TY - JOUR
T1 - Tunable exciton binding energy in 2D hybrid layered perovskites through donor–acceptor interactions within the organic layer
AU - Passarelli, James V.
AU - Mauck, Catherine M.
AU - Winslow, Samuel W.
AU - Perkinson, Collin F.
AU - Bard, Jacob C.
AU - Sai, Hiroaki
AU - Williams, Kristopher W.
AU - Narayanan, Ashwin
AU - Fairfield, Daniel J.
AU - Hendricks, Mark P.
AU - Tisdale, William A.
AU - Stupp, Samuel I.
N1 - Funding Information:
This work was supported by the US Department of Energy, Office of Science, Basic Energy Sciences, under awards numbers DE-FG02-00ER45810 (for synthesis at Northwestern University) and DE-SC0019345 (for spectroscopic studies at the Massachusetts Institute of Technology). Additional support for the X-ray characterization at Northwestern University was provided by the Center for Bio-Inspired Energy Science (CBES), an Energy Frontier Research Center (EFRC) funded by the US Department of Energy, Office of Science, Basic Energy Sciences under award number DE-SC0000989. J.V.P. acknowledges support from Northwestern University through a Ryan Fellowship. C.M.M. was supported by a Postdoctoral Fellowship in Environmental Chemistry from the Camille and Henry Dreyfus Foundation. C.F.P. was funded by the US Department of Energy, Office of Basic Energy Sciences, Division of Materials Science and Engineering (award number DE-FG02-07ER46454). NMR and mass spectrometry experiments made use of the Integrated Molecular Structure Education and Research Center at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental Resource (NSF ECCS-1542205), State of Illinois and International Institute for Nanotechnology (IIN). This work also made use of the Electron Probe Instrumentation Center, Keck-II and Scanned Probe Imaging and Development facilities of Northwestern University’s Atomic and Nanoscale Characterization Experimental Center, which has received support from the Soft and Hybrid Nanotechnology Experimental Resource (NSF ECCS-1542205), the Materials Research Science and Engineering Centers programme (DMR-1720139) at the Materials Research Center, the IIN, the Keck Foundation and the State of Illinois, through the IIN. This work made use of the Jerome B. Cohen X-ray Diffraction Facility supported by the Materials Research Science and Engineering Centers programme of the National Science Foundation (DMR-1720139) at the Materials Research Center of Northwestern University (LCP1). GIWAXS experiments were performed at the Advanced Photon Source (Sector 8-ID-E)—a US Department of Energy Office of Science User Facility operated for the Department of Energy Office of Science by Argonne National Laboratory under contract number DE-AC02-06CH11357.
PY - 2020/8/1
Y1 - 2020/8/1
N2 - The strength of electrostatic interactions within semiconductors strongly affects their performance in optoelectronic devices. An important target is the tuning of a material’s exciton binding energy—the energy binding an electron–hole pair through the electrostatic Coulomb force—independent of its electronic band gap. Here, we report on the doping of a family of two-dimensional hybrid perovskites, in which inorganic lead halide sheets alternate with naphthalene-based organic layers, with tetrachloro-1,2-benzoquinone (TCBQ). For four out of seven n = 1 perovskites, the incorporation of the electron-accepting TCBQ dopant into the organic sublattice containing the electron-donating naphthalene species enabled the tuning of the materials’ 1s exciton binding energy. The naphthalene–TCBQ electron donor–acceptor interactions increased the electrostatic screening of the exciton, in turn lowering its binding energy relative to the undoped perovskite—by almost 50% in one system. Structural and optical characterization showed that the inorganic lattice is not significantly perturbed even though the layer-to-layer spacing increases upon molecular dopant incorporation. [Figure not available: see fulltext.].
AB - The strength of electrostatic interactions within semiconductors strongly affects their performance in optoelectronic devices. An important target is the tuning of a material’s exciton binding energy—the energy binding an electron–hole pair through the electrostatic Coulomb force—independent of its electronic band gap. Here, we report on the doping of a family of two-dimensional hybrid perovskites, in which inorganic lead halide sheets alternate with naphthalene-based organic layers, with tetrachloro-1,2-benzoquinone (TCBQ). For four out of seven n = 1 perovskites, the incorporation of the electron-accepting TCBQ dopant into the organic sublattice containing the electron-donating naphthalene species enabled the tuning of the materials’ 1s exciton binding energy. The naphthalene–TCBQ electron donor–acceptor interactions increased the electrostatic screening of the exciton, in turn lowering its binding energy relative to the undoped perovskite—by almost 50% in one system. Structural and optical characterization showed that the inorganic lattice is not significantly perturbed even though the layer-to-layer spacing increases upon molecular dopant incorporation. [Figure not available: see fulltext.].
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U2 - 10.1038/s41557-020-0488-2
DO - 10.1038/s41557-020-0488-2
M3 - Article
C2 - 32632185
AN - SCOPUS:85087565274
VL - 12
SP - 672
EP - 682
JO - Nature Chemistry
JF - Nature Chemistry
SN - 1755-4330
IS - 8
ER -