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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-1M nX 3n+1[where A = Cs +, CH 3NH 3 +, HC(NH 2) 2 +; A' = ammonium cation acting as spacer; M = Ge 2+, Sn 2+, Pb 2+; 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 nvalue 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 (CH 3(CH 2) 2NH 3) 2(CH 3NH 3) 5Pb 6I 19( n= 6) and (CH 3(CH 2) 2NH 3) 2(CH 3NH 3) 6Pb 7I 22(more » n = 7), and confirm the crystal structure with single-crystal X-ray diffraction, and provide indirect evidence for “(CH 3(CH 2) 2NH 3) 2(CH 3NH 3) 8Pb 9I 28” (“ n = 9”). Direct HCl solution calorimetric measurements show the compounds with n > 7 have unfavorable enthalpies of formation (Δ H f), 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.« less

Authors:
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Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
U.S. OFFICE OF NAVAL RESEARCH
OSTI Identifier:
1576006
Resource Type:
Journal Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 116; Journal Issue: 1; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Soe, Chan Myae 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., and Kanatzidis, Mercouri G. Structural and thermodynamic limits of layer thickness in 2D halide perovskites. United States: N. p., 2018. Web. doi:10.1073/pnas.1811006115.
Soe, Chan Myae 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. United States. https://doi.org/10.1073/pnas.1811006115
Soe, Chan Myae 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., and Kanatzidis, Mercouri G. Tue . "Structural and thermodynamic limits of layer thickness in 2D halide perovskites". United States. https://doi.org/10.1073/pnas.1811006115.
@article{osti_1576006,
title = {Structural and thermodynamic limits of layer thickness in 2D halide perovskites},
author = {Soe, Chan Myae Myae and Nagabhushana, G. P. and Shivaramaiah, Radha and Tsai, Hsinhan and Nie, Wanyi and Blancon, Jean-Christophe and Melkonyan, Ferdinand and Cao, Duyen H. and Traoré, Boubacar and Pedesseau, Laurent and Kepenekian, Mikaël and Katan, Claudine and Even, Jacky and Marks, Tobin J. and Navrotsky, Alexandra and Mohite, Aditya D. and Stoumpos, Constantinos C. and Kanatzidis, Mercouri G.},
abstractNote = {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 nvalue 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.},
doi = {10.1073/pnas.1811006115},
url = {https://www.osti.gov/biblio/1576006}, journal = {Proceedings of the National Academy of Sciences of the United States of America},
issn = {0027-8424},
number = 1,
volume = 116,
place = {United States},
year = {2018},
month = {12}
}

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High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells
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2D Homologous Perovskites as Light-Absorbing Materials for Solar Cell Applications
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White-Light Emission and Structural Distortion in New Corrugated Two-Dimensional Lead Bromide Perovskites
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Conducting tin halides with a layered organic-based perovskite structure
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Organic-Inorganic Hybrid Materials as Semiconducting Channels in Thin-Film Field-Effect Transistors
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Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design
journal, March 2016


Templating and structural engineering in organic–inorganic perovskites
journal, January 2001


Decreasing the electronic confinement in layered perovskites through intercalation
journal, January 2017


A Layered Hybrid Perovskite Solar-Cell Absorber with Enhanced Moisture Stability
journal, September 2014


Perovskite energy funnels for efficient light-emitting diodes
journal, June 2016


Understanding Quantum Confinement of Charge Carriers in Layered 2D Hybrid Perovskites
journal, September 2014


Advances and Promises of Layered Halide Hybrid Perovskite Semiconductors
journal, October 2016


Ligand-Stabilized Reduced-Dimensionality Perovskites
journal, February 2016


Exciton state in two-dimensional perovskite semiconductor (C10H21NH3)2PbI4
journal, March 1989


Scintillation properties of (C6H13NH3)2PbI4: Exciton luminescence of an organic/inorganic multiple quantum well structure compound induced by 2.0 MeV protons
journal, August 2002


Preparation and characterization of layered lead halide compounds
journal, March 1991


New Type of 2D Perovskites with Alternating Cations in the Interlayer Space, (C(NH 2 ) 3 )(CH 3 NH 3 ) n Pb n I 3 n +1 : Structure, Properties, and Photovoltaic Performance
journal, November 2017


