O'Kane Mary E, Smith Joel A, Kilbride Rachel C, Spooner Emma L K, Duif Chris P, Catley Thomas E, Washington Adam L, King Stephen M, Parnell Steven R, Parnell Andrew J
Department of Physics and Astronomy, University of Sheffield, The Hicks Building, Sheffield S3 7RH, United Kingdom.
Faculty of Applied Sciences, Delft University of Technology, Mekelweg 15, 2629 JB Delft, The Netherlands.
Chem Mater. 2022 Aug 23;34(16):7232-7241. doi: 10.1021/acs.chemmater.2c00905. Epub 2022 Aug 3.
Tailoring the solution chemistry of metal halide perovskites requires a detailed understanding of precursor aggregation and coordination. In this work, we use various scattering techniques, including dynamic light scattering (DLS), small angle neutron scattering (SANS), and spin-echo SANS (SESANS) to probe the nanostructures from 1 nm to 10 μm within two different lead-halide perovskite solution inks (MAPbI and a triple-cation mixed-halide perovskite). We find that DLS can misrepresent the size distribution of the colloidal dispersion and use SANS/SESANS to confirm that these perovskite solutions are mostly comprised of 1-2 nm-sized particles. We further conclude that if there are larger colloids present, their concentration must be <0.005% of the total dispersion volume. With SANS, we apply a simple fitting model for two component microemulsions (Teubner-Strey), demonstrating this as a potential method to investigate the structure, chemical composition, and colloidal stability of perovskite solutions, and we here show that MAPbI solutions age more drastically than triple cation solutions.
定制金属卤化物钙钛矿的溶液化学需要对前驱体的聚集和配位有详细的了解。在这项工作中,我们使用了各种散射技术,包括动态光散射(DLS)、小角中子散射(SANS)和自旋回波SANS(SESANS),来探测两种不同的卤化铅钙钛矿溶液墨水(MAPbI和三阳离子混合卤化物钙钛矿)中从1纳米到10微米的纳米结构。我们发现DLS会错误呈现胶体分散体的尺寸分布,并使用SANS/SESANS来确认这些钙钛矿溶液主要由1-2纳米大小的颗粒组成。我们进一步得出结论,如果存在较大的胶体,其浓度必须小于总分散体积的0.005%。通过SANS,我们应用了一种用于双组分微乳液的简单拟合模型(Teubner-Strey),证明这是一种研究钙钛矿溶液的结构、化学成分和胶体稳定性的潜在方法,并且我们在此表明MAPbI溶液的老化比三阳离子溶液更剧烈。