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Title: Enhanced yield-mobility products in hybrid halide Ruddlesden–Popper compounds with aromatic ammonium spacers

Abstract

We show hybrid halide Ruddlesden–Popper compounds are related to three-dimensional hybrid AMX3 perovskites (e.g. where A is a monovalent cation, M is a divalent metal cation, and X is a halogen) with the general formula L2An–1MnX3n+1 where L is a monovalent spacer cation. The crystal structure comprises perovskite-like layers separated by organic cation spacers. Here two Ruddlesden–Popper compounds with a conjugated cation, 2-(4-biphenyl)ethylammonium (BPEA) prepared by solvothermal and solvent evaporation techniques are reported. The structures of the two compounds: (BPEA)2PbI4 and (BPEA)2(CH3NH3)Pb2I7, were solved by X-ray crystallography. The aromatic rings of the BPEA groups are well-separated in the organic layers leading to optical properties comparable to n = 1 and 2 hybrid halide Ruddlesden–Popper compounds with simpler alkyl ammonium cations. The ambient stability of both compounds over time was also confirmed by powder X-ray diffraction. Finally, the transient photoconductance, measured by time-resolved microwave conductivity, show that the compounds have maximum yield-mobility products respectively of 0.07 cm2 V–1 s–1 and 1.11 cm2 V–1 s–1 for (BPEA)2PbI4 and (BPEA)2(CH3NH3)Pb2I7, both slightly enhanced over what has been measured for compounds with simpler (n-butylammonium) spacer cations.

Authors:
ORCiD logo [1];  [2];  [2];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of California, Santa Barbara, CA (United States). Dept. of Materials
  2. Univ. of California, Santa Barbara, CA (United States). Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Univ. of California, Santa Barbara, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1594803
Alternate Identifier(s):
OSTI ID: 1560335
Grant/Contract Number:  
SC0012541; DMR-1720256
Resource Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 48; Journal Issue: 37; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Venkatesan, Naveen R., Mahdi, Ali, Barraza, Brian, Wu, Guang, Chabinyc, Michael L., and Seshadri, Ram. Enhanced yield-mobility products in hybrid halide Ruddlesden–Popper compounds with aromatic ammonium spacers. United States: N. p., 2019. Web. doi:10.1039/C9DT03074C.
Venkatesan, Naveen R., Mahdi, Ali, Barraza, Brian, Wu, Guang, Chabinyc, Michael L., & Seshadri, Ram. Enhanced yield-mobility products in hybrid halide Ruddlesden–Popper compounds with aromatic ammonium spacers. United States. https://doi.org/10.1039/C9DT03074C
Venkatesan, Naveen R., Mahdi, Ali, Barraza, Brian, Wu, Guang, Chabinyc, Michael L., and Seshadri, Ram. Thu . "Enhanced yield-mobility products in hybrid halide Ruddlesden–Popper compounds with aromatic ammonium spacers". United States. https://doi.org/10.1039/C9DT03074C. https://www.osti.gov/servlets/purl/1594803.
@article{osti_1594803,
title = {Enhanced yield-mobility products in hybrid halide Ruddlesden–Popper compounds with aromatic ammonium spacers},
author = {Venkatesan, Naveen R. and Mahdi, Ali and Barraza, Brian and Wu, Guang and Chabinyc, Michael L. and Seshadri, Ram},
abstractNote = {We show hybrid halide Ruddlesden–Popper compounds are related to three-dimensional hybrid AMX3 perovskites (e.g. where A is a monovalent cation, M is a divalent metal cation, and X is a halogen) with the general formula L2An–1MnX3n+1 where L is a monovalent spacer cation. The crystal structure comprises perovskite-like layers separated by organic cation spacers. Here two Ruddlesden–Popper compounds with a conjugated cation, 2-(4-biphenyl)ethylammonium (BPEA) prepared by solvothermal and solvent evaporation techniques are reported. The structures of the two compounds: (BPEA)2PbI4 and (BPEA)2(CH3NH3)Pb2I7, were solved by X-ray crystallography. The aromatic rings of the BPEA groups are well-separated in the organic layers leading to optical properties comparable to n = 1 and 2 hybrid halide Ruddlesden–Popper compounds with simpler alkyl ammonium cations. The ambient stability of both compounds over time was also confirmed by powder X-ray diffraction. Finally, the transient photoconductance, measured by time-resolved microwave conductivity, show that the compounds have maximum yield-mobility products respectively of 0.07 cm2 V–1 s–1 and 1.11 cm2 V–1 s–1 for (BPEA)2PbI4 and (BPEA)2(CH3NH3)Pb2I7, both slightly enhanced over what has been measured for compounds with simpler (n-butylammonium) spacer cations.},
doi = {10.1039/C9DT03074C},
journal = {Dalton Transactions},
number = 37,
volume = 48,
place = {United States},
year = {Thu Sep 05 00:00:00 EDT 2019},
month = {Thu Sep 05 00:00:00 EDT 2019}
}

