Prof Henry Snaith FRS

Abstract:

We explore silane-coated formamidinium lead bromide (FAPbBr₃) quantum dots (QDs) as single photon emitters and compare them to FAPbBr₃ QDs passivated with a phosphoethylammonium derivative (PEAC₈C₁₂), which represents current state-of-the-art ligand passivation. We compare properties including single-photon purity (g⁽²⁾(τ)), line width, blinking, and photostability. We find that at room temperature, these silane-coated dots perform comparably to PEAC₈C₁₂-passivated dots, while exhibiting improvements in photostability. However, we find that at 4 K, silane-coated FAPbBr₃ QDs perform worse than the PEAC₈C₁₂-passivated samples, exhibiting faster blue-shifting and photobleaching under illumination. Analysis of fluorescence lifetime intensity distributions from the photon-counting data indicates increased efficiency of fast nonradiative processes in the silane-coated QDs at 4 K. We propose a trion-related degradation pathway at low temperatures that is consistent with the observed kinetics and estimate that at 4 K with 6.1 μJ/cm², 472 nm excitation the silane-coated QDs build up double the trion population of their PEAC₈C₁₂-passivated counterparts.

Abstract:

Vacuum-based deposition is a scalable, solvent-free industrial method ideal for uniform coatings on complex substrates. However, all vacuum-deposited perovskite solar cells fabricated by thermal evaporation trail solution-processed counterparts in efficiency and stability due to film quality challenges, necessitating advancement and improved understanding. Here, we report a co-evaporation route for 1.67-eV wide-bandgap perovskites by introducing a PbCl2 co-source to optimize film quality. We promote perovskite formation with pronounced (100) “face-up” orientation and deliver a certified all vacuum-deposited solar cell with 18.35% efficiency (19.3% in the lab) for 0.25-cm2 devices (18.5% for 1-cm2 cells). These cells retain 80% of peak efficiency after 1,080 hours under the ISOS-L-2 protocol. Leveraging operando hyperspectral imaging, we provide spatiotemporal spectral insight into halide segregation and trap-mediated recombination, correlating microscopic luminescence features with macroscopic device performance while distinguishing radiative from non-ideal recombination channels. We further demonstrate 27.2%-efficient 1-cm2 evaporated perovskite-on-silicon tandems and outdoor stability of all vacuum-deposited tandems in Italy, retaining ~80% initial performance after 8 months.

Abstract:

The anisotropy of perovskite nanoplatelets (PeNPLs) opens up many opportunities in optoelectronics, including enabling the emission of linearly polarized light. But the limited stability of PeNPLs is a pressing challenge, especially for red-emitting CsPbI3. Herein, we address this limitation by alloying formamidinium (FA) into the perovskite cuboctahedral site. Unlike Cs/FA alloying in bulk thin films or nanocubes, FA incorporation in nanoplatelets requires meticulous control over the reaction conditions, given that nanoplatelets are obtained in kinetically-driven growth regimes instead of thermodynamically-driven conditions. Through in-situ photoluminescence (PL) measurements, we find that excess FA leads to uncontrolled growth, where phase impurities and nanoplatelets of multiple thicknesses co-exist. Restricting the FA content to up to 25% Cs substitution enables monodisperse PeNPLs, and increases the PL quantum yield (from 53% to 61%), exciton lifetime (from 18 ns to 27 ns), and stability in ambient air (from ~2 days to >7 days) compared to CsPbI3. This arises due to hydrogen bonding between FA and the oleate and oleylammonium ligands, anchoring them to the surface to improve optoelectronic properties and stability. The reduction in non-radiative recombination, improvement in the nanoplatelet aspect ratio, and higher ligand density lead to FA-containing PeNPLs more effectively forming edge-up superlattices, enhancing the PL degree of linear polarization from 5.1% (CsPbI3) to 9.4% (Cs0.75FA0.25PbI3). These fundamental insights show how the stability limitations of PeNPLs could be addressed, and these materials grown more precisely to improve their performance as polarized light emitters, critical for utilizing them in next-generation display, bioimaging, and communications applications.

Abstract:

Perovskite inks play critical roles in determining film quality and device performance, and ink stability is desired to ensure high device reproducibility. Here, we reveal the instability issue of current cesium-formamidinium lead triiodide (CsxFA1-xPbI3) inks whose aggregation and precipitation tendencies are induced by excessively strong solvent-lead-halide coordination. By modulating coordination strength between precursor salts and solvents, we identify solvent coordination-dispersion equilibrium as the governing factor for ink stability and develop a stable ink that exhibits a remarkable increase in the shelf life. It effectively tunes ink drying and film crystallization, resulting in blade-coated perovskite films with excellent uniformity and low defect density. This enhancement led to increased aperture efficiency of ambient-fabricated p-i-n perovskite modules to 23.5%. The resultant devices also exhibit high durability, and 99% of the initial PCE was retained after 1700 hours of maximum power point tracking following the ISOS-L-2 standard protocol.