From 2D to 1D Electronic Dimensionality in Halide Perovskites with Stepped and Flat Layers Using Propylammonium as a Spacer

Justin M. Hoffman; Xiaoyang Che; Siraj Sidhik; Xiaotong Li; Ido Hadar; Jean Christophe Blancon; Hisato Yamaguchi; Mikaël Kepenekian; Claudine Katan; Jacky Even; Constantinos C. Stoumpos; Aditya D. Mohite; Mercouri G. Kanatzidis

doi:10.1021/jacs.9b02846

From 2D to 1D Electronic Dimensionality in Halide Perovskites with Stepped and Flat Layers Using Propylammonium as a Spacer

Justin M. Hoffman, Xiaoyang Che, Siraj Sidhik, Xiaotong Li, Ido Hadar, Jean Christophe Blancon, Hisato Yamaguchi, Mikaël Kepenekian, Claudine Katan, Jacky Even, Constantinos C. Stoumpos, Aditya D. Mohite, Mercouri G. Kanatzidis^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

44 Scopus citations

Abstract

Two-dimensional (2D) hybrid halide perovskites are promising in optoelectronic applications, particularly solar cells and light-emitting devices (LEDs), and for their increased stability as compared to 3D perovskites. Here, we report a new series of structures using propylammonium (PA⁺), which results in a series of Ruddlesden-Popper (RP) structures with the formula (PA)₂(MA)_n-1Pb_nI_3n+1 (n = 3, 4) and a new homologous series of "step-like" (SL) structures where the PbI₆ octahedra connect in a corner- and face-sharing motif with the general formula (PA)_2m+4(MA)_m-2Pb_2m+1I_7m+4 (m = 2, 3, 4). The RP structures show a blue-shift in bandgap for decreasing n (1.90 eV for n = 4 and 2.03 eV for n = 3), while the SL structures have an even greater blue-shift (2.53 eV for m = 4, 2.74 eV for m = 3, and 2.93 eV for m = 2). DFT calculations show that, while the RP structures are electronically 2D quantum wells, the SL structures are electronically 1D quantum wires with chains of corner-sharing octahedra "insulated" by blocks of face-sharing octahedra. Dark measurements for RP crystals show high resistivity perpendicular to the layers (10¹¹ ω cm) but a lower resistivity parallel to them (10⁷ ω cm). The SL crystals have varying resistivity in all three directions, confirming both RP and SL crystals' utility as anisotropic electronic materials. The RP structures show strong photoresponse, whereas the SL materials exhibit resistivity trends that are dominated by ionic transport and no photoresponse. Solar cells were made with n = 3 giving an efficiency of 7.04% (average 6.28 ± 0.65%) with negligible hysteresis.

Original language	English (US)
Pages (from-to)	10661-10676
Number of pages	16
Journal	Journal of the American Chemical Society
Volume	141
Issue number	27
DOIs	https://doi.org/10.1021/jacs.9b02846
State	Published - Jul 10 2019

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.9b02846

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Hoffman, J. M., Che, X., Sidhik, S., Li, X., Hadar, I., Blancon, J. C., Yamaguchi, H., Kepenekian, M., Katan, C., Even, J., Stoumpos, C. C., Mohite, A. D., & Kanatzidis, M. G. (2019). From 2D to 1D Electronic Dimensionality in Halide Perovskites with Stepped and Flat Layers Using Propylammonium as a Spacer. Journal of the American Chemical Society, 141(27), 10661-10676. https://doi.org/10.1021/jacs.9b02846

@article{33a16f6543174019b9595c058fd9a49c,

title = "From 2D to 1D Electronic Dimensionality in Halide Perovskites with Stepped and Flat Layers Using Propylammonium as a Spacer",