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Works referenced in this record:

Understanding the Role of Cesium and Rubidium Additives in Perovskite Solar Cells: Trap States, Charge Transport, and Recombination
journal, January 2018

  • Hu, Yinghong; Hutter, Eline M.; Rieder, Philipp
  • Advanced Energy Materials, Vol. 8, Issue 16
  • DOI: 10.1002/aenm.201703057

Perovskite light-emitting diodes based on solution-processed self-organized multiple quantum wells
journal, September 2016


Formamidine and cesium-based quasi-two-dimensional perovskites as photovoltaic absorbers
journal, January 2017

  • Hamaguchi, R.; Yoshizawa-Fujita, M.; Miyasaka, T.
  • Chemical Communications, Vol. 53, Issue 31
  • DOI: 10.1039/C7CC00921F

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

  • Calabrese, J.; Jones, N. L.; Harlow, R. L.
  • Journal of the American Chemical Society, Vol. 113, Issue 6, p. 2328-2330
  • DOI: 10.1021/ja00006a076

Ruddlesden-Popper Perovskite Solar Cells
journal, March 2017


Metal Halide Perovskite Polycrystalline Films Exhibiting Properties of Single Crystals
journal, September 2017


Organometal Halide Perovskite Solar Cell Materials Rationalized: Ultrafast Charge Generation, High and Microsecond-Long Balanced Mobilities, and Slow Recombination
journal, February 2014

  • Ponseca, Carlito S.; Savenije, Tom J.; Abdellah, Mohamed
  • Journal of the American Chemical Society, Vol. 136, Issue 14
  • DOI: 10.1021/ja412583t

Iodide management in formamidinium-lead-halide–based perovskite layers for efficient solar cells
journal, June 2017


Ultrahydrophobic 3D/2D fluoroarene bilayer-based water-resistant perovskite solar cells with efficiencies exceeding 22%
journal, June 2019


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


Perovskite light-emitting diodes with external quantum efficiency exceeding 20 per cent
journal, October 2018


Structural origins of broadband emission from layered Pb–Br hybrid perovskites
journal, January 2017

  • Smith, Matthew D.; Jaffe, Adam; Dohner, Emma R.
  • Chemical Science, Vol. 8, Issue 6
  • DOI: 10.1039/C7SC01590A

Revealing the Dynamics of Charge Carriers in Polymer:Fullerene Blends Using Photoinduced Time-Resolved Microwave Conductivity
journal, October 2013

  • Savenije, Tom J.; Ferguson, Andrew J.; Kopidakis, Nikos
  • The Journal of Physical Chemistry C, Vol. 117, Issue 46
  • DOI: 10.1021/jp406706u

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

Phase Engineering in Quasi-2D Ruddlesden–Popper Perovskites
journal, April 2018


Electrons, Excitons, and Phonons in Two-Dimensional Hybrid Perovskites: Connecting Structural, Optical, and Electronic Properties
journal, February 2018


