mannsfeld, Stefan C. B., Ruck, Michael

Bismuth oxide iodide (BiOI) has been viewed as a suitable environmentally-friendly alternative to lead-halide perovskites for low-cost (opto-)electronic applications such as photodetectors, phototransistors and sensors. To enable its incorporation in these devices in a convenient, scalable, and economical way, BiOI thin films were investigated as part of heterojunctions with various p-type organic semiconductors (OSCs) and tested in a field-effect transistor (FET) configuration. The hybrid heterojunctions, which combine the respective functionalities of BiOI and the OSCs were processed from solution under ambient atmosphere. The characteristics of each of these hybrid systems were correlated with the physical and chemical properties of the respective materials using a concept based on heteropolar chemical interactions at the interface. Systems suitable for application in lateral transport devices were identified and it was demonstrated how materials in the hybrids interact to provide improved and synergistic properties. These indentified heterojunction FETs are a first instance of successful incorporation of solution-processed BiOI thin films in a three-terminal device. They show a significant threshold voltage shift and retained carrier mobility compared to pristine OSC devices and open up possibilities for future optoelectronic applications.

2023, Goetz, Katelyn P., Thome, Fabian T. F., An, Qingzhi, Hofstetter, Yvonne J., Schramm, Tim, Yangui, Aymen, Kiligaridis, Alexander, Loeffler, Markus, Taylor, Alexander D., Scheblykin, Ivan G., Vaynzof, Yana

Exposure to environmental factors is generally expected to cause degradation in perovskite films and solar cells. Herein, we show that films with certain defect profiles can display the opposite effect, healing upon exposure to oxygen under illumination. We tune the iodine content of methylammonium lead triiodide perovskite from understoichiometric to overstoichiometric and expose them to oxygen and light prior to the addition of the top layers of the device, thereby examining the defect dependence of their photooxidative response in the absence of storage-related chemical processes. The contrast between the photovoltaic properties of the cells with different defects is stark. Understoichiometric samples indeed degrade, demonstrating performance at 33% of their untreated counterparts, while stoichiometric samples maintain their performance levels. Surprisingly, overstoichiometric samples, which show low current density and strong reverse hysteresis when untreated, heal to maximum performance levels (the same as untreated, stoichiometric samples) upon the photooxidative treatment. A similar, albeit smaller-scale, effect is observed for triple cation and methylammonium-free compositions, demonstrating the general application of this treatment to state-of-the-art compositions. We examine the reasons behind this response by a suite of characterization techniques, finding that the performance changes coincide with microstructural decay at the crystal surface, reorientation of the bulk crystal structure for the understoichiometric cells, and a decrease in the iodine-to-lead ratio of all films. These results indicate that defect engineering is a powerful tool to manipulate the stability of perovskite solar cells.