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

Research output: Contribution to journalArticle

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.

Original languageEnglish
JournalJournal of the American Chemical Society
DOIs
Publication statusPublished - Jan 1 2019

Fingerprint

Crystals
Solar cells
Semiconductor quantum wires
Light
Discrete Fourier transforms
Equipment and Supplies
Optoelectronic devices
Semiconductor quantum wells
Hysteresis
Energy gap
Direction compound
6-hydroxy-7-methoxyphthalide
MA 4

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

From 2D to 1D Electronic Dimensionality in Halide Perovskites with Stepped and Flat Layers Using Propylammonium as a Spacer. / Hoffman, Justin M.; Che, Xiaoyang; Sidhik, Siraj; Li, Xiaotong; Hadar, Ido; Blancon, Jean Christophe; Yamaguchi, Hisato; Kepenekian, Mikaël; Katan, Claudine; Even, Jacky; Stoumpos, Constantinos C.; Mohite, Aditya D.; Kanatzidis, Mercouri G.

In: Journal of the American Chemical Society, 01.01.2019.

Research output: Contribution to journalArticle

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. https://doi.org/10.1021/jacs.9b02846
Hoffman, Justin M. ; Che, Xiaoyang ; Sidhik, Siraj ; Li, Xiaotong ; Hadar, Ido ; Blancon, Jean Christophe ; Yamaguchi, Hisato ; Kepenekian, Mikaël ; Katan, Claudine ; Even, Jacky ; Stoumpos, Constantinos C. ; Mohite, Aditya D. ; Kanatzidis, Mercouri G. / From 2D to 1D Electronic Dimensionality in Halide Perovskites with Stepped and Flat Layers Using Propylammonium as a Spacer. In: Journal of the American Chemical Society. 2019.
@article{942ac044ff0c4fe28e4259fb77c194dd,
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}",
year = "2019",
month = "1",
day = "1",
doi = "10.1021/jacs.9b02846",
language = "English",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",

}

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

PY - 2019/1/1

Y1 - 2019/1/1

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.

UR - http://www.scopus.com/inward/record.url?scp=85068314974&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85068314974&partnerID=8YFLogxK

U2 - 10.1021/jacs.9b02846

DO - 10.1021/jacs.9b02846

M3 - Article

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

ER -