Phasing methods for protein crystallography
journal, October 1997


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

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

  • Mao, Lingling; Ke, Weijun; Pedesseau, Laurent
  • Journal of the American Chemical Society, Vol. 140, Issue 10
  • DOI: 10.1021/jacs.8b00542

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

  • Grancini, G.; Roldán-Carmona, C.; Zimmermann, I.
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15684

Thermally Activated Exciton Dissociation and Recombination Control the Carrier Dynamics in Organometal Halide Perovskite
journal, June 2014

  • Savenije, Tom J.; Ponseca, Carlito S.; Kunneman, Lucas
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 13
  • DOI: 10.1021/jz500858a

Correction of intensities for preferred orientation in powder diffractometry: application of the March model
journal, August 1986


Properties and potential optoelectronic applications of lead halide perovskite nanocrystals
journal, November 2017

  • Kovalenko, Maksym V.; Protesescu, Loredana; Bodnarchuk, Maryna I.
  • Science, Vol. 358, Issue 6364
  • DOI: 10.1126/science.aam7093

Photovoltaic materials: Present efficiencies and future challenges
journal, April 2016


Improved Understanding of the Electronic and Energetic Landscapes of Perovskite Solar Cells: High Local Charge Carrier Mobility, Reduced Recombination, and Extremely Shallow Traps
journal, September 2014

  • Oga, Hikaru; Saeki, Akinori; Ogomi, Yuhei
  • Journal of the American Chemical Society, Vol. 136, Issue 39
  • DOI: 10.1021/ja506936f

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

  • Smith, Ian C.; Hoke, Eric T.; Solis-Ibarra, Diego
  • Angewandte Chemie, Vol. 126, Issue 42
  • DOI: 10.1002/ange.201406466

Phase Intergrowth and Structural Defects in Organic Metal Halide Ruddlesden–Popper Thin Films
journal, November 2018


Grain-Size-Limited Mobility in Methylammonium Lead Iodide Perovskite Thin Films
journal, August 2016


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

  • Yuan, Mingjian; Quan, Li Na; Comin, Riccardo
  • Nature Nanotechnology, Vol. 11, Issue 10
  • DOI: 10.1038/nnano.2016.110

Tailoring Organic Cation of 2D Air-Stable Organometal Halide Perovskites for Highly Efficient Planar Solar Cells
journal, May 2017


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

  • Mitzi, D. B.; Feild, C. A.; Harrison, W. T. A.
  • Nature, Vol. 369, Issue 6480, p. 467-469
  • DOI: 10.1038/369467a0

High-mobility ultrathin semiconducting films prepared by spin coating
journal, March 2004

  • Mitzi, David B.; Kosbar, Laura L.; Murray, Conal E.
  • Nature, Vol. 428, Issue 6980, p. 299-303
  • DOI: 10.1038/nature02389

2D Ruddlesden-Popper Perovskites for Optoelectronics
journal, October 2017


High-Performance Color-Tunable Perovskite Light Emitting Devices through Structural Modulation from Bulk to Layered Film
journal, December 2016

  • Chen, Ziming; Zhang, Chongyang; Jiang, Xiao-Fang
  • Advanced Materials, Vol. 29, Issue 8
  • DOI: 10.1002/adma.201603157

Charge transport in a two-dimensional hybrid metal halide thiocyanate compound
journal, January 2017

  • Labram, John G.; Venkatesan, Naveen R.; Takacs, Christopher J.
  • Journal of Materials Chemistry C, Vol. 5, Issue 24
  • DOI: 10.1039/C7TC01161J

Dimensionality and Interface Engineering of 2D Homologous Perovskites for Boosted Charge-Carrier Transport and Photodetection Performances
journal, May 2017


Recombination at high carrier density in methylammonium lead iodide studied using time-resolved microwave conductivity
journal, August 2017

  • Labram, John G.; Chabinyc, Michael L.
  • Journal of Applied Physics, Vol. 122, Issue 6
  • DOI: 10.1063/1.4990802

