Structural and thermodynamic limits of layer thickness in 2D halide perovskites

Chan Myae Myae Soe, G. P. Nagabhushana, Radha Shivaramaiah, Hsinhan Tsai, Wanyi Nie, Jean Christophe Blancon, Ferdinand Melkonyan, Duyen H. Cao, Boubacar Traoré, Laurent Pedesseau, Mikaël Kepenekian, Claudine Katan, Jacky Even, Tobin J Marks, Alexandra Navrotsky, Aditya D. Mohite, Constantinos C. Stoumpos, Mercouri G Kanatzidis

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

In the fast-evolving field of halide perovskite semiconductors, the 2D perovskites (A′)2(A)n1MnX3n+1 [where A = Cs+, CH3NH3 +, HC(NH2)2 +; A′ = ammonium cation acting as spacer; M = Ge2+, Sn2+, Pb2+; and X = Cl, Br, I] have recently made a critical entry. The n value defines the thickness of the 2D layers, which controls the optical and electronic properties. The 2D perovskites have demonstrated preliminary optoelectronic device lifetime superior to their 3D counterparts. They have also attracted fundamental interest as solution-processed quantum wells with structural and physical properties tunable via chemical composition, notably by the n value defining the perovskite layer thickness. The higher members (n > 5) have not been documented, and there are important scientific questions underlying fundamental limits for n. To develop and utilize these materials in technology, it is imperative to understand their thermodynamic stability, fundamental synthetic limitations, and the derived structure–function relationships. We report the effective synthesis of the highest iodide n-members yet, namely (CH3(CH2)2NH3)2(CH3NH3)5Pb6I19 (n = 6) and (CH3(CH2)2NH3)2(CH3NH3)6Pb7I22 (n = 7), and confirm the crystal structure with single-crystal X-ray diffraction, and provide indirect evidence for “(CH3(CH2)2NH3)2(CH3NH3)8Pb9I28” (“n = 9”). Direct HCl solution calorimetric measurements show the compounds with n > 7 have unfavorable enthalpies of formation (ΔHf), suggesting the formation of higher homologs to be challenging. Finally, we report preliminary n-dependent solar cell efficiency in the range of 9–12.6% in these higher n-members, highlighting the strong promise of these materials for high-performance devices.

Original languageEnglish
Pages (from-to)58-66
Number of pages9
JournalProceedings of the National Academy of Sciences of the United States of America
Volume116
Issue number1
DOIs
Publication statusPublished - Jan 2 2019

Fingerprint

Thermodynamics
Equipment and Supplies
Semiconductors
Iodides
Ammonium Compounds
X-Ray Diffraction
Cations
Technology
perovskite

Keywords

  • Formation enthalpy
  • Homologous series
  • Layered compounds
  • Perovskites
  • Photovoltaics
  • Ruddlesden–Popper halide

ASJC Scopus subject areas

  • General

Cite this

Structural and thermodynamic limits of layer thickness in 2D halide perovskites. / Myae Soe, Chan Myae; Nagabhushana, G. P.; Shivaramaiah, Radha; Tsai, Hsinhan; Nie, Wanyi; Blancon, Jean Christophe; Melkonyan, Ferdinand; Cao, Duyen H.; Traoré, Boubacar; Pedesseau, Laurent; Kepenekian, Mikaël; Katan, Claudine; Even, Jacky; Marks, Tobin J; Navrotsky, Alexandra; Mohite, Aditya D.; Stoumpos, Constantinos C.; Kanatzidis, Mercouri G.

In: Proceedings of the National Academy of Sciences of the United States of America, Vol. 116, No. 1, 02.01.2019, p. 58-66.

