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

Title: Bulk assembly of organic metal halide nanotubes

Abstract

The organic metal halide hybrids welcome a new member with a one-dimensional (1D) tubular structure. Herein we report the synthesis and characterization of a single crystalline bulk assembly of organic metal halide nanotubes, (C 6H 13N 4) 3Pb 2Br 7. In a metal halide nanotube, six face-sharing metal halide dimers (Pb 2Br 9 5–) connect at the corners to form rings that extend in one dimension, of which the inside and outside surfaces are coated with protonated hexamethylenetetramine (HMTA) cations (C 6H 13N 4 +). This unique 1D tubular structure possesses highly localized electronic states with strong quantum confinement, resulting in the formation of self-trapped excitons that give strongly Stokes shifted broadband yellowish-white emission with a photoluminescence quantum efficiency (PLQE) of ~7%. Finally, having realized single crystalline bulk assemblies of two-dimensional (2D) wells, 1D wires, and now 1D tubes using organic metal halide hybrids, our work significantly advances the research on bulk assemblies of quantum-confined materials.

Authors:
 [1];  [1];  [2]; ORCiD logo [2];  [2];  [3];  [2];  [4]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [5]; ORCiD logo [3]
  1. FAMU-FSU College of Engineering, Tallahassee, FL (United States)
  2. Florida State Univ., Tallahassee, FL (United States)
  3. FAMU-FSU College of Engineering, Tallahassee, FL (United States); Florida State Univ., Tallahassee, FL (United States)
  4. Univ. of Florida, Gainesville, FL (United States)
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1410201
Grant/Contract Number:  
[AC05-00OR22725]
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
[ Journal Volume: 8; Journal Issue: 12]; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Lin, Haoran, Zhou, Chenkun, Tian, Yu, Besara, Tiglet, Neu, Jennifer, Siegrist, Theo, Zhou, Yan, Bullock, James, Schanze, Kirk S., Ming, Wenmei, Du, Mao -Hua, and Ma, Biwu. Bulk assembly of organic metal halide nanotubes. United States: N. p., 2017. Web. doi:10.1039/c7sc03675b.
Lin, Haoran, Zhou, Chenkun, Tian, Yu, Besara, Tiglet, Neu, Jennifer, Siegrist, Theo, Zhou, Yan, Bullock, James, Schanze, Kirk S., Ming, Wenmei, Du, Mao -Hua, & Ma, Biwu. Bulk assembly of organic metal halide nanotubes. United States. doi:10.1039/c7sc03675b.
Lin, Haoran, Zhou, Chenkun, Tian, Yu, Besara, Tiglet, Neu, Jennifer, Siegrist, Theo, Zhou, Yan, Bullock, James, Schanze, Kirk S., Ming, Wenmei, Du, Mao -Hua, and Ma, Biwu. Mon . "Bulk assembly of organic metal halide nanotubes". United States. doi:10.1039/c7sc03675b. https://www.osti.gov/servlets/purl/1410201.
@article{osti_1410201,
title = {Bulk assembly of organic metal halide nanotubes},
author = {Lin, Haoran and Zhou, Chenkun and Tian, Yu and Besara, Tiglet and Neu, Jennifer and Siegrist, Theo and Zhou, Yan and Bullock, James and Schanze, Kirk S. and Ming, Wenmei and Du, Mao -Hua and Ma, Biwu},
abstractNote = {The organic metal halide hybrids welcome a new member with a one-dimensional (1D) tubular structure. Herein we report the synthesis and characterization of a single crystalline bulk assembly of organic metal halide nanotubes, (C6H13N4)3Pb2Br7. In a metal halide nanotube, six face-sharing metal halide dimers (Pb2Br95–) connect at the corners to form rings that extend in one dimension, of which the inside and outside surfaces are coated with protonated hexamethylenetetramine (HMTA) cations (C6H13N4+). This unique 1D tubular structure possesses highly localized electronic states with strong quantum confinement, resulting in the formation of self-trapped excitons that give strongly Stokes shifted broadband yellowish-white emission with a photoluminescence quantum efficiency (PLQE) of ~7%. Finally, having realized single crystalline bulk assemblies of two-dimensional (2D) wells, 1D wires, and now 1D tubes using organic metal halide hybrids, our work significantly advances the research on bulk assemblies of quantum-confined materials.},
doi = {10.1039/c7sc03675b},
journal = {Chemical Science},
number = [12],
volume = [8],
place = {United States},
year = {2017},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1 Fig. 1: (a) View of the structure of (HMTA)3Pb2Br7 (red: lead atoms; green: bromine atoms; blue: nitrogen atoms; gray: carbon atoms; purple polyhedra: PbBr6 octahedra and Pb2Br9 dimers; hydrogen atoms are hidden for clarity). (b) Side view of an individual lead bromide nanotube. (c) Side view of an individual leadmore » bromide nanotube surrounded by organic cations. (d) Ball-and-stick model of an individual HMTA unit (hydrogen atoms are omitted). (e) Ball-and-stick model of an individual face-sharing lead bromide dimer Pb2Br9 with detailed bond lengths and bond angles listed in the ESI.† (f) Top view of a rugged ring formed by six lead bromide dimers. (g) Top view of a rugged metal halide ring coated with organic cations inside and outside.« less