Tunable White-Light Emission in Single-Cation-Templated Three-Layered 2D Perovskites (CH 3 CH 2 NH 3 ) 4 Pb 3 Br 10– x Cl x
journal, August 2017


Hybrid Dion–Jacobson 2D Lead Iodide Perovskites
journal, February 2018


Understanding Film Formation Morphology and Orientation in High Member 2D Ruddlesden-Popper Perovskites for High-Efficiency Solar Cells
journal, September 2017


Image charge effect on two-dimensional excitons in an inorganic-organic quantum-well crystal
journal, January 2005


Structural, optical and related properties of some natural three- and lower-dimensional semiconductor systems
journal, April 1995


Electronic properties of three- and low-dimensional semiconducting materials with Pb halide and Sn halide units
journal, February 1996


Excitons in ultrathin organic-inorganic perovskite crystals
journal, July 2015


Dielectric confinement effect on excitons in PbI 4 -based layered semiconductors
journal, March 1992


Direct calorimetric verification of thermodynamic instability of lead halide hybrid perovskites
journal, June 2016


Precise Facet Engineering of Perovskite Single Crystals by Ligand-Mediated Strategy
journal, October 2017


Efficient perovskite light-emitting diodes featuring nanometre-sized crystallites
journal, January 2017


Effect of reduced dimensionality on the optical band gap of SrTiO 3
journal, March 2013


Exploiting dimensionality and defect mitigation to create tunable microwave dielectrics
journal, October 2013


Point Defects and Extended Defects in Niobium Oxides
journal, May 1973


Scaling law for excitons in 2D perovskite quantum wells
journal, June 2018


Room Temperature Phase Transition in Methylammonium Lead Iodide Perovskite Thin Films Induced by Hydrohalic Acid Additives
journal, September 2016


Calorimetric and IR spectroscopic studies of phase transitions in methylammonium trihalogenoplumbates (II)†
journal, January 1990


Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3)PbI3 for solid-state sensitised solar cell applications
journal, January 2013


Alkylammonium lead halides. Part 2. CH 3 NH 3 PbX 3 (X = Cl, Br, I) perovskites: cuboctahedral halide cages with isotropic cation reorientation
journal, March 1990


Local Polar Fluctuations in Lead Halide Perovskite Crystals
journal, March 2017


High-efficiency solution-processed perovskite solar cells with millimeter-scale grains
journal, January 2015


One-Year stable perovskite solar cells by 2D/3D interface engineering
journal, June 2017


Magnetoabsorption of the lowest exciton in perovskite-type compound (CH3NH3)PbI3
journal, July 1994


Synthesis, Crystal Structure, and Optical and Thermal Properties of (C4H9NH3)2MI4 (M = Ge, Sn, Pb)
journal, January 1996


Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties
journal, July 2013


A Layered Hybrid Perovskite Solar-Cell Absorber with Enhanced Moisture Stability
journal, September 2014


    Works referencing / citing this record:

    Electronic properties of three- and low-dimensional semiconducting materials with Pb halide and Sn halide units
    journal, February 1996


    Perovskite energy funnels for efficient light-emitting diodes
    journal, June 2016


    A Layered Hybrid Perovskite Solar-Cell Absorber with Enhanced Moisture Stability
    journal, September 2014


    Ruddlesden–Popper Hybrid Lead Iodide Perovskite 2D Homologous Semiconductors
    journal, April 2016


    Magnetoabsorption of the lowest exciton in perovskite-type compound (CH3NH3)PbI3
    journal, July 1994


    Hybrid Dion–Jacobson 2D Lead Iodide Perovskites
    journal, February 2018


    High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells
    journal, July 2016


    Efficient perovskite light-emitting diodes featuring nanometre-sized crystallites
    journal, January 2017


    Scaling law for excitons in 2D perovskite quantum wells
    journal, June 2018


    Preparation and characterization of layered lead halide compounds
    journal, March 1991


    Synthesis, Crystal Structure, and Optical and Thermal Properties of (C4H9NH3)2MI4 (M = Ge, Sn, Pb)
    journal, January 1996


    Local Polar Fluctuations in Lead Halide Perovskite Crystals
    journal, March 2017


    Tunable White-Light Emission in Single-Cation-Templated Three-Layered 2D Perovskites (CH 3 CH 2 NH 3 ) 4 Pb 3 Br 10– x Cl x
    journal, August 2017