Colloidal Halide Perovskite Nanoplatelets: An Exciting New Class of Semiconductor Nanomaterials
journal, May 2017


Nanocrystals of Cesium Lead Halide Perovskites (CsPbX 3 , X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut
journal, February 2015

  • Protesescu, Loredana; Yakunin, Sergii; Bodnarchuk, Maryna I.
  • Nano Letters, Vol. 15, Issue 6
  • DOI: 10.1021/nl5048779

Light-Induced Degradation of CH 3 NH 3 PbI 3 Hybrid Perovskite Thin Film
journal, February 2017

  • Li, Youzhen; Xu, Xuemei; Wang, Congcong
  • The Journal of Physical Chemistry C, Vol. 121, Issue 7
  • DOI: 10.1021/acs.jpcc.6b11853

Ab Initio Molecular Dynamics Simulations of Methylammonium Lead Iodide Perovskite Degradation by Water
journal, June 2015


The compound Sr 3 Ti 2 O 7 and its structure
journal, January 1958


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


New compounds of the K 2 NIF 4 type
journal, August 1957


Charge-Carrier Dynamics and Crystalline Texture of Layered Ruddlesden–Popper Hybrid Lead Iodide Perovskite Thin Films
journal, January 2018


Metal halide perovskites for energy applications
journal, May 2016


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


The Role of Oxygen in the Degradation of Methylammonium Lead Trihalide Perovskite Photoactive Layers
journal, May 2015

  • Aristidou, Nicholas; Sanchez-Molina, Irene; Chotchuangchutchaval, Thana
  • Angewandte Chemie International Edition, Vol. 54, Issue 28
  • DOI: 10.1002/anie.201503153

GSAS-II : the genesis of a modern open-source all purpose crystallography software package
journal, March 2013


Maximizing and stabilizing luminescence from halide perovskites with potassium passivation
journal, March 2018

  • Abdi-Jalebi, Mojtaba; Andaji-Garmaroudi, Zahra; Cacovich, Stefania
  • Nature, Vol. 555, Issue 7697
  • DOI: 10.1038/nature25989

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011


Quantitative analysis of time-resolved microwave conductivity data
journal, November 2017

  • Reid, Obadiah G.; Moore, David T.; Li, Zhen
  • Journal of Physics D: Applied Physics, Vol. 50, Issue 49
  • DOI: 10.1088/1361-6463/aa9559

Design, Structure, and Optical Properties of Organic−Inorganic Perovskites Containing an Oligothiophene Chromophore
journal, December 1999

  • Mitzi, David B.; Chondroudis, Konstantinos; Kagan, Cherie R.
  • Inorganic Chemistry, Vol. 38, Issue 26
  • DOI: 10.1021/ic991048k

Solar cell efficiency tables (version 49): Solar cell efficiency tables (version 49)
journal, November 2016

  • Green, Martin A.; Emery, Keith; Hishikawa, Yoshihiro
  • Progress in Photovoltaics: Research and Applications, Vol. 25, Issue 1
  • DOI: 10.1002/pip.2855

Organometal halide perovskite solar cells: degradation and stability
journal, January 2016

  • Berhe, Taame Abraha; Su, Wei-Nien; Chen, Ching-Hsiang
  • Energy & Environmental Science, Vol. 9, Issue 2
  • DOI: 10.1039/C5EE02733K

Highly Tunable Colloidal Perovskite Nanoplatelets through Variable Cation, Metal, and Halide Composition
journal, July 2016


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

Charge-Carrier Dynamics in 2D Hybrid Metal–Halide Perovskites
journal, October 2016


2D perovskite stabilized phase-pure formamidinium perovskite solar cells
journal, August 2018


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

Vertically Oriented 2D Layered Perovskite Solar Cells with Enhanced Efficiency and Good Stability
journal, July 2017


In situ observation of heat-induced degradation of perovskite solar cells
journal, January 2016