Save / Share:

Works referenced in this record:

A Metal−Organic Nanotube Exhibiting Reversible Adsorption of (H 2 O) 12 Cluster
journal, October 2008

  • Dai, Fangna; He, Haiyan; Sun, Daofeng
  • Journal of the American Chemical Society, Vol. 130, Issue 43
  • DOI: 10.1021/ja805920t

Intriguing Optoelectronic Properties of Metal Halide Perovskites
journal, June 2016


One-dimensional organic lead halide perovskites with efficient bluish white-light emission
journal, January 2017

  • Yuan, Zhao; Zhou, Chenkun; Tian, Yu
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14051

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

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

Helical microtubules of graphitic carbon
journal, November 1991


Excitonic and Polaronic Properties of 2D Hybrid Organic–Inorganic Perovskites
journal, January 2017


Alkali halide crystals containing impurity ions with the ns2 ground-state electronic configuration†
journal, January 1991


Low-Dimensional Organic Tin Bromide Perovskites and Their Photoinduced Structural Transformation
journal, July 2017

  • Zhou, Chenkun; Tian, Yu; Wang, Mingchao
  • Angewandte Chemie International Edition, Vol. 56, Issue 31
  • DOI: 10.1002/anie.201702825

Polaron self-localization in white-light emitting hybrid perovskites
journal, January 2017

  • Cortecchia, Daniele; Yin, Jun; Bruno, Annalisa
  • Journal of Materials Chemistry C, Vol. 5, Issue 11
  • DOI: 10.1039/C7TC00366H

Synthesis and Characterization of [NH2C(I):NH2]3MI5 (M = Sn, Pb): Stereochemical Activity in Divalent Tin and Lead Halides Containing Single .ltbbrac.110.rtbbrac. Perovskite Sheets
journal, May 1995

  • Wang, Shumin; Mitzi, David B.; Feild, Chris A.
  • Journal of the American Chemical Society, Vol. 117, Issue 19
  • DOI: 10.1021/ja00124a012

A Microscale Perovskite as Single Component Broadband Phosphor for Downconversion White-Light-Emitting Devices
journal, September 2016

  • Yuan, Zhao; Zhou, Chenkun; Messier, Joshua
  • Advanced Optical Materials, Vol. 4, Issue 12
  • DOI: 10.1002/adom.201600667

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

Intrinsic White-Light Emission from Layered Hybrid Perovskites
journal, September 2014

  • Dohner, Emma R.; Jaffe, Adam; Bradshaw, Liam R.
  • Journal of the American Chemical Society, Vol. 136, Issue 38
  • DOI: 10.1021/ja507086b

A Prototypical Zeolitic Lanthanide−Organic Framework with Nanotubular Structure
journal, January 2008

  • Huang, You-Gui; Jiang, Fei-Long; Yuan, Da-Qiang
  • Crystal Growth & Design, Vol. 8, Issue 1
  • DOI: 10.1021/cg700927s

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


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

Connecting Thermoelectric Performance and Topological-Insulator Behavior: Bi 2 Te 3 and Bi 2 Te 2 Se from First Principles
journal, January 2015


Self-Assembly of Broadband White-Light Emitters
journal, January 2014

  • Dohner, Emma R.; Hoke, Eric T.; Karunadasa, Hemamala I.
  • Journal of the American Chemical Society, Vol. 136, Issue 5
  • DOI: 10.1021/ja411045r

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


Using DFT Methods to Study Activators in Optical Materials
journal, August 2015

  • Du, Mao-Hua
  • ECS Journal of Solid State Science and Technology, Vol. 5, Issue 1
  • DOI: 10.1149/2.0011601jss

Self-assembled arrays of polyoxometalate-based metal–organic nanotubes for proton conduction and magnetism
journal, January 2015