Research output: Contribution to journalArticle

Myae Soe, CM, Nagabhushana, GP, Shivaramaiah, R, Tsai, H, Nie, W, Blancon, JC, Melkonyan, F, Cao, DH, Traoré, B, Pedesseau, L, Kepenekian, M, Katan, C, Even, J, Marks, TJ, Navrotsky, A, Mohite, AD, Stoumpos, CC & Kanatzidis, MG 2019, 'Structural and thermodynamic limits of layer thickness in 2D halide perovskites', Proceedings of the National Academy of Sciences of the United States of America, vol. 116, no. 1, pp. 58-66. https://doi.org/10.1073/pnas.1811006115
Myae Soe, Chan Myae ; Nagabhushana, G. P. ; Shivaramaiah, Radha ; Tsai, Hsinhan ; Nie, Wanyi ; Blancon, Jean Christophe ; Melkonyan, Ferdinand ; Cao, Duyen H. ; Traoré, Boubacar ; Pedesseau, Laurent ; Kepenekian, Mikaël ; Katan, Claudine ; Even, Jacky ; Marks, Tobin J ; Navrotsky, Alexandra ; Mohite, Aditya D. ; Stoumpos, Constantinos C. ; Kanatzidis, Mercouri G. / Structural and thermodynamic limits of layer thickness in 2D halide perovskites. In: Proceedings of the National Academy of Sciences of the United States of America. 2019 ; Vol. 116, No. 1. pp. 58-66.
@article{2e40dcaf943a4f1481a0b357b651a01c,
title = "Structural and thermodynamic limits of layer thickness in 2D halide perovskites",
abstract = "In the fast-evolving field of halide perovskite semiconductors, the 2D perovskites (A′)2(A)n−1MnX3n+1 [where A = Cs+, CH3NH3 +, HC(NH2)2 +; A′ = ammonium cation acting as spacer; M = Ge2+, Sn2+, Pb2+; and X = Cl−, Br−, I−] have recently made a critical entry. The n value defines the thickness of the 2D layers, which controls the optical and electronic properties. The 2D perovskites have demonstrated preliminary optoelectronic device lifetime superior to their 3D counterparts. They have also attracted fundamental interest as solution-processed quantum wells with structural and physical properties tunable via chemical composition, notably by the n value defining the perovskite layer thickness. The higher members (n > 5) have not been documented, and there are important scientific questions underlying fundamental limits for n. To develop and utilize these materials in technology, it is imperative to understand their thermodynamic stability, fundamental synthetic limitations, and the derived structure–function relationships. We report the effective synthesis of the highest iodide n-members yet, namely (CH3(CH2)2NH3)2(CH3NH3)5Pb6I19 (n = 6) and (CH3(CH2)2NH3)2(CH3NH3)6Pb7I22 (n = 7), and confirm the crystal structure with single-crystal X-ray diffraction, and provide indirect evidence for “(CH3(CH2)2NH3)2(CH3NH3)8Pb9I28” (“n = 9”). Direct HCl solution calorimetric measurements show the compounds with n > 7 have unfavorable enthalpies of formation (ΔHf), suggesting the formation of higher homologs to be challenging. Finally, we report preliminary n-dependent solar cell efficiency in the range of 9–12.6{\%} in these higher n-members, highlighting the strong promise of these materials for high-performance devices.",
keywords = "Formation enthalpy, Homologous series, Layered compounds, Perovskites, Photovoltaics, Ruddlesden–Popper halide",
author = "{Myae Soe}, {Chan Myae} and Nagabhushana, {G. P.} and Radha Shivaramaiah and Hsinhan Tsai and Wanyi Nie and Blancon, {Jean Christophe} and Ferdinand Melkonyan and Cao, {Duyen H.} and Boubacar Traor{\'e} and Laurent Pedesseau and Mika{\"e}l Kepenekian and Claudine Katan and Jacky Even and Marks, {Tobin J} and Alexandra Navrotsky and Mohite, {Aditya D.} and Stoumpos, {Constantinos C.} and Kanatzidis, {Mercouri G}",
year = "2019",
month = "1",
day = "2",
doi = "10.1073/pnas.1811006115",
language = "English",
volume = "116",
pages = "58--66",
journal = "Proceedings of the National Academy of Sciences of the United States of America",
issn = "0027-8424",
number = "1",

}

TY - JOUR

T1 - Structural and thermodynamic limits of layer thickness in 2D halide perovskites

AU - Myae Soe, Chan Myae

AU - Nagabhushana, G. P.

AU - Shivaramaiah, Radha

AU - Tsai, Hsinhan

AU - Nie, Wanyi

AU - Blancon, Jean Christophe

AU - Melkonyan, Ferdinand

AU - Cao, Duyen H.

AU - Traoré, Boubacar

AU - Pedesseau, Laurent

AU - Kepenekian, Mikaël

AU - Katan, Claudine

AU - Even, Jacky

AU - Marks, Tobin J

AU - Navrotsky, Alexandra

AU - Mohite, Aditya D.

