@article{69a1cf1a801e4f2daea068bed07a1516,
title = "Sulfur-Donor Solvents Strongly Coordinate Pb2+in Hybrid Organic-Inorganic Perovskite Precursor Solutions",
abstract = "Strong coordination between Lewis-basic processing additives and the Lewis-acidic lead halide in hybrid organic-inorganic perovskite (HOIP) precursor solutions is required to solubilize the lead halide, and subsequently access the appropriate crystallization kinetics and attain the desired morphology of perovskite active layers. While oxygen-donor solvents and additives, such as dimethylformamide and dimethyl sulfoxide, are widely used for perovskite processing, we demonstrate that {"}soft{"}sulfur-donor solvents exhibit stronger coordination to the {"}borderline soft{"}Lewis acid Pb2+ center of PbI2 relative to {"}hard{"}O-donor solvents in the precursor solution. The stronger coordination of S-donor solvents compared to O-donor solvents to Pb2+ implies that such compounds can be useful additives to HOIP precursor solutions. Density-functional calculations of the enthalpy change resulting from the coordination of solvents to Pb2+ provide direct numerical comparison of the strength of O-donor and S-donor coordination with Pb2+ and expands the library of candidate S-donor compounds. Our results provide a roadmap for processing additive selection and expand the previously limited choice of perovskite processing additives to include strongly coordinating S-donor compounds.",
author = "Hamill, {J. Clay} and Oluwaseun Romiluyi and Thomas, {Sara A.} and Jacquelyn Cetola and Jeffrey Schwartz and Toney, {Michael F.} and Paulette Clancy and Loo, {Yueh Lin}",
note = "Funding Information: Use of the Stanford Synchrotron Radiation Lightsource (SSRL), SLAC National Accelerator Laboratory, is supported by the US DOE, Office of Science, Office of Basic Energy Sciences under Contract DE-AC02-76SF00515. The authors acknowledge financial support from the National Science Foundation through Grant CMMI-1537011, the U.S. Department of Energy{\textquoteright}s Office of Energy Efficiency and Renewable Energy (EERE) under Solar Energy Technologies Office (SETO) Agreement No. DE-EE0008560, and the Princeton Catalysis Initiative. J.C.H. is supported by the Department of Defense by a National Defense Science and Engineering Graduate Fellowship (NDSEG). S.A.T. is supported by an Innovative Research in Energy and the Environment award from the Andlinger Center for Energy and the Environment at Princeton University. The authors acknowledge the use of Princeton{\textquoteright}s Imaging and Analysis Center, which is partially supported by the Princeton Center for Complex Materials, a National Science Foundation MRSEC program (DMR-1420541). The authors would also like to acknowledge SSRL staff engineer Ryan Davis for his assistance setting up the experimental equipment and conducting the synchrotron experiments, as well as Rachel Beal and Maged Abdelsamie for their kind help in providing laboratory space for the experiments. Funding Information: Use of the Stanford Synchrotron Radiation Lightsource (SSRL) SLAC National Accelerator Laboratory, is supported by the US DOE Office of Science, Office of Basic Energy Sciences under Contract DE-AC02-76SF00515. The authors acknowledge financial support from the National Science Foundation through Grant CMMI-1537011, the U.S. Department of Energy's Office of Energy Efficiency and Renewable Energy (EERE) under Solar Energy Technologies Office (SETO) Agreement No. DE-EE0008560, and the Princeton Catalysis Initiative. J.C.H. is supported by the Department of Defense by a National Defense Science and Engineering Graduate Fellowship (NDSEG). S.A.T. is supported by an Innovative Research in Energy and the Environment award from the Andlinger Center for Energy and the Environment at Princeton University. The authors acknowledge the use of Princeton's Imaging and Analysis Center, which is partially supported by the Princeton Center for Complex Materials, a National Science Foundation MRSEC program (DMR-1420541). The authors would also like to acknowledge SSRL staff engineer Ryan Davis for his assistance setting up the experimental equipment and conducting the synchrotron experiments, as well as Rachel Beal and Maged Abdelsamie for their kind help in providing laboratory space for the experiments. Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society.",
year = "2020",
month = jul,
day = "9",
doi = "10.1021/acs.jpcc.0c03465",
language = "English (US)",
volume = "124",
pages = "14496--14502",
journal = "Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "27",
}