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

Title: Ultrafast carrier dynamics in bimetallic nanostructure-enhanced methylammonium lead bromide perovskites

Abstract

In this paper, we examine the impact of hybrid bimetallic Au/Ag core/shell nanostructures on the carrier dynamics of methylammonium lead tribromide (MAPbBr 3) mesoporous perovskite solar cells (PSCs). Plasmon-enhanced PSCs incorporated with Au/Ag nanostructures demonstrated improved light harvesting and increased power conversion efficiency by 26% relative to reference devices. Two complementary spectral techniques, transient absorption spectroscopy (TAS) and time-resolved photoluminescence (trPL), were employed to gain a mechanistic understanding of plasmonic enhancement processes. TAS revealed a decrease in the photobleach formation time, which suggests that the nanostructures improve hot carrier thermalization to an equilibrium distribution, relieving hot phonon bottleneck in MAPbBr3 perovskites. TAS also showed a decrease in carrier decay lifetimes, indicating that nanostructures enhance photoinduced carrier generation and promote efficient electron injection into TiO 2 prior to bulk recombination. Furthermore, nanostructure-incorporated perovskite films demonstrated quenching in steady-state PL and decreases in trPL carrier lifetimes, providing further evidence of improved carrier injection in plasmon-enhanced mesoporous PSCs.

Authors:
 [1];  [2];  [2];  [1];  [1];  [1];  [2];  [1]
  1. Vanderbilt Univ., Nashville, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1350929
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Nanoscale
Additional Journal Information:
Journal Volume: 9; Journal Issue: 4; Journal ID: ISSN 2040-3364
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Ultrafast dynamics; Perovskites; Nanostructures

Citation Formats

Zarick, Holly F., Boulesbaa, Abdelaziz, Puretzky, Alexander A., Talbert, Eric M., DeBra, Zachary R., Soetan, Naiya, Geohegan, David B., and Bardhan, Rizia. Ultrafast carrier dynamics in bimetallic nanostructure-enhanced methylammonium lead bromide perovskites. United States: N. p., 2016. Web. doi:10.1039/C6NR08347A.
Zarick, Holly F., Boulesbaa, Abdelaziz, Puretzky, Alexander A., Talbert, Eric M., DeBra, Zachary R., Soetan, Naiya, Geohegan, David B., & Bardhan, Rizia. Ultrafast carrier dynamics in bimetallic nanostructure-enhanced methylammonium lead bromide perovskites. United States. doi:10.1039/C6NR08347A.
Zarick, Holly F., Boulesbaa, Abdelaziz, Puretzky, Alexander A., Talbert, Eric M., DeBra, Zachary R., Soetan, Naiya, Geohegan, David B., and Bardhan, Rizia. Wed . "Ultrafast carrier dynamics in bimetallic nanostructure-enhanced methylammonium lead bromide perovskites". United States. doi:10.1039/C6NR08347A. https://www.osti.gov/servlets/purl/1350929.
@article{osti_1350929,
title = {Ultrafast carrier dynamics in bimetallic nanostructure-enhanced methylammonium lead bromide perovskites},
author = {Zarick, Holly F. and Boulesbaa, Abdelaziz and Puretzky, Alexander A. and Talbert, Eric M. and DeBra, Zachary R. and Soetan, Naiya and Geohegan, David B. and Bardhan, Rizia},
abstractNote = {In this paper, we examine the impact of hybrid bimetallic Au/Ag core/shell nanostructures on the carrier dynamics of methylammonium lead tribromide (MAPbBr3) mesoporous perovskite solar cells (PSCs). Plasmon-enhanced PSCs incorporated with Au/Ag nanostructures demonstrated improved light harvesting and increased power conversion efficiency by 26% relative to reference devices. Two complementary spectral techniques, transient absorption spectroscopy (TAS) and time-resolved photoluminescence (trPL), were employed to gain a mechanistic understanding of plasmonic enhancement processes. TAS revealed a decrease in the photobleach formation time, which suggests that the nanostructures improve hot carrier thermalization to an equilibrium distribution, relieving hot phonon bottleneck in MAPbBr3 perovskites. TAS also showed a decrease in carrier decay lifetimes, indicating that nanostructures enhance photoinduced carrier generation and promote efficient electron injection into TiO2 prior to bulk recombination. Furthermore, nanostructure-incorporated perovskite films demonstrated quenching in steady-state PL and decreases in trPL carrier lifetimes, providing further evidence of improved carrier injection in plasmon-enhanced mesoporous PSCs.},
doi = {10.1039/C6NR08347A},
journal = {Nanoscale},
number = 4,
volume = 9,
place = {United States},
year = {2016},
month = {12}
}

