Snaith group

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.

Abstract:

Mixed lead-tin halide perovskites have sufficiently low bandgaps (∼1.2 eV) to be promising absorbers for perovskite-perovskite tandem solar cells. Previous reports on lead-tin perovskites have typically shown poor optoelectronic properties compared to neat lead counterparts: short photoluminescence lifetimes (<100 ns) and low photoluminescence quantum efficiencies (<1%). Here, we obtain films with carrier lifetimes exceeding 1 μs and, through addition of small quantities of zinc iodide to the precursor solutions, photoluminescence quantum efficiencies under solar illumination intensities of 2.5%. The zinc additives also substantially enhance the film stability in air, and we use cross-sectional chemical mapping to show that this enhanced stability is because of a reduction in tin-rich clusters. By fabricating field-effect transistors, we observe that the introduction of zinc results in controlled p-doping. Finally, we show that zinc additives also enhance power conversion efficiencies and the stability of solar cells. Our results demonstrate substantially improved low-bandgap perovskites for solar cells and versatile electronic applications.

Abstract:

We demonstrate a method for controlled p-doping of the halide perovskite surface using molecular dopants, resulting in reduced non-radiative recombination losses and improved device performance.