Identifying the acceptor state in NiO hole collection layers: direct observation of exciton dissociation and interfacial hole transfer across a Fe2O3/NiO heterojunction
Abstract
NiO is widely utilized as a hole transport layer in solar energy devices where light absorption in a photoactive layer is followed by charge separation and hole injection into a NiO collection layer. Due to the complex electronic structure of the hybridized valence band in NiO, the chemical nature of the hole acceptor state has remained an open question, despite the fact that hole localization in this material significantly influences device efficiency. To comment on this, we present results of ultrafast charge carrier dynamics in a NiO based model heterojunction (Fe2O3/NiO) using extreme ultraviolet reflection–absorption (XUV-RA) spectroscopy. Element specific XUV-RA spectroscopy demonstrates the formation of transient Ni3+ within 10 ps following selective photoexcitation of the underlying Fe2O3 substrate. This indicates that hole transfer in this system occurs to NiO valence band states composed of significant Ni 3d character. Additionally, we show that this hole injection process proceeds via a two-step sequential mechanism where fast, field-driven exciton dissociation occurs in Fe2O3 in 680 ± 60 fs, followed by subsequent hole injection to NiO in 9.2 ± 2.9 ps. Furthermore, these results reveal the chemical nature of the hole acceptor state in widely used NiO hole transport layers and provides a directmore »
- Publication Date:
- Research Org.:
- The Ohio State Univ., Columbus, OH (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1594155
- Alternate Identifier(s):
- OSTI ID: 1469409
- Grant/Contract Number:
- SC0014051
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP
- Additional Journal Information:
- Journal Volume: 20; Journal Issue: 38; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Biswas, Somnath, Husek, Jakub, Londo, Stephen, Fugate, Elizabeth A., and Baker, L. Robert. Identifying the acceptor state in NiO hole collection layers: direct observation of exciton dissociation and interfacial hole transfer across a Fe2O3/NiO heterojunction. United States: N. p., 2018.
Web. doi:10.1039/c8cp04502j.
Biswas, Somnath, Husek, Jakub, Londo, Stephen, Fugate, Elizabeth A., & Baker, L. Robert. Identifying the acceptor state in NiO hole collection layers: direct observation of exciton dissociation and interfacial hole transfer across a Fe2O3/NiO heterojunction. United States. https://doi.org/10.1039/c8cp04502j
Biswas, Somnath, Husek, Jakub, Londo, Stephen, Fugate, Elizabeth A., and Baker, L. Robert. Wed .
"Identifying the acceptor state in NiO hole collection layers: direct observation of exciton dissociation and interfacial hole transfer across a Fe2O3/NiO heterojunction". United States. https://doi.org/10.1039/c8cp04502j. https://www.osti.gov/servlets/purl/1594155.
@article{osti_1594155,
title = {Identifying the acceptor state in NiO hole collection layers: direct observation of exciton dissociation and interfacial hole transfer across a Fe2O3/NiO heterojunction},
author = {Biswas, Somnath and Husek, Jakub and Londo, Stephen and Fugate, Elizabeth A. and Baker, L. Robert},
abstractNote = {NiO is widely utilized as a hole transport layer in solar energy devices where light absorption in a photoactive layer is followed by charge separation and hole injection into a NiO collection layer. Due to the complex electronic structure of the hybridized valence band in NiO, the chemical nature of the hole acceptor state has remained an open question, despite the fact that hole localization in this material significantly influences device efficiency. To comment on this, we present results of ultrafast charge carrier dynamics in a NiO based model heterojunction (Fe2O3/NiO) using extreme ultraviolet reflection–absorption (XUV-RA) spectroscopy. Element specific XUV-RA spectroscopy demonstrates the formation of transient Ni3+ within 10 ps following selective photoexcitation of the underlying Fe2O3 substrate. This indicates that hole transfer in this system occurs to NiO valence band states composed of significant Ni 3d character. Additionally, we show that this hole injection process proceeds via a two-step sequential mechanism where fast, field-driven exciton dissociation occurs in Fe2O3 in 680 ± 60 fs, followed by subsequent hole injection to NiO in 9.2 ± 2.9 ps. Furthermore, these results reveal the chemical nature of the hole acceptor state in widely used NiO hole transport layers and provides a direct observation of exciton dissociation and interfacial hole transfer in this model system.},
doi = {10.1039/c8cp04502j},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 38,
volume = 20,
place = {United States},
year = {Wed Sep 05 00:00:00 EDT 2018},
month = {Wed Sep 05 00:00:00 EDT 2018}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 23 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Role of the Charge Transfer State in Organic Donor-Acceptor Solar Cells
journal, August 2010
- Deibel, Carsten; Strobel, Thomas; Dyakonov, Vladimir
- Advanced Materials, Vol. 22, Issue 37
Glotaran : A Java -Based Graphical User Interface for the R Package TIMP
journal, January 2012
- Snellenburg, Joris J.; Laptenok, Sergey P.; Seger, Ralf
- Journal of Statistical Software, Vol. 49, Issue 3
Femtosecond tracking of carrier relaxation in germanium with extreme ultraviolet transient reflectivity
journal, May 2018
- Kaplan, Christopher J.; Kraus, Peter M.; Ross, Andrew D.
- Physical Review B, Vol. 97, Issue 20
X-ray Transient Absorption and Picosecond IR Spectroscopy of Fulvalene(tetracarbonyl)diruthenium on Photoexcitation
journal, June 2012
- Harpham, Michael R.; Nguyen, Son C.; Hou, Zongrui
- Angewandte Chemie International Edition, Vol. 51, Issue 31
NiO x Hole Transport Layer for Perovskite Solar Cells with Improved Stability and Reproducibility
journal, May 2017
- Islam, Md. Bodiul; Yanagida, Masatoshi; Shirai, Yasuhiro
- ACS Omega, Vol. 2, Issue 5
Experimental determination of band offsets of NiO-based thin film heterojunctions
journal, October 2014
- Kawade, Daisuke; Chichibu, Shigefusa F.; Sugiyama, Mutsumi
- Journal of Applied Physics, Vol. 116, Issue 16
Carrier-Specific Femtosecond XUV Transient Absorption of PbI 2 Reveals Ultrafast Nonradiative Recombination
journal, December 2017
- Lin, Ming-Fu; Verkamp, Max A.; Leveillee, Joshua
- The Journal of Physical Chemistry C, Vol. 121, Issue 50
Band gaps and electronic structure of transition-metal compounds
journal, July 1985
- Zaanen, J.; Sawatzky, G. A.; Allen, J. W.
- Physical Review Letters, Vol. 55, Issue 4
Picosecond X-ray Absorption Spectroscopy of a Photoinduced Iron(II) Spin Crossover Reaction in Solution
journal, January 2006
- Khalil, Munira; Marcus, Matthew A.; Smeigh, Amanda L.
- The Journal of Physical Chemistry A, Vol. 110, Issue 1
Charge Separation and Exciton Dynamics at Polymer/ZnO Interface from First-Principles Simulations
journal, July 2014
- Wu, Guangfen; Li, Zi; Zhang, Xu
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 15
How fast is interfacial hole transfer? In situ monitoring of carrier dynamics in anatase TiO2 nanoparticles by femtosecond laser spectroscopy
journal, January 2001
- Yang, Xiujuan; Tamai, Naoto
- Physical Chemistry Chemical Physics, Vol. 3, Issue 16
Highly Localized Charge Transfer Excitons in Metal Oxide Semiconductors
journal, January 2018
- Biswas, Somnath; Husek, Jakub; Londo, Stephen
- Nano Letters, Vol. 18, Issue 2
Ultrafast carrier thermalization and trapping in silicon-germanium alloy probed by extreme ultraviolet transient absorption spectroscopy
journal, July 2017
- Zürch, Michael; Chang, Hung-Tzu; Kraus, Peter M.
