Snaith group

Abstract:

Abstract:

Additive engineering is among the most commonly used strategies to enhance the performance and stability of perovskite solar cells. Prior research often focused on optimizing device performance by using additives in the perovskite precursor solution to influence the rate of crystallization and film formation, but a fundamental understanding of the effect of additives on the stoichiometry of the absorber remains elusive. In this study, we reveal how additives affect the ABX3 stoichiometry of the perovskite absorber and its photovoltaic properties. We find that the solar cell performance of a wide-bandgap (1.77 eV) Cs0.2FA0.8Pb-(I0.6Br0.4)3 perovskite decreases when processed with either of two common additives, lead thiocyanate and lead chloride, because the additive disturbs the stoichiometry. Interestingly, the addition of excess formamidinium iodide (FAI) to the precursor solution can restore the initial ABX3 stoichiometry and fully recover the device performance. The excess of FAI that is required depends on whether the halide or pseudohalide additive is incorporated into the crystal lattice. Finally, we alter the stoichiometry of an additive-free perovskite absorber by inducing either an excess or a deficiency of FAI or lead iodide in the precursor and show that slight deviations from the ideal stoichiometry rapidly degrade the device performance. This work provides fundamental insights into the importance of bulk stoichiometry in perovskite absorbers and can serve as a basis for future rational additive engineering.

Abstract:

Metal halide perovskites could form the basis of future display technology due to their powerful optical properties. However, the commercialization of electroluminescent perovskites has been hindered by key challenges, including limited operational lifetime and instability in blue emission. Here we highlight the potential of perovskites in colour conversion displays. We examine the particular advantages of perovskite materials as colour conversion layers: narrow emission spectrum, high absorption coefficients, high-brightness operation, photon recycling and ease of manufacturing. We provide a framework for the development of RoHS (Restriction of Hazardous Substances)-compliant and colour-filter-free perovskite-based colour conversion displays and offer guidelines for commercialization. We also explore the potential of using perovskite colour conversion layers to create advanced augmented reality and virtual reality technologies.

Abstract:

Tin-halide perovskites currently offer the best photovoltaic performance of lead-free metal-halide semiconductors. However, their transport properties are mostly dominated by holes, owing to ubiquitous self-doping. Here we demonstrate a noncontact, optical spectroscopic method to determine the effective mass of the dominant hole species in FASnI3, by investigating a series of thin films with hole densities finely tuned through either SnF2 additive concentration or controlled exposure to air. We accurately determine the plasma frequency from mid-infrared reflectance spectra by modeling changes in the vibrational response of the FA cation as the plasma edge shifts through the molecular resonance. Our approach yields a hole effective mass of 0.28m e for FASnI3 and demonstrates parabolicity within ∼100 meV of the valence band edge. An absence of Fano contributions further highlights insignificant coupling between the hole plasma and FA cation. Overall, this approach enables noncontact screening of thin-film materials for optimized charge-carrier transport properties.

Abstract:

<jats:title>Abstract</jats:title><jats:p>The properties of metal‐centred species in metal halide perovskite precursor solutions substantially influence the formation and evolution of colloidal particles, which in turn dictate the crystallisation process and the film quality. In this work, we assess the “hard” and “soft” Lewis acid characteristics of Sn<jats:sup>2+</jats:sup> and Pb<jats:sup>2+</jats:sup> cations as a strategy to modulate the chemical environment of these metal‐containing species in mixed‐metal tin–lead perovskite precursor solutions. We observe enhanced simultaneous access to both metal centres upon adding compounds with functional groups suggested by the hard–soft acid–base principle. Theoretical calculations suggest that the hard base carboxyl group preferentially interacts with Sn<jats:sup>2+</jats:sup>‐based species, while the softer base thiol group also targets Pb<jats:sup>2+</jats:sup>‐based species. By effectively accessing and manipulating possible classes of inorganic species and their colloidal particle properties in the precursor solutions, we achieve 1.26 eV perovskite polycrystalline films exhibiting enhanced structural and optoelectronic quality, giving the best quasi‐Fermi level splitting values of up to 0.95 eV. As a result, the solar cell devices demonstrate efficiency values of up to 23.3% with an extended operational lifetime, retaining 80% of their initial efficiency after over 280 and 180 h of maximum power point tracking under simulated AM1.5G illumination at 25 and 65 °C, respectively.</jats:p>