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Title: Cross-plane coherent acoustic phonons in two-dimensional organic-inorganic hybrid perovskites

Abstract

Two-dimensional, Ruddlesden-Popper organic-inorganic hybrid layered perovskites (2D-RPs) are solution-grown semiconductors with prospective applications in next-generation optoelectronics. The heat-carrying, low-energy acoustic vibrations of 2D-RPs, which are important for heat management of 2D-RP-based devices, have remained unexplored. Here we report on the propagation of coherent longitudinal acoustic phonons along the cross-plane direction of 2D-RPs, following separate characterizations of below-bandgap refractive index for each 2D-RP. Through experiments on crystals of systematically varied perovskite layer thickness, we demonstrate significant reduction in both group velocity and propagation length of acoustic phonons in 2D-RPs as compared to the three-dimensional methylammonium lead iodide. As borne out by a minimal coarse-grained model, these vibrational properties arise from a large acoustic impedance mismatch between the alternating layers of perovskite sheets and bulky organic cations. Furthermore, our results inform on thermal transport in highly impedance-mismatched crystal sub-lattices and provide insights towards design of materials that exhibit highly anisotropic thermal dissipation properties.

Authors:
 [1]; ORCiD logo [2];  [2];  [1];  [2];  [1];  [2];  [3]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Northwestern Univ., Evanston, IL (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States); Northwestern Univ., Evanston, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
OSTI Identifier:
1461512
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Guo, Peijun, Stoumpos, Constantinos C., Mao, Lingling, Sadasivam, Sridhar, Ketterson, John B., Darancet, Pierre, Kanatzidis, Mercouri G., and Schaller, Richard D. Cross-plane coherent acoustic phonons in two-dimensional organic-inorganic hybrid perovskites. United States: N. p., 2018. Web. doi:10.1038/s41467-018-04429-9.
Guo, Peijun, Stoumpos, Constantinos C., Mao, Lingling, Sadasivam, Sridhar, Ketterson, John B., Darancet, Pierre, Kanatzidis, Mercouri G., & Schaller, Richard D. Cross-plane coherent acoustic phonons in two-dimensional organic-inorganic hybrid perovskites. United States. doi:10.1038/s41467-018-04429-9.
Guo, Peijun, Stoumpos, Constantinos C., Mao, Lingling, Sadasivam, Sridhar, Ketterson, John B., Darancet, Pierre, Kanatzidis, Mercouri G., and Schaller, Richard D. Tue . "Cross-plane coherent acoustic phonons in two-dimensional organic-inorganic hybrid perovskites". United States. doi:10.1038/s41467-018-04429-9. https://www.osti.gov/servlets/purl/1461512.
@article{osti_1461512,
title = {Cross-plane coherent acoustic phonons in two-dimensional organic-inorganic hybrid perovskites},
author = {Guo, Peijun and Stoumpos, Constantinos C. and Mao, Lingling and Sadasivam, Sridhar and Ketterson, John B. and Darancet, Pierre and Kanatzidis, Mercouri G. and Schaller, Richard D.},
abstractNote = {Two-dimensional, Ruddlesden-Popper organic-inorganic hybrid layered perovskites (2D-RPs) are solution-grown semiconductors with prospective applications in next-generation optoelectronics. The heat-carrying, low-energy acoustic vibrations of 2D-RPs, which are important for heat management of 2D-RP-based devices, have remained unexplored. Here we report on the propagation of coherent longitudinal acoustic phonons along the cross-plane direction of 2D-RPs, following separate characterizations of below-bandgap refractive index for each 2D-RP. Through experiments on crystals of systematically varied perovskite layer thickness, we demonstrate significant reduction in both group velocity and propagation length of acoustic phonons in 2D-RPs as compared to the three-dimensional methylammonium lead iodide. As borne out by a minimal coarse-grained model, these vibrational properties arise from a large acoustic impedance mismatch between the alternating layers of perovskite sheets and bulky organic cations. Furthermore, our results inform on thermal transport in highly impedance-mismatched crystal sub-lattices and provide insights towards design of materials that exhibit highly anisotropic thermal dissipation properties.},
doi = {10.1038/s41467-018-04429-9},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {5}
}