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

Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Chemical Management for Colorful, Efficient, and Stable Inorganic–Organic Hybrid Nanostructured Solar Cells
journal, March 2013

  • Noh, Jun Hong; Im, Sang Hyuk; Heo, Jin Hyuck
  • Nano Letters, Vol. 13, Issue 4, p. 1764-1769
  • DOI: 10.1021/nl400349b

Hot-carrier cooling and photoinduced refractive index changes in organic–inorganic lead halide perovskites
journal, September 2015

  • Price, Michael B.; Butkus, Justinas; Jellicoe, Tom C.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9420

Ultrafast Carrier Dynamics in Methylammonium Lead Bromide Perovskite
journal, February 2016

  • Deng, Xiaofan; Wen, Xiaoming; Huang, Shujuan
  • The Journal of Physical Chemistry C, Vol. 120, Issue 5
  • DOI: 10.1021/acs.jpcc.5b11640

The Optical Properties of Metal Nanoparticles:  The Influence of Size, Shape, and Dielectric Environment
journal, January 2003

  • Kelly, K. Lance; Coronado, Eduardo; Zhao, Lin Lin
  • The Journal of Physical Chemistry B, Vol. 107, Issue 3
  • DOI: 10.1021/jp026731y

Plasmonic Dye-Sensitized Solar Cells Using Core−Shell Metal−Insulator Nanoparticles
journal, February 2011

  • Brown, Michael D.; Suteewong, Teeraporn; Kumar, R. Sai Santosh
  • Nano Letters, Vol. 11, Issue 2
  • DOI: 10.1021/nl1031106

Enhancement of Perovskite-Based Solar Cells Employing Core–Shell Metal Nanoparticles
journal, August 2013

  • Zhang, Wei; Saliba, Michael; Stranks, Samuel D.
  • Nano Letters, Vol. 13, Issue 9
  • DOI: 10.1021/nl4024287

Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals
journal, January 2015


Improving Light Harvesting in Dye-Sensitized Solar Cells Using Hybrid Bimetallic Nanostructures
journal, February 2016


Plasmon-induced resonance energy transfer for solar energy conversion
journal, August 2015


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

Advances in Perovskite Solar Cells
journal, January 2016


Highly Efficient Plasmon-Enhanced Dye-Sensitized Solar Cells through Metal@Oxide Core–Shell Nanostructure
journal, August 2011

  • Qi, Jifa; Dang, Xiangnan; Hammond, Paula T.
  • ACS Nano, Vol. 5, Issue 9
  • DOI: 10.1021/nn201808g

Plasmonically enhanced hot electron based photovoltaic device
journal, January 2013

  • Atar, Fatih B.; Battal, Enes; Aygun, Levent E.
  • Optics Express, Vol. 21, Issue 6
  • DOI: 10.1364/OE.21.007196

High Open-Circuit Voltage Solar Cells Based on Organic–Inorganic Lead Bromide Perovskite
journal, March 2013

  • Edri, Eran; Kirmayer, Saar; Cahen, David
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 6, p. 897-902
  • DOI: 10.1021/jz400348q

Spectral Features and Charge Dynamics of Lead Halide Perovskites: Origins and Interpretations
journal, January 2016


Enhanced Efficiency in Dye-Sensitized Solar Cells with Shape-Controlled Plasmonic Nanostructures
journal, September 2014

  • Zarick, Holly F.; Hurd, Olivia; Webb, Joseph A.
  • ACS Photonics, Vol. 1, Issue 9
  • DOI: 10.1021/ph500281v

Plasmonics for extreme light concentration and manipulation
journal, February 2010

  • Schuller, Jon A.; Barnard, Edward S.; Cai, Wenshan
  • Nature Materials, Vol. 9, Issue 3
  • DOI: 10.1038/nmat2630

Plasmonic-Induced Photon Recycling in Metal Halide Perovskite Solar Cells
journal, July 2015

  • Saliba, Michael; Zhang, Wei; Burlakov, Victor M.
  • Advanced Functional Materials, Vol. 25, Issue 31
  • DOI: 10.1002/adfm.201500669

Plasmon-phonon coupling in graphene
journal, November 2010


Investigation of CH 3 NH 3 PbI 3 Degradation Rates and Mechanisms in Controlled Humidity Environments Using in Situ Techniques
journal, January 2015

