Two advances that address the main challenges of all-perovskite two-terminal tandem solar cell fabrication are reported. First, a nucleation layer is used to enable high-quality atomic layer deposition-based recombination layers that reduce electronic losses. Second, cation tuning is used for wide-band-gap perovskite solar cells that produce high, stable voltages. Combining these advances allows us to fabricate tandem perovskite solar cells on both rigid and flexible plastic substrates that have high efficiency and promising stability.

Extrinsic ions (e.g., Li+) migrate across perovskite solar cells and modify the TiO2 layer, affecting device performance and hysteresis.

We modify the fundamental electronic properties of metallic (1T phase) nanosheets of molybdenum disulfide (MoS) through covalent chemical functionalization, and thereby directly influence the kinetics of the hydrogen evolution reaction (HER), surface energetics, and stability. Chemically exfoliated, metallic MoS nanosheets are functionalized with organic phenyl rings containing electron donating or withdrawing groups. We find that MoS functionalized with the most electron donating functional group (p-(CHCH)NPh-MoS) is the most efficient catalyst for HER in this series, with initial activity that is slightly worse compared to the pristine metallic phase of MoS. The p-(CHCH)NPh-MoS is more stable than unfunctionalized metallic MoS and outperforms unfunctionalized metallic MoS for continuous H evolution within 10 min under the same conditions. With regards to the entire studied series, the overpotential and Tafel slope for catalytic HER are both directly correlated with the electron donating strength of the functional group. The results are consistent with a mechanism involving ground-state electron donation or withdrawal to/from the MoS nanosheets, which modifies the electron transfer kinetics and catalytic activity of the MoS nanosheet. The functional groups preserve the metallic nature of the MoS nanosheets, inhibiting conversion to the thermodynamically stable semiconducting state (2H) when mildly annealed in a nitrogen atmosphere. We propose that the electron density and, therefore, reactivity of the MoS nanosheets are controlled by the attached functional groups. Functionalizing nanosheets of MoS and other transition metal dichalcogenides provides a synthetic chemical route for controlling the electronic properties and stability within the traditionally thermally unstable metallic state.