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Works referenced in this record:

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


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

  • Lee, Che-Hui; Podraza, Nikolas J.; Zhu, Ye
  • Applied Physics Letters, Vol. 102, Issue 12
  • DOI: 10.1063/1.4798241

Ultralow Self-Doping in Two-dimensional Hybrid Perovskite Single Crystals
journal, June 2017


Ultralow Thermal Conductivity in Disordered, Layered WSe2 Crystals
journal, January 2007


Polar Fluctuations in Metal Halide Perovskites Uncovered by Acoustic Phonon Anomalies
journal, September 2017


Phonon wave interference and thermal bandgap materials
journal, June 2015


Structures, Phase Transitions and Tricritical Behavior of the Hybrid Perovskite Methyl Ammonium Lead Iodide
journal, October 2016

  • Whitfield, P. S.; Herron, N.; Guise, W. E.
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep35685

Elastic Constants, Optical Phonons, and Molecular Relaxations in the High Temperature Plastic Phase of the CH 3 NH 3 PbBr 3 Hybrid Perovskite
journal, September 2016

  • Létoublon, Antoine; Paofai, Serge; Rufflé, Benoît
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 19
  • DOI: 10.1021/acs.jpclett.6b01709

Metal halide perovskites for energy applications
journal, May 2016


Heat Capacities, Speeds of Sound, and Isothermal Compressibilities of Some n -Amines and Tri- n -amines at 298.15 K
journal, January 2002

  • Góralski, P.; Wasiak, M.; Bald, A.
  • Journal of Chemical & Engineering Data, Vol. 47, Issue 1
  • DOI: 10.1021/je010206v

Elastic Moduli of Organic Electronic Materials by the Buckling Method
journal, September 2009

  • Tahk, Dongha; Lee, Hong H.; Khang, Dahl-Young
  • Macromolecules, Vol. 42, Issue 18
  • DOI: 10.1021/ma900137k

QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

Self-Assembled Monolayers of Thiolates on Metals as a Form of Nanotechnology
journal, April 2005

  • Love, J. Christopher; Estroff, Lara A.; Kriebel, Jennah K.
  • Chemical Reviews, Vol. 105, Issue 4
  • DOI: 10.1021/cr0300789

Atomically thin two-dimensional organic-inorganic hybrid perovskites
journal, September 2015


Bright light-emitting diodes based on organometal halide perovskite
journal, August 2014

  • Tan, Zhi-Kuang; Moghaddam, Reza Saberi; Lai, May Ling
  • Nature Nanotechnology, Vol. 9, Issue 9
  • DOI: 10.1038/nnano.2014.149

Phonon Speed, Not Scattering, Differentiates Thermal Transport in Lead Halide Perovskites
journal, August 2017


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

  • Stoumpos, Constantinos C.; Cao, Duyen H.; Clark, Daniel J.
  • Chemistry of Materials, Vol. 28, Issue 8, p. 2852-2867
  • DOI: 10.1021/acs.chemmater.6b00847

Exceptional elastic anisotropy of hybrid organic-inorganic perovskite CH 3 NH 3 PbBr 3 measured by laser ultrasonic technique
journal, July 2016

  • Lomonosov, Alexey M.; Yan, Xiaoliang; Sheng, Chuanxiang
  • physica status solidi (RRL) - Rapid Research Letters, Vol. 10, Issue 8
  • DOI: 10.1002/pssr.201600156

Thermal properties of AlAs/GaAs superlattices
journal, November 1987

  • Yao, Takafumi
  • Applied Physics Letters, Vol. 51, Issue 22
  • DOI: 10.1063/1.98526

