skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Solvent-free synthesis of organometallic halides CH 3NH 3PbI 3 and (CH 3NH 3) 3Bi 2I 9 and their thermoelectric transport properties

Abstract

Organometallic halides are great candidates for optoelectronics. As an important family of semiconductors, understanding their thermoelectric transport properties is also important. This has been a challenging task as many of such compounds are highly intrinsic. In this work, we synthesized two halides, CH3NH3PbI3 and (CH3NH3)3Bi2I9, using a solvent-free method. We found an extraordinarily high Seebeck coefficient of +2600 ± 200 μV/K in (CH3NH3)3Bi2I9. For CH3NH3PbI3, our synthesis method led to a negative Seebeck coefficient of -1350 ± 50 μV/K, in contrast to positive values observed in solvent synthesized samples. We also found the thermal conductivity of CH3NH3PbI3 to be 0.38 W/m K, largely independent of temperature from 300 K to 450 K, despite a tetragonal-to-cubic phase transition. (CH3NH3)3Bi2I9 has an even lower thermal conductivity of 0.21 W/m K (also temperature independent) which is due to its soft phonon dispersion and weak bonds.

Authors:
 [1];  [1];  [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Department of Mechanical, Materials, and Aerospace Engineering, Illinois Institute of Technology, Chicago, Illinois 60616, USA
  2. The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1567169
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Applied Physics Letters
Additional Journal Information:
Journal Volume: 115; Journal Issue: 7; Journal ID: ISSN 0003-6951
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English

Citation Formats

Long, Xiang, Pan, Zhenyu, Zhang, Zhuolei, Urban, Jeffrey J., and Wang, Heng. Solvent-free synthesis of organometallic halides CH3NH3PbI3 and (CH3NH3)3Bi2I9 and their thermoelectric transport properties. United States: N. p., 2019. Web. doi:10.1063/1.5113535.
Long, Xiang, Pan, Zhenyu, Zhang, Zhuolei, Urban, Jeffrey J., & Wang, Heng. Solvent-free synthesis of organometallic halides CH3NH3PbI3 and (CH3NH3)3Bi2I9 and their thermoelectric transport properties. United States. doi:10.1063/1.5113535.
Long, Xiang, Pan, Zhenyu, Zhang, Zhuolei, Urban, Jeffrey J., and Wang, Heng. Mon . "Solvent-free synthesis of organometallic halides CH3NH3PbI3 and (CH3NH3)3Bi2I9 and their thermoelectric transport properties". United States. doi:10.1063/1.5113535.
@article{osti_1567169,
title = {Solvent-free synthesis of organometallic halides CH3NH3PbI3 and (CH3NH3)3Bi2I9 and their thermoelectric transport properties},
author = {Long, Xiang and Pan, Zhenyu and Zhang, Zhuolei and Urban, Jeffrey J. and Wang, Heng},
abstractNote = {Organometallic halides are great candidates for optoelectronics. As an important family of semiconductors, understanding their thermoelectric transport properties is also important. This has been a challenging task as many of such compounds are highly intrinsic. In this work, we synthesized two halides, CH3NH3PbI3 and (CH3NH3)3Bi2I9, using a solvent-free method. We found an extraordinarily high Seebeck coefficient of +2600 ± 200 μV/K in (CH3NH3)3Bi2I9. For CH3NH3PbI3, our synthesis method led to a negative Seebeck coefficient of -1350 ± 50 μV/K, in contrast to positive values observed in solvent synthesized samples. We also found the thermal conductivity of CH3NH3PbI3 to be 0.38 W/m K, largely independent of temperature from 300 K to 450 K, despite a tetragonal-to-cubic phase transition. (CH3NH3)3Bi2I9 has an even lower thermal conductivity of 0.21 W/m K (also temperature independent) which is due to its soft phonon dispersion and weak bonds.},
doi = {10.1063/1.5113535},
journal = {Applied Physics Letters},
issn = {0003-6951},
number = 7,
volume = 115,
place = {United States},
year = {2019},
month = {8}
}

Works referenced in this record:

Organic-inorganic electronics
journal, January 2001

  • Mitzi, D. B.; Chondroudis, K.; Kagan, C. R.
  • IBM Journal of Research and Development, Vol. 45, Issue 1
  • DOI: 10.1147/rd.451.0029

Halide Perovskites: Poor Man's High-Performance Semiconductors
journal, May 2016

  • Stoumpos, Constantinos C.; Kanatzidis, Mercouri G.
  • Advanced Materials, Vol. 28, Issue 28
  • DOI: 10.1002/adma.201600265

Perovskite-Based Solar Cells
journal, October 2013


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

  • Mitzi, David B.
  • Journal of the Chemical Society, Dalton Transactions, Issue 1
  • DOI: 10.1039/b007070j

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


Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells
journal, May 2009

  • Kojima, Akihiro; Teshima, Kenjiro; Shirai, Yasuo
  • Journal of the American Chemical Society, Vol. 131, Issue 17, p. 6050-6051
  • DOI: 10.1021/ja809598r