Stability Issues on Perovskite Solar Cells
journal, November 2015


Crystal structure refinement with SHELXL
journal, January 2015

  • Sheldrick, George M.
  • Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053229614024218

Some new organic-inorganic hybrid semiconductors based on metal halide units: structural, optical and related properties
journal, November 1999


Characterization of the Valence and Conduction Band Levels of n = 1 2D Perovskites: A Combined Experimental and Theoretical Investigation
journal, February 2018


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

White-Light Emission from Layered Halide Perovskites
journal, February 2018


Bifunctional Organic Spacers for Formamidinium-Based Hybrid Dion–Jacobson Two-Dimensional Perovskite Solar Cells
journal, December 2018


Phase Stability and Diffusion in Lateral Heterostructures of Methyl Ammonium Lead Halide Perovskites
journal, June 2019

  • Kennard, Rhys M.; Dahlman, Clayton J.; Nakayama, Hidenori
  • ACS Applied Materials & Interfaces, Vol. 11, Issue 28
  • DOI: 10.1021/acsami.9b06069

Hybrid Organic-Inorganic Perovskites (HOIPs): Opportunities and Challenges
journal, July 2015

  • Berry, Joseph; Buonassisi, Tonio; Egger, David A.
  • Advanced Materials, Vol. 27, Issue 35
  • DOI: 10.1002/adma.201502294

The Role of Oxygen in the Degradation of Methylammonium Lead Trihalide Perovskite Photoactive Layers
journal, May 2015

  • Aristidou, Nicholas; Sanchez-Molina, Irene; Chotchuangchutchaval, Thana
  • Angewandte Chemie, Vol. 127, Issue 28
  • DOI: 10.1002/ange.201503153

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

  • Smith, Ian C.; Hoke, Eric T.; Solis-Ibarra, Diego
  • Angewandte Chemie International Edition, Vol. 53, Issue 42
  • DOI: 10.1002/anie.201406466

High-Mobility Ultrathin Semiconducting Films Prepared by Spin Coating.
journal, June 2004

  • Mitzi, David B.; Kosbar, Laura L.; Murray, Conal E.
  • ChemInform, Vol. 35, Issue 22
  • DOI: 10.1002/chin.200422013

Lead palladium titanate: A room temperature nanoscale multiferroic thin film
journal, February 2020


Metal Halide Perovskite Polycrystalline Films Exhibiting Properties of Single Crystals
text, January 2017

  • Brenes, R.; Guo, D.; Osherov, A.
  • Apollo - University of Cambridge Repository
  • DOI: 10.17863/cam.12467

Highly Tunable Colloidal Perovskite Nanoplatelets through Variable Cation, Metal, and Halide Composition.
text, January 2016

  • Weidman, Mark C.; Seitz, Michael; Stranks, Samuel
  • Apollo - University of Cambridge Repository
  • DOI: 10.17863/cam.12469

Maximizing and stabilizing luminescence from halide perovskites with potassium passivation
journalarticle, January 2018

  • Abdi Jalebi, Mojtaba; Andaji Garmaroudi, Zahra; Cacovich, Stefania
  • Springer Nature
  • DOI: 10.17863/cam.18795

Perovskite light-emitting diodes based on solution-processed self-organized multiple quantum wells
text, January 2016

  • Wang, Nana; Cheng, L.; Ge, R.
  • Apollo - University of Cambridge Repository
  • DOI: 10.17863/cam.9307

Direct-indirect character of the bandgap in methylammonium lead iodide perovskite.
text, January 2017

  • Hutter, Em; Gélvez-Rueda, Mc; Osherov, A.
  • Apollo - University of Cambridge Repository
  • DOI: 10.17863/cam.12468

Works referencing / citing this record:

Exciton-band tuning induced by the width of the cation in 2D lead iodide perovskite hybrids
journal, January 2020

  • Tremblay, Marie-Hélène; Bacsa, John; Barlow, Stephen
  • Materials Chemistry Frontiers
  • DOI: 10.1039/d0qm00118j