  • Jiao, Yan-Qing; Zang, Hong-Ying; Wang, Xin-Long
  • Chemical Communications, Vol. 51, Issue 56
  • DOI: 10.1039/C5CC03357H

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


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

Two-Dimensional Metal Halide Perovskites: Theory, Synthesis, and Optoelectronics
journal, January 2017


Self-Assembled Arrays of Single-Walled Metal-Organic Nanotubes
journal, November 2009

  • Luo, Tzuoo-Tsair; Wu, Huang-Chun; Jao, Yu-Chen
  • Angewandte Chemie International Edition, Vol. 48, Issue 50
  • DOI: 10.1002/anie.200904501

Carrier Self-trapping and Luminescence in Intrinsically Activated Scintillator: Cesium Hafnium Chloride (Cs 2 HfCl 6 )
journal, May 2016


Crystal structure and mechanism of a calcium-gated potassium channel
journal, May 2002

  • Jiang, Youxing; Lee, Alice; Chen, Jiayun
  • Nature, Vol. 417, Issue 6888
  • DOI: 10.1038/417515a

Recent developments in single-crystal inorganic nanotubes synthesised from removable templates
journal, January 2007

  • Shen, Guozhen; Bando, Yoshio; Golberg, Dmitri
  • International Journal of Nanotechnology, Vol. 4, Issue 6
  • DOI: 10.1504/IJNT.2007.015467

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 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

A journey in search of single-walled metal–organic nanotubes
journal, January 2011

  • Thanasekaran, Pounraj; Luo, Tzuoo-Tsair; Lee, Cheng-Hua
  • Journal of Materials Chemistry, Vol. 21, Issue 35
  • DOI: 10.1039/c1jm11153a

Broadband Emission in Two-Dimensional Hybrid Perovskites: The Role of Structural Deformation
journal, December 2016

  • Cortecchia, Daniele; Neutzner, Stefanie; Srimath Kandada, Ajay Ram
  • Journal of the American Chemical Society, Vol. 139, Issue 1
  • DOI: 10.1021/jacs.6b10390

Alkylammonium lead halides. Part 1. Isolated PbI 6 4− ions in (CH 3 NH 3 ) 4 PbI 6 •2H 2 O
journal, May 1987

  • Vincent, Beverly R.; Robertson, Katherine N.; Cameron, T. Stanley
  • Canadian Journal of Chemistry, Vol. 65, Issue 5
  • DOI: 10.1139/v87-176

Optical Investigation of Broadband White-Light Emission in Self-Assembled Organic–Inorganic Perovskite (C 6 H 11 NH 3 ) 2 PbBr 4
journal, October 2015

  • Yangui, A.; Garrot, D.; Lauret, J. S.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 41
  • DOI: 10.1021/acs.jpcc.5b06211

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

    Works referencing / citing this record:

    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

    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

    A Microscale Perovskite as Single Component Broadband Phosphor for Downconversion White-Light-Emitting Devices
    journal, September 2016

    • Yuan, Zhao; Zhou, Chenkun; Messier, Joshua
    • Advanced Optical Materials, Vol. 4, Issue 12
    • DOI: 10.1002/adom.201600667

    Self-Assembled Arrays of Single-Walled Metal-Organic Nanotubes
    journal, November 2009

    • Luo, Tzuoo-Tsair; Wu, Huang-Chun; Jao, Yu-Chen
    • Angewandte Chemie International Edition, Vol. 48, Issue 50
    • DOI: 10.1002/anie.200904501

    Low-Dimensional Organic Tin Bromide Perovskites and Their Photoinduced Structural Transformation
    journal, July 2017

    • Zhou, Chenkun; Tian, Yu; Wang, Mingchao
    • Angewandte Chemie International Edition, Vol. 56, Issue 31
    • DOI: 10.1002/anie.201702825

    Intrinsic White-Light-Emitting Metal-Organic Frameworks with Structurally Deformable Secondary Building Units
    journal, April 2019

    • Peng, Chengdong; Song, Xueling; Yin, Jinlin
    • Angewandte Chemie International Edition, Vol. 58, Issue 23
    • DOI: 10.1002/anie.201903665

    Two-Dimensional Metal Halide Perovskites: Theory, Synthesis, and Optoelectronics
    journal, January 2017


    Alkali halide crystals containing impurity ions with the ns2 ground-state electronic configuration†
    journal, January 1991


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


    Intriguing Optoelectronic Properties of Metal Halide Perovskites
    journal, June 2016


    Optical Investigation of Broadband White-Light Emission in Self-Assembled Organic–Inorganic Perovskite (C 6 H 11 NH 3 ) 2 PbBr 4
    journal, October 2015