AU - Stoumpos, Constantinos C.

AU - Kanatzidis, Mercouri G

PY - 2019/1/2

Y1 - 2019/1/2

N2 - In the fast-evolving field of halide perovskite semiconductors, the 2D perovskites (A′)2(A)n−1MnX3n+1 [where A = Cs+, CH3NH3 +, HC(NH2)2 +; A′ = ammonium cation acting as spacer; M = Ge2+, Sn2+, Pb2+; and X = Cl−, Br−, I−] have recently made a critical entry. The n value defines the thickness of the 2D layers, which controls the optical and electronic properties. The 2D perovskites have demonstrated preliminary optoelectronic device lifetime superior to their 3D counterparts. They have also attracted fundamental interest as solution-processed quantum wells with structural and physical properties tunable via chemical composition, notably by the n value defining the perovskite layer thickness. The higher members (n > 5) have not been documented, and there are important scientific questions underlying fundamental limits for n. To develop and utilize these materials in technology, it is imperative to understand their thermodynamic stability, fundamental synthetic limitations, and the derived structure–function relationships. We report the effective synthesis of the highest iodide n-members yet, namely (CH3(CH2)2NH3)2(CH3NH3)5Pb6I19 (n = 6) and (CH3(CH2)2NH3)2(CH3NH3)6Pb7I22 (n = 7), and confirm the crystal structure with single-crystal X-ray diffraction, and provide indirect evidence for “(CH3(CH2)2NH3)2(CH3NH3)8Pb9I28” (“n = 9”). Direct HCl solution calorimetric measurements show the compounds with n > 7 have unfavorable enthalpies of formation (ΔHf), suggesting the formation of higher homologs to be challenging. Finally, we report preliminary n-dependent solar cell efficiency in the range of 9–12.6% in these higher n-members, highlighting the strong promise of these materials for high-performance devices.

AB - In the fast-evolving field of halide perovskite semiconductors, the 2D perovskites (A′)2(A)n−1MnX3n+1 [where A = Cs+, CH3NH3 +, HC(NH2)2 +; A′ = ammonium cation acting as spacer; M = Ge2+, Sn2+, Pb2+; and X = Cl−, Br−, I−] have recently made a critical entry. The n value defines the thickness of the 2D layers, which controls the optical and electronic properties. The 2D perovskites have demonstrated preliminary optoelectronic device lifetime superior to their 3D counterparts. They have also attracted fundamental interest as solution-processed quantum wells with structural and physical properties tunable via chemical composition, notably by the n value defining the perovskite layer thickness. The higher members (n > 5) have not been documented, and there are important scientific questions underlying fundamental limits for n. To develop and utilize these materials in technology, it is imperative to understand their thermodynamic stability, fundamental synthetic limitations, and the derived structure–function relationships. We report the effective synthesis of the highest iodide n-members yet, namely (CH3(CH2)2NH3)2(CH3NH3)5Pb6I19 (n = 6) and (CH3(CH2)2NH3)2(CH3NH3)6Pb7I22 (n = 7), and confirm the crystal structure with single-crystal X-ray diffraction, and provide indirect evidence for “(CH3(CH2)2NH3)2(CH3NH3)8Pb9I28” (“n = 9”). Direct HCl solution calorimetric measurements show the compounds with n > 7 have unfavorable enthalpies of formation (ΔHf), suggesting the formation of higher homologs to be challenging. Finally, we report preliminary n-dependent solar cell efficiency in the range of 9–12.6% in these higher n-members, highlighting the strong promise of these materials for high-performance devices.

KW - Formation enthalpy

KW - Homologous series

KW - Layered compounds

KW - Perovskites

KW - Photovoltaics

KW - Ruddlesden–Popper halide

UR - http://www.scopus.com/inward/record.url?scp=85059459063&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85059459063&partnerID=8YFLogxK

U2 - 10.1073/pnas.1811006115

DO - 10.1073/pnas.1811006115

M3 - Article

VL - 116

SP - 58

EP - 66

JO - Proceedings of the National Academy of Sciences of the United States of America

JF - Proceedings of the National Academy of Sciences of the United States of America

SN - 0027-8424

IS - 1

ER -