abstract = "Two-dimensional (2D) hybrid halide perovskites are promising in optoelectronic applications, particularly solar cells and light-emitting devices (LEDs), and for their increased stability as compared to 3D perovskites. Here, we report a new series of structures using propylammonium (PA+), which results in a series of Ruddlesden-Popper (RP) structures with the formula (PA)2(MA)n-1PbnI3n+1 (n = 3, 4) and a new homologous series of {"}step-like{"} (SL) structures where the PbI6 octahedra connect in a corner- and face-sharing motif with the general formula (PA)2m+4(MA)m-2Pb2m+1I7m+4 (m = 2, 3, 4). The RP structures show a blue-shift in bandgap for decreasing n (1.90 eV for n = 4 and 2.03 eV for n = 3), while the SL structures have an even greater blue-shift (2.53 eV for m = 4, 2.74 eV for m = 3, and 2.93 eV for m = 2). DFT calculations show that, while the RP structures are electronically 2D quantum wells, the SL structures are electronically 1D quantum wires with chains of corner-sharing octahedra {"}insulated{"} by blocks of face-sharing octahedra. Dark measurements for RP crystals show high resistivity perpendicular to the layers (1011 ω cm) but a lower resistivity parallel to them (107 ω cm). The SL crystals have varying resistivity in all three directions, confirming both RP and SL crystals' utility as anisotropic electronic materials. The RP structures show strong photoresponse, whereas the SL materials exhibit resistivity trends that are dominated by ionic transport and no photoresponse. Solar cells were made with n = 3 giving an efficiency of 7.04% (average 6.28 ± 0.65%) with negligible hysteresis.",

author = "Hoffman, {Justin M.} and Xiaoyang Che and Siraj Sidhik and Xiaotong Li and Ido Hadar and Blancon, {Jean Christophe} and Hisato Yamaguchi and Mika{\"e}l Kepenekian and Claudine Katan and Jacky Even and Stoumpos, {Constantinos C.} and Mohite, {Aditya D.} and Kanatzidis, {Mercouri G.}",

note = "Funding Information: Work on the synthesis and characterization of the materials was supported by the Office of Naval Research (ONR). This project was supported in part by a fellowship award through the National Defense Science and Engineering Graduate (NDSEG) Fellowship Program, sponsored by the Air Force Research Laboratory (AFRL), the Office of Naval Research (ONR), and the Army Research Office (ARO). Work on the solar cell fabrication and evaluation was supported by the LEAP Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (award no. DE-SC0001059). Work at Los Alamos National Laboratory (LANL) was supported by the EERE program. DFT calculations were performed at the Institut des Sciences Chimiques de Rennes, which received funding from Agence Nationale pour la Recherche (TRANS-HYPERO project), and the work was granted access to the HPC resources of TGCC/CINES/IDRIS under the allocation 2018-A0030907682 made by GENCI. J.E. is a senior member of Institut Universitaire de France. This work made use of the SPID facility of Northwestern University{\textquoteright}s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = jul,

day = "10",

doi = "10.1021/jacs.9b02846",

language = "English (US)",

volume = "141",

pages = "10661--10676",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "27",

}

Hoffman, JM, Che, X, Sidhik, S, Li, X, Hadar, I, Blancon, JC, Yamaguchi, H, Kepenekian, M, Katan, C, Even, J, Stoumpos, CC, Mohite, AD & Kanatzidis, MG 2019, 'From 2D to 1D Electronic Dimensionality in Halide Perovskites with Stepped and Flat Layers Using Propylammonium as a Spacer', Journal of the American Chemical Society, vol. 141, no. 27, pp. 10661-10676. https://doi.org/10.1021/jacs.9b02846

TY - JOUR

T1 - From 2D to 1D Electronic Dimensionality in Halide Perovskites with Stepped and Flat Layers Using Propylammonium as a Spacer

AU - Hoffman, Justin M.

AU - Che, Xiaoyang

AU - Sidhik, Siraj

AU - Li, Xiaotong

AU - Hadar, Ido

AU - Blancon, Jean Christophe

AU - Yamaguchi, Hisato

AU - Kepenekian, Mikaël

AU - Katan, Claudine

AU - Even, Jacky

AU - Stoumpos, Constantinos C.

AU - Mohite, Aditya D.

AU - Kanatzidis, Mercouri G.

N1 - Funding Information: Work on the synthesis and characterization of the materials was supported by the Office of Naval Research (ONR). This project was supported in part by a fellowship award through the National Defense Science and Engineering Graduate (NDSEG) Fellowship Program, sponsored by the Air Force Research Laboratory (AFRL), the Office of Naval Research (ONR), and the Army Research Office (ARO). Work on the solar cell fabrication and evaluation was supported by the LEAP Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (award no. DE-SC0001059). Work at Los Alamos National Laboratory (LANL) was supported by the EERE program. DFT calculations were performed at the Institut des Sciences Chimiques de Rennes, which received funding from Agence Nationale pour la Recherche (TRANS-HYPERO project), and the work was granted access to the HPC resources of TGCC/CINES/IDRIS under the allocation 2018-A0030907682 made by GENCI. J.E. is a senior member of Institut Universitaire de France. This work made use of the SPID facility of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. Publisher Copyright: © 2019 American Chemical Society.