    • Yangui, A.; Garrot, D.; Lauret, J. S.
    • The Journal of Physical Chemistry C, Vol. 119, Issue 41
    • DOI: 10.1021/acs.jpcc.5b06211

    Carrier Self-trapping and Luminescence in Intrinsically Activated Scintillator: Cesium Hafnium Chloride (Cs 2 HfCl 6 )
    journal, May 2016


    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

    Excitonic and Polaronic Properties of 2D Hybrid Organic–Inorganic Perovskites
    journal, January 2017


    A Prototypical Zeolitic Lanthanide−Organic Framework with Nanotubular Structure
    journal, January 2008

    • Huang, You-Gui; Jiang, Fei-Long; Yuan, Da-Qiang
    • Crystal Growth & Design, Vol. 8, Issue 1
    • DOI: 10.1021/cg700927s

    Synthesis and Characterization of [NH2C(I):NH2]3MI5 (M = Sn, Pb): Stereochemical Activity in Divalent Tin and Lead Halides Containing Single .ltbbrac.110.rtbbrac. Perovskite Sheets
    journal, May 1995

    • Wang, Shumin; Mitzi, David B.; Feild, Chris A.
    • Journal of the American Chemical Society, Vol. 117, Issue 19
    • DOI: 10.1021/ja00124a012

    Self-Assembly of Broadband White-Light Emitters
    journal, January 2014

    • Dohner, Emma R.; Hoke, Eric T.; Karunadasa, Hemamala I.
    • Journal of the American Chemical Society, Vol. 136, Issue 5
    • DOI: 10.1021/ja411045r

    Intrinsic White-Light Emission from Layered Hybrid Perovskites
    journal, September 2014

    • Dohner, Emma R.; Jaffe, Adam; Bradshaw, Liam R.
    • Journal of the American Chemical Society, Vol. 136, Issue 38
    • DOI: 10.1021/ja507086b

    A Metal−Organic Nanotube Exhibiting Reversible Adsorption of (H 2 O) 12 Cluster
    journal, October 2008

    • Dai, Fangna; He, Haiyan; Sun, Daofeng
    • Journal of the American Chemical Society, Vol. 130, Issue 43
    • DOI: 10.1021/ja805920t

    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

    Broadband Emission in Two-Dimensional Hybrid Perovskites: The Role of Structural Deformation
    journal, December 2016

    • Cortecchia, Daniele; Neutzner, Stefanie; Srimath Kandada, Ajay Ram
    • Journal of the American Chemical Society, Vol. 139, Issue 1
    • DOI: 10.1021/jacs.6b10390

    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

    Helical microtubules of graphitic carbon
    journal, November 1991


    Crystal structure and mechanism of a calcium-gated potassium channel
    journal, May 2002

    • Jiang, Youxing; Lee, Alice; Chen, Jiayun
    • Nature, Vol. 417, Issue 6888
    • DOI: 10.1038/417515a

    One-dimensional organic lead halide perovskites with efficient bluish white-light emission
    journal, January 2017

    • Yuan, Zhao; Zhou, Chenkun; Tian, Yu
    • Nature Communications, Vol. 8, Issue 1
    • DOI: 10.1038/ncomms14051

    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

    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

    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

    A journey in search of single-walled metal–organic nanotubes
    journal, January 2011

    • Thanasekaran, Pounraj; Luo, Tzuoo-Tsair; Lee, Cheng-Hua
    • Journal of Materials Chemistry, Vol. 21, Issue 35
    • DOI: 10.1039/c1jm11153a

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


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


    Alkylammonium lead halides. Part 1. Isolated PbI 6 4− ions in (CH 3 NH 3 ) 4 PbI 6 •2H 2 O
    journal, May 1987

    • Vincent, Beverly R.; Robertson, Katherine N.; Cameron, T. Stanley
    • Canadian Journal of Chemistry, Vol. 65, Issue 5
    • DOI: 10.1139/v87-176

    Using DFT Methods to Study Activators in Optical Materials
    journal, August 2015

    • Du, Mao-Hua
    • ECS Journal of Solid State Science and Technology, Vol. 5, Issue 1
    • DOI: 10.1149/2.0011601jss

    Direct emission from quartet excited states triggered by upconversion phenomena in solid-phase synthesized fluorescent lead-free organic–inorganic hybrid compounds
    journal, January 2019

    • Jana, Atanu; Zhumagali, Shynggys; Ba, Qiankai
    • Journal of Materials Chemistry A, Vol. 7, Issue 46
    • DOI: 10.1039/c9ta08268a

      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.