  • Yang, Jinli; Siempelkamp, Braden D.; Liu, Dianyi
  • ACS Nano, Vol. 9, Issue 2
  • DOI: 10.1021/nn506864k

Light-Induced Increase of Electron Diffusion Length in a p–n Junction Type CH 3 NH 3 PbBr 3 Perovskite Solar Cell
journal, June 2015

  • Kedem, Nir; Brenner, Thomas M.; Kulbak, Michael
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 13
  • DOI: 10.1021/acs.jpclett.5b00889

4-fold photocurrent enhancement in ultrathin nanoplasmonic perovskite solar cells
journal, January 2015

  • Cai, Boyuan; Peng, Yong; Cheng, Yi-Bing
  • Optics Express, Vol. 23, Issue 24
  • DOI: 10.1364/OE.23.0A1700

Plasmonic Nanoparticles as Light-Harvesting Enhancers in Perovskite Solar Cells: A User’s Guide
journal, June 2016


How Important Is the Organic Part of Lead Halide Perovskite Photovoltaic Cells? Efficient CsPbBr 3 Cells
journal, June 2015

  • Kulbak, Michael; Cahen, David; Hodes, Gary
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 13
  • DOI: 10.1021/acs.jpclett.5b00968

Influence of dielectric function properties on the optical response of plasmon resonant metallic nanoparticles
journal, November 2004


Plasmonic-enhanced perovskite solar cells using alloy popcorn nanoparticles
journal, January 2015

  • Lu, Zelin; Pan, Xujie; Ma, Yingzhuang
  • RSC Advances, Vol. 5, Issue 15
  • DOI: 10.1039/C4RA16385K

Optical Constants of the Noble Metals
journal, December 1972


Tuning the Optical Properties of Perovskite Nanoplatelets through Composition and Thickness by Ligand-Assisted Exfoliation
journal, September 2016

  • Hintermayr, Verena A.; Richter, Alexander F.; Ehrat, Florian
  • Advanced Materials, Vol. 28, Issue 43
  • DOI: 10.1002/adma.201602897

Plasmonic-enhanced polymer photovoltaic devices incorporating solution-processable metal nanoparticles
journal, July 2009

  • Chen, Fang-Chung; Wu, Jyh-Lih; Lee, Chia-Ling
  • Applied Physics Letters, Vol. 95, Issue 1
  • DOI: 10.1063/1.3174914

Ultrafast Spectroscopy of Photoexcitations in Organometal Trihalide Perovskites
journal, February 2016

  • Zhai, Yaxin; Sheng, Chuan Xiang; Zhang, Chuang
  • Advanced Functional Materials, Vol. 26, Issue 10
  • DOI: 10.1002/adfm.201505115

Trap States in Lead Iodide Perovskites
journal, January 2015

  • Wu, Xiaoxi; Trinh, M. Tuan; Niesner, Daniel
  • Journal of the American Chemical Society, Vol. 137, Issue 5
  • DOI: 10.1021/ja512833n

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

Solar cell efficiency tables (version 47): Solar cell efficiency tables
journal, November 2015

  • Green, Martin A.; Emery, Keith; Hishikawa, Yoshihiro
  • Progress in Photovoltaics: Research and Applications, Vol. 24, Issue 1
  • DOI: 10.1002/pip.2728

Femtosecond Excitonic Relaxation Dynamics of Perovskite on Mesoporous Films of Al 2 O 3 and NiO Nanoparticles
journal, July 2014

  • Hsu, Hung-Yu; Wang, Chi-Yung; Fathi, Amir
  • Angewandte Chemie International Edition, Vol. 53, Issue 35
  • DOI: 10.1002/anie.201404213

Plasmon-phonon coupling in GaAs
journal, December 1973


Highly Luminescent Cesium Lead Halide Perovskite Nanocrystals with Tunable Composition and Thickness by Ultrasonication
journal, September 2016

  • Tong, Yu; Bladt, Eva; Aygüler, Meltem F.
  • Angewandte Chemie International Edition, Vol. 55, Issue 44
  • DOI: 10.1002/anie.201605909

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

Long-Range Balanced Electron- and Hole-Transport Lengths in Organic-Inorganic CH3NH3PbI3
journal, October 2013


Localized Surface Plasmon Resonance Sensors
journal, June 2011

  • Mayer, Kathryn M.; Hafner, Jason H.
  • Chemical Reviews, Vol. 111, Issue 6
  • DOI: 10.1021/cr100313v