Lead Iodide Perovskite Sensitized All-Solid-State Submicron Thin Film Mesoscopic Solar Cell with Efficiency Exceeding 9%
journal, August 2012

  • Kim, Hui-Seon; Lee, Chang-Ryul; Im, Jeong-Hyeok
  • Scientific Reports, Vol. 2, Issue 1
  • DOI: 10.1038/srep00591

Sequential deposition as a route to high-performance perovskite-sensitized solar cells
journal, July 2013

  • Burschka, Julian; Pellet, Norman; Moon, Soo-Jin
  • Nature, Vol. 499, Issue 7458, p. 316-319
  • DOI: 10.1038/nature12340

High-performance photovoltaic perovskite layers fabricated through intramolecular exchange
journal, May 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

Low-temperature solution-processed wavelength-tunable perovskites for lasing
journal, March 2014

  • Xing, Guichuan; Mathews, Nripan; Lim, Swee Sien
  • Nature Materials, Vol. 13, Issue 5
  • DOI: 10.1038/nmat3911

Lead halide perovskite nanowire lasers with low lasing thresholds and high quality factors
journal, April 2015

  • Zhu, Haiming; Fu, Yongping; Meng, Fei
  • Nature Materials, Vol. 14, Issue 6
  • DOI: 10.1038/nmat4271

High-Performance Flexible Broadband Photodetector Based on Organolead Halide Perovskite
journal, September 2014

  • Hu, Xin; Zhang, Xiaodong; Liang, Lin
  • Advanced Functional Materials, Vol. 24, Issue 46
  • DOI: 10.1002/adfm.201402020

Identifying defect-tolerant semiconductors with high minority-carrier lifetimes: beyond hybrid lead halide perovskites
journal, May 2015

  • Brandt, Riley E.; Stevanović, Vladan; Ginley, David S.
  • MRS Communications, Vol. 5, Issue 2
  • DOI: 10.1557/mrc.2015.26

Electron-hole diffusion lengths > 175 μm in solution-grown CH 3 NH 3 PbI 3 single crystals
journal, January 2015


Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber
journal, October 2013

  • Stranks, S. D.; Eperon, G. E.; Grancini, G.
  • Science, Vol. 342, Issue 6156, p. 341-344
  • DOI: 10.1126/science.1243982

Temperature-Dependent Charge-Carrier Dynamics in CH 3 NH 3 PbI 3 Perovskite Thin Films
journal, September 2015

  • Milot, Rebecca L.; Eperon, Giles E.; Snaith, Henry J.
  • Advanced Functional Materials, Vol. 25, Issue 39
  • DOI: 10.1002/adfm.201502340

Atomistic Origins of High-Performance in Hybrid Halide Perovskite Solar Cells
journal, April 2014

  • Frost, Jarvist M.; Butler, Keith T.; Brivio, Federico
  • Nano Letters, Vol. 14, Issue 5
  • DOI: 10.1021/nl500390f

Are Mobilities in Hybrid Organic–Inorganic Halide Perovskites Actually “High”?
journal, November 2015

  • Brenner, Thomas M.; Egger, David A.; Rappe, Andrew M.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 23
  • DOI: 10.1021/acs.jpclett.5b02390

Lead-Free Halide Double Perovskites via Heterovalent Substitution of Noble Metals
journal, March 2016

  • Volonakis, George; Filip, Marina R.; Haghighirad, Amir Abbas
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 7
  • DOI: 10.1021/acs.jpclett.6b00376

Bismuth Based Hybrid Perovskites A 3 Bi 2 I 9 (A: Methylammonium or Cesium) for Solar Cell Application
journal, September 2015

  • Park, Byung-Wook; Philippe, Bertrand; Zhang, Xiaoliang
  • Advanced Materials, Vol. 27, Issue 43
  • DOI: 10.1002/adma.201501978

Cooling, Heating, Generating Power, and Recovering Waste Heat with Thermoelectric Systems
journal, September 2008


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

Hall mobility in tin iodide perovskite CH3NH3SnI3: Evidence for a doped semiconductor
journal, September 2013

  • Takahashi, Yukari; Hasegawa, Hiroyuki; Takahashi, Yukihiro
  • Journal of Solid State Chemistry, Vol. 205
  • DOI: 10.1016/j.jssc.2013.07.008

Lead-free solid-state organic–inorganic halide perovskite solar cells
journal, May 2014

  • Hao, Feng; Stoumpos, Constantinos C.; Cao, Duyen Hanh
  • Nature Photonics, Vol. 8, Issue 6
  • DOI: 10.1038/nphoton.2014.82

Ultralow thermal conductivity in all-inorganic halide perovskites
journal, July 2017

  • Lee, Woochul; Li, Huashan; Wong, Andrew B.
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 33
  • DOI: 10.1073/pnas.1711744114

CsSnI3 : Semiconductor or Metal? High Electrical Conductivity and Strong Near-Infrared Photoluminescence from a Single Material. High Hole Mobility and Phase-Transitions
journal, May 2012

