Snaith group

Abstract:

A crosslinkable acrylate random copolymer with both hole-transporting bis(triarylamine) and photocrosslinkable cinnamate side chains is compared to the widely used poly(4-butyl-triphenylamine-4′,4′′-diyl) (PolyTPD) as a hole-transport material (HTM) in positive–intrinsic–negative (p–i–n) perovskite solar cells (PSCs). The crosslinked films of this HTM exhibit improved wettability by precursor solutions of the perovskite relative to PolyTPD; this facilitates high-quality full film coverage by the subsequently deposited perovskite layer on smooth substrates, which is difficult to achieve with PolyTPD without the use of additional interlayers. PSCs fabricated using undoped and crosslinked copolymer achieve steady-state power outputs that are comparable to those of cells incorporating p-doped PolyTPD (with interlayers) as the HTM. The devices made with this material also exhibited improved initial stability under high-intensity ultraviolet LED irradiation, in comparison to those with the PolyTPD analogue. Remarkably, after 3000 h of aging in an oven at 85 °C in a nitrogen-filled glovebox, device efficiency showed no degradation; the SPO was comparable to the initial performance.

Abstract:

Exciton fine structure splitting in semiconductors reflects the underlying symmetry of the crystal and quantum confinement. Since the latter factor strongly enhances the exchange interaction, most work has focused on nanostructures. Here, we report on the first observation of the bright exciton fine structure splitting in a bulk semiconductor crystal, where the impact of quantum confinement can be specifically excluded, giving access to the intrinsic properties of the material. Detailed investigation of the exciton photoluminescence and reflection spectra of a bulk methylammonium lead tribromide single crystal reveals a zero magnetic field splitting as large as ~200μeV. This result provides an important starting point for the discussion of the origin of the large bright exciton fine structure observed in perovskite nanocrystals.

Abstract:

Successful isolation and characterization of a series of Er-based dimetallofullerenes present valuable insights into the realm of metal-metal bonding. These species are crystallographically identified as Er₂ @C_s (6)-C₈₂ , Er₂ @C_3v (8)-C₈₂ , Er₂ @C₁ (12)-C₈₄ , and Er₂ @C_2v (9)-C₈₆ , in which the structure of the C₁ (12)-C₈₄ cage is unambiguously characterized for the first time by single-crystal X-ray diffraction. Interestingly, natural bond orbital analysis demonstrates that the two Er atoms in Er₂ @C_s (6)-C₈₂ , Er₂ @C_3v (8)-C₈₂ , and Er₂ @C_2v (9)-C₈₆ form a two-electron-two-center Er-Er bond. However, for Er₂ @C₁ (12)-C₈₄ , with the longest Er⋅⋅⋅Er distance, a one-electron-two-center Er-Er bond may exist. Thus, the difference in the Er⋅⋅⋅Er separation indicates distinct metal bonding natures, suggesting a distance-dependent bonding behavior for the internal dimetallic cluster. Additionally, electrochemical studies suggest that Er₂ @C_82-86 are good electron donors instead of electron acceptors. Hence, this finding initiates a connection between metal-metal bonding chemistry and fullerene chemistry.