Screening in crystalline liquids protects energetic carriers in hybrid perovskites
journal, September 2016


Phonon Dynamics at Surfaces and Interfaces and Its Implications in Energy Transport in Nanostructured Materials—An opinion Paper
journal, April 2015


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


Surface generation and detection of phonons by picosecond light pulses
journal, September 1986


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

  • Mao, Lingling; Wu, Yilei; Stoumpos, Constantinos C.
  • Journal of the American Chemical Society, Vol. 139, Issue 14
  • DOI: 10.1021/jacs.7b01312

Orientational order controls crystalline and amorphous thermal transport in superatomic crystals
journal, September 2016

  • Ong, Wee-Liat; O’Brien, Evan S.; Dougherty, Patrick S. M.
  • Nature Materials, Vol. 16, Issue 1
  • DOI: 10.1038/nmat4739

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

  • Tsai, Hsinhan; Nie, Wanyi; Blancon, Jean-Christophe
  • Nature, Vol. 536, Issue 7616
  • DOI: 10.1038/nature18306

Electron–Phonon Scattering in Atomically Thin 2D Perovskites
journal, October 2016


Extremely efficient internal exciton dissociation through edge states in layered 2D perovskites
journal, March 2017


Mechanism for Broadband White-Light Emission from Two-Dimensional (110) Hybrid Perovskites
journal, May 2016

  • Hu, Te; Smith, Matthew D.; Dohner, Emma R.
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 12
  • DOI: 10.1021/acs.jpclett.6b00793

Surface chemistry mediates thermal transport in three-dimensional nanocrystal arrays
journal, March 2013

  • Ong, Wee-Liat; Rupich, Sara M.; Talapin, Dmitri V.
  • Nature Materials, Vol. 12, Issue 5
  • DOI: 10.1038/nmat3596

Direct–indirect character of the bandgap in methylammonium lead iodide perovskite
journal, October 2016

  • Hutter, Eline M.; Gélvez-Rueda, María C.; Osherov, Anna
  • Nature Materials, Vol. 16, Issue 1
  • DOI: 10.1038/nmat4765

Coherent Phonon Heat Conduction in Superlattices
journal, November 2012


Electron–acoustic phonon coupling in single crystal CH3NH3PbI3 perovskites revealed by coherent acoustic phonons
journal, February 2017

  • Mante, Pierre-Adrien; Stoumpos, Constantinos C.; Kanatzidis, Mercouri G.
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14398

Thermal conductivity of Si–Ge superlattices
journal, June 1997

  • Lee, S. -M.; Cahill, David G.; Venkatasubramanian, Rama
  • Applied Physics Letters, Vol. 70, Issue 22
  • DOI: 10.1063/1.118755

Van der Waals heterostructures
journal, July 2013

  • Geim, A. K.; Grigorieva, I. V.
  • Nature, Vol. 499, Issue 7459, p. 419-425
  • DOI: 10.1038/nature12385

Three- and low-dimensional inorganic semiconductors
journal, January 1997


Acoustic-phonon propagation in superlattices
journal, July 1988


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


Minimum Thermal Conductivity of Superlattices
journal, January 2000


Ultra-Low Thermal Conductivity in Organic–Inorganic Hybrid Perovskite CH 3 NH 3 PbI 3
journal, July 2014

  • Pisoni, Andrea; Jaćimović, Jaćim; Barišić, Osor S.
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 14
  • DOI: 10.1021/jz5012109

25th Anniversary Article: MXenes: A New Family of Two-Dimensional Materials
journal, December 2013

  • Naguib, Michael; Mochalin, Vadym N.; Barsoum, Michel W.
  • Advanced Materials, Vol. 26, Issue 7, p. 992-1005
  • DOI: 10.1002/adma.201304138

Charge-Carrier Dynamics in Organic-Inorganic Metal Halide Perovskites
journal, May 2016


