TY - JOUR
T1 - Solvent-Molecule Interactions Govern Crystal-Habit Selection in Naphthalene Tetracarboxylic Diimides
AU - Purdum, Geoffrey E.
AU - Chen, Xiangyu
AU - Telesz, Nicholas
AU - Ryno, Sean M.
AU - Sengar, Nikita
AU - Gessner, Thomas
AU - Risko, Chad
AU - Clancy, Paulette
AU - Weitz, R. Thomas
AU - Loo, Yueh Lin
N1 - Funding Information:
G.E.P. would like to thank Prof Jeff Schwartz for helping with the quartz crystal microbalance setup. G.E.P. and Y.-L.L acknowledge NSF funding under award DMR-1627453 as well as that from the Princeton Center for Complex Materials, a MRSEC supported by NSF under award DMR-1420541. A portion of this work was conducted at the Cornell High Energy Synchrotron Source (CHESS), which is supported by the National Science Foundation (NSF) under award DMR-1332208. G.E.P. acknowledges financial support from the Department of Defense (DoD) through the National Defense Science and Engineering Graduate Fellowship (NDSEG) Program. N.T., S.M.R, and C.R. acknowledge NSF funding under award DMR-1627428. Supercomputing resources on the Lipscomb High Performance Computing Cluster were provided by the University of Kentucky Information Technology Department and Center for Computational Sciences (CCS). P.C., N.S., and Y.-L.L. acknowledge NSF funding under award CMMI-1536895. P.C., X.C., and N.S. thank the Cornell Institute for Computational Sciences (ICSE) and the Maryland Advanced Research Computing Center (MARCC), partially funded by the state of Maryland, for access to the extensive computational resources needed for this work.
Funding Information:
G.E.P. would like to thank Prof Jeff Schwartz for helping with the quartz crystal microbalance setup. G.E.P. and Y.-L.L acknowledge NSF funding under award DMR-1627453 as well as that from the Princeton Center for Complex Materials, a MRSEC supported by NSF under award DMR-1420541. A portion of this work was conducted at the Cornell High Energy Synchrotron Source (CHESS), which is supported by the National Science Foundation (NSF) under award DMR-1332208. G.E.P. acknowledges financial support from the Department of Defense (DoD) through the National Defense Science and Engineering Graduate Fellowship (NDSEG) Program. N.T., S.M.R, and C.R. acknowledge NSF funding under award DMR-1627428. Supercomputing resources on the Lipscomb High Performance Computing Cluster were provided by the University of Kentucky Information Technology Department and Center for Computational Sciences (CCS). P.C., N.S., and Y.-L.L. acknowledge NSF funding under award CMMI-1536895. P.C., X.C., and N.S. thank the Cornell Institute for Computational Sciences (ICSE) and the Maryland Advanced Research Computing Center (MARCC), partially funded by the state of Maryland, for access to the extensive computational resources needed for this work.
Publisher Copyright:
Copyright © 2019 American Chemical Society.
PY - 2019/12/10
Y1 - 2019/12/10
N2 - Controlling hierarchical structural development in organic semiconductors, and across synthetic materials more broadly, is critical to the performance of the material in device applications. Such regulation across multiple scales, from the atomic level to the macroscale, however, is a challenging task given the often-heterogeneous nature of interactions in the processing environment that determines the kinetics and thermodynamics of material growth. Here, we elucidate factors that govern the crystal habit of a core-chlorinated naphthalene diimide (NTCDI-1) and demonstrate the ability to tune its shape in thin films during post-deposition solvent-vapor annealing. Judicious selection of solvent choice and solvent-vapor concentration controls the growth kinetics along different crystallographic axes, and, thus, the resulting habit; we can access isotropic plates that span hundreds of microns to highly anisotropic needles whose long axis can be many millimeters of crystals adopting the same packing polymorph. We find the growth rate along the π-stacking direction of NTCDI-1 during solvent-vapor annealing to scale with its solubility in the solvent and the solvent's viscosity and dielectric constant, with the two former facilitating plasticization. The dielectric constant of the solvent matters because it captures NTCDI-1-solvent interactions. Polar solvents promote π-interactions between neighboring NTCDI-1 molecules, whereas aromatic solvents disrupt these same interactions. Our quantitative understanding of the factors governing crystal-habit selection affords the ability to determine proper post-deposition processing conditions a priori and to access prespecified crystal morphologies in thin films accordingly.
AB - Controlling hierarchical structural development in organic semiconductors, and across synthetic materials more broadly, is critical to the performance of the material in device applications. Such regulation across multiple scales, from the atomic level to the macroscale, however, is a challenging task given the often-heterogeneous nature of interactions in the processing environment that determines the kinetics and thermodynamics of material growth. Here, we elucidate factors that govern the crystal habit of a core-chlorinated naphthalene diimide (NTCDI-1) and demonstrate the ability to tune its shape in thin films during post-deposition solvent-vapor annealing. Judicious selection of solvent choice and solvent-vapor concentration controls the growth kinetics along different crystallographic axes, and, thus, the resulting habit; we can access isotropic plates that span hundreds of microns to highly anisotropic needles whose long axis can be many millimeters of crystals adopting the same packing polymorph. We find the growth rate along the π-stacking direction of NTCDI-1 during solvent-vapor annealing to scale with its solubility in the solvent and the solvent's viscosity and dielectric constant, with the two former facilitating plasticization. The dielectric constant of the solvent matters because it captures NTCDI-1-solvent interactions. Polar solvents promote π-interactions between neighboring NTCDI-1 molecules, whereas aromatic solvents disrupt these same interactions. Our quantitative understanding of the factors governing crystal-habit selection affords the ability to determine proper post-deposition processing conditions a priori and to access prespecified crystal morphologies in thin films accordingly.
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U2 - 10.1021/acs.chemmater.9b03142
DO - 10.1021/acs.chemmater.9b03142
M3 - Article
AN - SCOPUS:85076391484
SN - 0897-4756
VL - 31
SP - 9691
EP - 9698
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 23
ER -