  • Chung, In; Song, Jung-Hwan; Im, Jino
  • Journal of the American Chemical Society, Vol. 134, Issue 20, p. 8579-8587
  • DOI: 10.1021/ja301539s

Unusual defect physics in CH 3 NH 3 PbI 3 perovskite solar cell absorber
journal, February 2014

  • Yin, Wan-Jian; Shi, Tingting; Yan, Yanfa
  • Applied Physics Letters, Vol. 104, Issue 6
  • DOI: 10.1063/1.4864778

Materials Processing Routes to Trap-Free Halide Perovskites
journal, October 2014

  • Buin, Andrei; Pietsch, Patrick; Xu, Jixian
  • Nano Letters, Vol. 14, Issue 11
  • DOI: 10.1021/nl502612m

Reconstructive Phase Transformation and Kinetics of Cs3Sb2I9by Means of Rietveld Analysis of X-Ray Diffraction and127I NQR
journal, December 1997

  • Yamada, Koji; Sera, Hiroshi; Sawada, Shigeko
  • Journal of Solid State Chemistry, Vol. 134, Issue 2
  • DOI: 10.1006/jssc.1997.7562

Thin-Film Preparation and Characterization of Cs 3 Sb 2 I 9 : A Lead-Free Layered Perovskite Semiconductor
journal, August 2015


Crystal and Electronic Structures of Complex Bismuth Iodides A 3 Bi 2 I 9 ( A = K, Rb, Cs) Related to Perovskite: Aiding the Rational Design of Photovoltaics
journal, October 2015


Structural Variety of Defect Perovskite Variants M 3 E 2 X 9 ( M = Rb, Tl, E = Bi, Sb, X = Br, I) : Structural Variety of Defect Perovskite
journal, June 2016

  • Chang, Jen-Hui; Doert, Thomas; Ruck, Michael
  • Zeitschrift für anorganische und allgemeine Chemie, Vol. 642, Issue 13
  • DOI: 10.1002/zaac.201600179

Ultra-high Seebeck coefficient and low thermal conductivity of a centimeter-sized perovskite single crystal acquired by a modified fast growth method
journal, January 2017

  • Ye, Tao; Wang, Xizu; Li, Xianqiang
  • Journal of Materials Chemistry C, Vol. 5, Issue 5
  • DOI: 10.1039/C6TC04594D

Tuning of the Thermoelectric Figure of Merit of CH 3 NH 3 MI 3 (M═Pb,Sn) Photovoltaic Perovskites
journal, May 2015

  • Mettan, Xavier; Pisoni, Riccardo; Matus, Péter
  • The Journal of Physical Chemistry C, Vol. 119, Issue 21
  • DOI: 10.1021/acs.jpcc.5b03939

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

  • Stoumpos, Constantinos C.; Malliakas, Christos D.; Kanatzidis, Mercouri G.
  • Inorganic Chemistry, Vol. 52, Issue 15, p. 9019-9038
  • DOI: 10.1021/ic401215x

Band gap estimation from temperature dependent Seebeck measurement—Deviations from the 2e|S|maxTmax relation
journal, January 2015

  • Gibbs, Zachary M.; Kim, Hyun-Sik; Wang, Heng
  • Applied Physics Letters, Vol. 106, Issue 2
  • DOI: 10.1063/1.4905922

The maximum possible conversion efficiency of silicon‐germanium thermoelectric generators
journal, September 1991

  • Slack, Glen A.; Hussain, Moayyed A.
  • Journal of Applied Physics, Vol. 70, Issue 5
  • DOI: 10.1063/1.349385

Colossal Seebeck coefficient in strongly correlated semiconductor FeSb 2
journal, September 2007


Discovery of colossal Seebeck effect in metallic Cu2Se
journal, January 2019


Cellulose ionic conductors with high differential thermal voltage for low-grade heat harvesting
journal, March 2019


The Effects of the Organic–Inorganic Interactions on the Thermal Transport Properties of CH 3 NH 3 PbI 3
journal, March 2016


Lattice thermal conductivity of organic-inorganic hybrid perovskite CH 3 NH 3 PbI 3
journal, February 2016

  • Qian, Xin; Gu, Xiaokun; Yang, Ronggui
  • Applied Physics Letters, Vol. 108, Issue 6
  • DOI: 10.1063/1.4941921

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

  • Onoda-Yamamuro, Noriko; Matsuo, Takasuke; Suga, Hiroshi
  • Journal of Physics and Chemistry of Solids, Vol. 51, Issue 12
  • DOI: 10.1016/0022-3697(90)90021-7

Cation Dynamics Governed Thermal Properties of Lead Halide Perovskite Nanowires
journal, April 2018


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


Thermal Conductivity of Methylammonium Lead Halide Perovskite Single Crystals and Thin Films: A Comparative Study
journal, December 2017

  • Heiderhoff, Ralf; Haeger, Tobias; Pourdavoud, Neda
  • The Journal of Physical Chemistry C, Vol. 121, Issue 51
  • DOI: 10.1021/acs.jpcc.7b11495