PY - 2019/7/10

Y1 - 2019/7/10

N2 - Two-dimensional (2D) hybrid halide perovskites are promising in optoelectronic applications, particularly solar cells and light-emitting devices (LEDs), and for their increased stability as compared to 3D perovskites. Here, we report a new series of structures using propylammonium (PA+), which results in a series of Ruddlesden-Popper (RP) structures with the formula (PA)2(MA)n-1PbnI3n+1 (n = 3, 4) and a new homologous series of "step-like" (SL) structures where the PbI6 octahedra connect in a corner- and face-sharing motif with the general formula (PA)2m+4(MA)m-2Pb2m+1I7m+4 (m = 2, 3, 4). The RP structures show a blue-shift in bandgap for decreasing n (1.90 eV for n = 4 and 2.03 eV for n = 3), while the SL structures have an even greater blue-shift (2.53 eV for m = 4, 2.74 eV for m = 3, and 2.93 eV for m = 2). DFT calculations show that, while the RP structures are electronically 2D quantum wells, the SL structures are electronically 1D quantum wires with chains of corner-sharing octahedra "insulated" by blocks of face-sharing octahedra. Dark measurements for RP crystals show high resistivity perpendicular to the layers (1011 ω cm) but a lower resistivity parallel to them (107 ω cm). The SL crystals have varying resistivity in all three directions, confirming both RP and SL crystals' utility as anisotropic electronic materials. The RP structures show strong photoresponse, whereas the SL materials exhibit resistivity trends that are dominated by ionic transport and no photoresponse. Solar cells were made with n = 3 giving an efficiency of 7.04% (average 6.28 ± 0.65%) with negligible hysteresis.

AB - Two-dimensional (2D) hybrid halide perovskites are promising in optoelectronic applications, particularly solar cells and light-emitting devices (LEDs), and for their increased stability as compared to 3D perovskites. Here, we report a new series of structures using propylammonium (PA+), which results in a series of Ruddlesden-Popper (RP) structures with the formula (PA)2(MA)n-1PbnI3n+1 (n = 3, 4) and a new homologous series of "step-like" (SL) structures where the PbI6 octahedra connect in a corner- and face-sharing motif with the general formula (PA)2m+4(MA)m-2Pb2m+1I7m+4 (m = 2, 3, 4). The RP structures show a blue-shift in bandgap for decreasing n (1.90 eV for n = 4 and 2.03 eV for n = 3), while the SL structures have an even greater blue-shift (2.53 eV for m = 4, 2.74 eV for m = 3, and 2.93 eV for m = 2). DFT calculations show that, while the RP structures are electronically 2D quantum wells, the SL structures are electronically 1D quantum wires with chains of corner-sharing octahedra "insulated" by blocks of face-sharing octahedra. Dark measurements for RP crystals show high resistivity perpendicular to the layers (1011 ω cm) but a lower resistivity parallel to them (107 ω cm). The SL crystals have varying resistivity in all three directions, confirming both RP and SL crystals' utility as anisotropic electronic materials. The RP structures show strong photoresponse, whereas the SL materials exhibit resistivity trends that are dominated by ionic transport and no photoresponse. Solar cells were made with n = 3 giving an efficiency of 7.04% (average 6.28 ± 0.65%) with negligible hysteresis.

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From 2D to 1D Electronic Dimensionality in Halide Perovskites with Stepped and Flat Layers Using Propylammonium as a Spacer

Abstract

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CCDC 1937882: Experimental Crystal Structure Determination

CCDC 1937883: Experimental Crystal Structure Determination

CCDC 1937884: Experimental Crystal Structure Determination

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From 2D to 1D Electronic Dimensionality in Halide Perovskites with Stepped and Flat Layers Using Propylammonium as a Spacer

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CCDC 1937882: Experimental Crystal Structure Determination

CCDC 1937883: Experimental Crystal Structure Determination

CCDC 1937884: Experimental Crystal Structure Determination

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