Methylammonium Lead Bromide Perovskite-Based Solar Cells by Vapor-Assisted Deposition
journal, February 2015

  • Sheng, Rui; Ho-Baillie, Anita; Huang, Shujuan
  • The Journal of Physical Chemistry C, Vol. 119, Issue 7
  • DOI: 10.1021/jp512936z

Comparative investigation on temperature-dependent photoluminescence of CH 3 NH 3 PbBr 3 and CH(NH 2 ) 2 PbBr 3 microstructures
journal, January 2016

  • Dai, Jun; Zheng, Hongge; Zhu, Can
  • Journal of Materials Chemistry C, Vol. 4, Issue 20
  • DOI: 10.1039/C6TC00563B

Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites
journal, October 2012


Metal-Insulator-Semiconductor Photodetectors
journal, September 2010


Chemistry and Properties of Nanocrystals of Different Shapes
journal, April 2005

  • Burda, Clemens; Chen, Xiaobo; Narayanan, Radha
  • Chemical Reviews, Vol. 105, Issue 4
  • DOI: 10.1021/cr030063a

Perovskite-based solar cells: impact of morphology and device architecture on device performance
journal, January 2015

  • Salim, Teddy; Sun, Shuangyong; Abe, Yuichiro
  • Journal of Materials Chemistry A, Vol. 3, Issue 17
  • DOI: 10.1039/C4TA05226A

Femtosecond Time-Resolved Transient Absorption Spectroscopy of CH 3 NH 3 PbI 3 Perovskite Films: Evidence for Passivation Effect of PbI 2
journal, August 2014

  • Wang, Lili; McCleese, Christopher; Kovalsky, Anton
  • Journal of the American Chemical Society, Vol. 136, Issue 35
  • DOI: 10.1021/ja504632z

Light trapping in mesoporous solar cells with plasmonic nanostructures
journal, January 2016

  • Erwin, William R.; Zarick, Holly F.; Talbert, Eric M.
  • Energy & Environmental Science, Vol. 9, Issue 5
  • DOI: 10.1039/C5EE03847B

Degradation observations of encapsulated planar CH 3 NH 3 PbI 3 perovskite solar cells at high temperatures and humidity
journal, January 2015

  • Han, Yu; Meyer, Steffen; Dkhissi, Yasmina
  • Journal of Materials Chemistry A, Vol. 3, Issue 15
  • DOI: 10.1039/C5TA00358J

Shape and size dependence of radiative, non-radiative and photothermal properties of gold nanocrystals
journal, July 2000

  • Link, Stephan; El-Sayed, Mostafa A.
  • International Reviews in Physical Chemistry, Vol. 19, Issue 3
  • DOI: 10.1080/01442350050034180

Theory of surface plasmons and surface-plasmon polaritons
journal, December 2006


Carbon nanotubes as an efficient hole collector for high voltage methylammonium lead bromide perovskite solar cells
journal, January 2016

  • Li, Zhen; Boix, Pablo P.; Xing, Guichuan
  • Nanoscale, Vol. 8, Issue 12
  • DOI: 10.1039/C5NR06177F

Advancements in perovskite solar cells: photophysics behind the photovoltaics
journal, January 2014

  • Sum, Tze Chien; Mathews, Nripan
  • Energy Environ. Sci., Vol. 7, Issue 8
  • DOI: 10.1039/C4EE00673A

Absorption Enhancement in Organic–Inorganic Halide Perovskite Films with Embedded Plasmonic Gold Nanoparticles
journal, July 2015

  • Carretero-Palacios, S.; Calvo, M. E.; Míguez, H.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 32
  • DOI: 10.1021/acs.jpcc.5b06473

Excited state and charge-carrier dynamics in perovskite solar cell materials
journal, January 2016


Gold and Silver Nanoparticles in Sensing and Imaging:  Sensitivity of Plasmon Response to Size, Shape, and Metal Composition
journal, October 2006

  • Lee, Kyeong-Seok; El-Sayed, Mostafa A.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 39
  • DOI: 10.1021/jp062536y

Interplay of structural and compositional effects on carrier recombination in mixed-halide perovskites
journal, January 2016

  • Talbert, Eric M.; Zarick, Holly F.; Orfield, Noah J.
  • RSC Advances, Vol. 6, Issue 90
  • DOI: 10.1039/C6RA16505B

Observation of a hot-phonon bottleneck in lead-iodide perovskites
journal, October 2015