    Alkylammonium lead halides. Part 2. CH 3 NH 3 PbX 3 (X = Cl, Br, I) perovskites: cuboctahedral halide cages with isotropic cation reorientation
    journal, March 1990


    New Type of 2D Perovskites with Alternating Cations in the Interlayer Space, (C(NH 2 ) 3 )(CH 3 NH 3 ) n Pb n I 3 n +1 : Structure, Properties, and Photovoltaic Performance
    journal, November 2017


    Direct calorimetric verification of thermodynamic instability of lead halide hybrid perovskites
    journal, June 2016


    One-Year stable perovskite solar cells by 2D/3D interface engineering
    journal, June 2017


    Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3)PbI3 for solid-state sensitised solar cell applications
    journal, January 2013


    Decreasing the electronic confinement in layered perovskites through intercalation
    journal, January 2017


    2D Homologous Perovskites as Light-Absorbing Materials for Solar Cell Applications
    journal, June 2015


    Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design
    journal, March 2016


    Scintillation properties of (C6H13NH3)2PbI4: Exciton luminescence of an organic/inorganic multiple quantum well structure compound induced by 2.0 MeV protons
    journal, August 2002


    Conducting Layered Organic-inorganic Halides Containing <110>-Oriented Perovskite Sheets
    journal, March 1995


    Room Temperature Phase Transition in Methylammonium Lead Iodide Perovskite Thin Films Induced by Hydrohalic Acid Additives
    journal, September 2016


    Ligand-Stabilized Reduced-Dimensionality Perovskites
    journal, February 2016


    Excitons in ultrathin organic-inorganic perovskite crystals
    journal, July 2015


    Templating and structural engineering in organic–inorganic perovskites
    journal, January 2001


    Advances and Promises of Layered Halide Hybrid Perovskite Semiconductors
    journal, October 2016


    Exploiting dimensionality and defect mitigation to create tunable microwave dielectrics
    journal, October 2013


    Understanding Quantum Confinement of Charge Carriers in Layered 2D Hybrid Perovskites
    journal, September 2014


    Exciton state in two-dimensional perovskite semiconductor (C10H21NH3)2PbI4
    journal, March 1989


    Effect of reduced dimensionality on the optical band gap of SrTiO 3
    journal, March 2013


    High-efficiency solution-processed perovskite solar cells with millimeter-scale grains
    journal, January 2015


    Dielectric confinement effect on excitons in PbI 4 -based layered semiconductors
    journal, March 1992


    Structural, optical and related properties of some natural three- and lower-dimensional semiconductor systems
    journal, April 1995


    Point Defects and Extended Defects in Niobium Oxides
    journal, May 1973


    Conducting tin halides with a layered organic-based perovskite structure
    journal, June 1994


    Calorimetric and IR spectroscopic studies of phase transitions in methylammonium trihalogenoplumbates (II)†
    journal, January 1990


    Image charge effect on two-dimensional excitons in an inorganic-organic quantum-well crystal
    journal, January 2005


    Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties
    journal, July 2013


    Understanding Film Formation Morphology and Orientation in High Member 2D Ruddlesden-Popper Perovskites for High-Efficiency Solar Cells
    journal, September 2017


    White-Light Emission and Structural Distortion in New Corrugated Two-Dimensional Lead Bromide Perovskites
    journal, March 2017


    Precise Facet Engineering of Perovskite Single Crystals by Ligand-Mediated Strategy
    journal, October 2017


    Organic-Inorganic Hybrid Materials as Semiconducting Channels in Thin-Film Field-Effect Transistors
    journal, October 1999


    Exploring Lead‐Free Hybrid Double Perovskite Crystals of (BA) 2 CsAgBiBr 7 with Large Mobility‐Lifetime Product toward X‐Ray Detection
    journal, September 2019


    Two‐Dimensional Halide Perovskites in Solar Cells: 2D or not 2D?
    journal, March 2019


    Long-range exciton transport and slow annihilation in two-dimensional hybrid perovskites
    journal, January 2020


    Chemical stability and instability of inorganic halide perovskites
    journal, January 2019


    Searching for stability at lower dimensions: current trends and future prospects of layered perovskite solar cells
    journal, January 2019


    Luminescent perovskites: recent advances in theory and experiments
    journal, January 2019