Snaith group

Abstract:

Understanding and controlling grain growth in metal halide perovskite polycrystalline thin films is an important step in improving the performance of perovskite solar cells. We demonstrate accurate control of crystallite size in CH3NH3PbI3 thin films by regulating substrate temperature during vacuum co-deposition of inorganic (PbI2) and organic (CH3NH3I) precursors. Films co-deposited onto a cold (−2 °C) substrate exhibited large, micrometer-sized crystal grains, while films that formed at room temperature (23 °C) only produced grains of 100 nm extent. We isolated the effects of substrate temperature on crystal growth by developing a new method to control sublimation of the organic precursor, and CH3NH3PbI3 solar cells deposited in this way yielded a power conversion efficiency of up to 18.2%. Furthermore, we found substrate temperature directly affects the adsorption rate of CH3NH3I, thus impacting crystal formation and hence solar cell device performance via changes to the conversion rate of PbI2 to CH3NH3PbI3 and stoichiometry. These findings offer new routes to developing efficient solar cells through reproducible control of crystal morphology and composition.

Abstract:

The production of highly efficient single‐ and multijunction metal halide perovskite (MHP) solar cells requires careful optimization of the optical and electrical properties of these devices. Here, precise control of CH3NH3PbI3 perovskite layers is demonstrated in solar cell devices through the use of dual source coevaporation. Light absorption and device performance are tracked for incorporated MHP films ranging from ≈67 nm to ≈1.4 µm thickness and transfer‐matrix optical modeling is utilized to quantify optical losses that arise from interference effects. Based on these results, a device with 19.2% steady‐state power conversion efficiency is achieved through incorporation of a perovskite film with near‐optimum predicted thickness (≈709 nm). Significantly, a clear signature of photon reabsorption is observed in perovskite films that have the same thickness (≈709 nm) as in the optimized device. Despite the positive effect of photon recycling associated with photon reabsorption, devices with thicker (>750 nm) MHP layers exhibit poor performance owing to competing nonradiative charge recombination in a “dead‐volume” of MHP. Overall, these findings demonstrate the need for fine control over MHP thickness to achieve the highest efficiency cells, and accurate consideration of photon reabsorption, optical interference, and charge transport properties.

Abstract:

Six dierbium carbide endohedral metallofullerenes have been synthesized and chromatographically isolated. Single-crystal X-ray diffractometry unambiguously ascertains their structures as Er₂C₂@C_2v(5)-C₈₀, Er₂C₂@C_s(6)-C₈₂, Er₂C₂@C_s(15)-C₈₄, Er₂C₂@C_2v(9)-C₈₆, Er₂C₂@C_s(15)-C₈₆, and Er₂C₂@C_s(32)-C₈₈, respectively. The Er···Er distances of the major erbium sites inside the C_s(6)-C₈₂, C_2v(5)-C₈₀, C_s(15)-C₈₄, C_s(15)-C₈₆, C_2v(9)-C₈₆, and C_s(32)-C₈₈ cages are 3.801, 3.860, 4.062, 4.066, 4.307, and 4.372 Å, respectively, which show a linear tendency with an increase in the major axis of the fullerene cages (8.064, 8.238, 8.508, 8.582, 8.815, and 8.953 Å, respectively). Furthermore, the electrochemical and molecular orbital analyses reveal that the redox chemistry of the Er₂C₂@C_80-88 isomers is associated with the carbon cage, which is different from the situations found for typical dimetallofullerenes, such as Y₂@C₈₂, Er₂@C_82-84, and Lu₂@C_82,86 isomers, which show metal-dependent oxidation processes, indicating the importance of C₂ insertion in carbide cluster metallofullerenes.