Relations between the Refractive Index and Energy Gap of Semiconductors
journal, October 1985


Effects of chemical bonding on heat transport across interfaces
journal, April 2012

  • Losego, Mark D.; Grady, Martha E.; Sottos, Nancy R.
  • Nature Materials, Vol. 11, Issue 6
  • DOI: 10.1038/nmat3303

Physical mechanisms of coherent acoustic phonons generation by ultrafast laser action
journal, February 2015


Atomic and molecular layer deposition: off the beaten track
journal, January 2017

  • Van Bui, H.; Grillo, F.; van Ommen, J. R.
  • Chemical Communications, Vol. 53, Issue 1
  • DOI: 10.1039/C6CC05568K

Targeted Magnetic Nanoparticles for Remote Magnetothermal Disruption of Amyloid-β Aggregates
journal, August 2015

  • Loynachan, Colleen N.; Romero, Gabriela; Christiansen, Michael G.
  • Advanced Healthcare Materials, Vol. 4, Issue 14
  • DOI: 10.1002/adhm.201500487

Ultrasonic study of liquid crystals
journal, August 1975


Crossover from incoherent to coherent phonon scattering in epitaxial oxide superlattices
journal, December 2013

  • Ravichandran, Jayakanth; Yadav, Ajay K.; Cheaito, Ramez
  • Nature Materials, Vol. 13, Issue 2
  • DOI: 10.1038/nmat3826

Tailoring the Energy Landscape in Quasi-2D Halide Perovskites Enables Efficient Green-Light Emission
journal, May 2017


Low-Dimensional-Networked Metal Halide Perovskites: The Next Big Thing
journal, March 2017


Size and Interface Effects on Thermal Conductivity of Superlattices and Periodic Thin-Film Structures
journal, May 1997


Role of Organic Counterion in Lead- and Tin-Based Two-Dimensional Semiconducting Iodide Perovskites and Application in Planar Solar Cells
journal, October 2016


Chemically diverse and multifunctional hybrid organic–inorganic perovskites
journal, February 2017


Direct Observation of Electron–Phonon Coupling and Slow Vibrational Relaxation in Organic–Inorganic Hybrid Perovskites
journal, October 2016

  • Straus, Daniel B.; Hurtado Parra, Sebastian; Iotov, Natasha
  • Journal of the American Chemical Society, Vol. 138, Issue 42
  • DOI: 10.1021/jacs.6b08175

Long-range hot-carrier transport in hybrid perovskites visualized by ultrafast microscopy
journal, April 2017


Selective enhancement of optical nonlinearity in two-dimensional organic-inorganic lead iodide perovskites
journal, September 2017


Acoustic-optical phonon up-conversion and hot-phonon bottleneck in lead-halide perovskites
journal, January 2017

  • Yang, Jianfeng; Wen, Xiaoming; Xia, Hongze
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14120

Near infrared two photon imaging using a bright cationic Yb( iii ) bioprobe spontaneously internalized into live cells
journal, January 2017

  • Bui, Anh Thy; Beyler, Maryline; Grichine, Alexei
  • Chemical Communications, Vol. 53, Issue 44
  • DOI: 10.1039/C7CC02835K

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    Broadband white-light emission from supramolecular piperazinium-based lead halide perovskites linked by hydrogen bonds
    journal, January 2019

    • Jung, Mi-Hee; Ko, Kyoung Chul; Lee, Woo Ram
    • Dalton Transactions, Vol. 48, Issue 40
    • DOI: 10.1039/c9dt03469b

    Broadband white-light emission from supramolecular piperazinium-based lead halide perovskites linked by hydrogen bonds
    journal, January 2019

    • Jung, Mi-Hee; Ko, Kyoung Chul; Lee, Woo Ram
    • Dalton Transactions, Vol. 48, Issue 40
    • DOI: 10.1039/c9dt03469b