- Structural Dynamics, Vol. 4, Issue 4
Nickel Oxide Electrode Interlayer in CH 3 NH 3 PbI 3 Perovskite/PCBM Planar-Heterojunction Hybrid Solar Cells
journal, March 2014
- Jeng, Jun-Yuan; Chen, Kuo-Cheng; Chiang, Tsung-Yu
- Advanced Materials, Vol. 26, Issue 24
Electrochemical Behavior of Reactively Sputtered Iron-Doped Nickel Oxide
journal, January 1997
- Miller, Eric L.
- Journal of The Electrochemical Society, Vol. 144, Issue 9
Optical and thermal electron transfer in metal complexes
journal, March 1978
- Meyer, Thomas J.
- Accounts of Chemical Research, Vol. 11, Issue 3
Femtosecond M 2,3 -Edge Spectroscopy of Transition-Metal Oxides: Photoinduced Oxidation State Change in α-Fe 2 O 3
journal, October 2013
- Vura-Weis, Josh; Jiang, Chang-Ming; Liu, Chong
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 21
Field-Assisted Exciton Dissociation in Highly Efficient PffBT4T-2OD:Fullerene Organic Solar Cells
journal, March 2018
- Weu, Andreas; Hopper, Thomas R.; Lami, Vincent
- Chemistry of Materials, Vol. 30, Issue 8
Electronic and nuclear contributions to time-resolved optical and X-ray absorption spectra of hematite and insights into photoelectrochemical performance
journal, January 2016
- Hayes, Dugan; Hadt, Ryan G.; Emery, Jonathan D.
- Energy & Environmental Science, Vol. 9, Issue 12
Tabletop Femtosecond M-edge X-ray Absorption Near-Edge Structure of FeTPPCl: Metalloporphyrin Photophysics from the Perspective of the Metal
journal, March 2018
- Ryland, Elizabeth S.; Lin, Ming-Fu; Verkamp, Max A.
- Journal of the American Chemical Society, Vol. 140, Issue 13
Excitation-wavelength-dependent small polaron trapping of photoexcited carriers in α-Fe2O3
journal, July 2017
- Carneiro, Lucas M.; Cushing, Scott K.; Liu, Chong
- Nature Materials, Vol. 16, Issue 8
Influence of interface properties on charge density, band edge shifts and kinetics of the photoelectrochemical process in p-type NiO photocathodes
journal, January 2015
- Liu, Qian; Wei, Lifang; Yuan, Shuai
- RSC Advances, Vol. 5, Issue 88
Improved Exciton Dissociation at Semiconducting Polymer:ZnO Donor:Acceptor Interfaces via Nitrogen Doping of ZnO
journal, March 2014
- Musselman, Kevin P.; Albert-Seifried, Sebastian; Hoye, Robert L. Z.
- Advanced Functional Materials, Vol. 24, Issue 23
Inorganic p-type contact materials for perovskite-based solar cells
journal, January 2015
- Li, Ming-Hsien; Shen, Po-Shen; Wang, Kuo-Chin
- Journal of Materials Chemistry A, Vol. 3, Issue 17
Probing electronic binding potentials with attosecond photoelectron wavepackets
journal, October 2017
- Kiesewetter, D.; Jones, R. R.; Camper, A.
- Nature Physics, Vol. 14, Issue 1
New interpretations of XPS spectra of nickel metal and oxides
journal, May 2006
- Grosvenor, Andrew P.; Biesinger, Mark C.; Smart, Roger St. C.
- Surface Science, Vol. 600, Issue 9
p-Type semiconducting nickel oxide as an efficiency-enhancing anode interfacial layer in polymer bulk-heterojunction solar cells
journal, February 2008
- Irwin, M. D.; Buchholz, D. B.; Hains, A. W.
- Proceedings of the National Academy of Sciences, Vol. 105, Issue 8, p. 2783-2787
Elucidating ultrafast electron dynamics at surfaces using extreme ultraviolet (XUV) reflection–absorption spectroscopy
journal, January 2018
- Biswas, Somnath; Husek, Jakub; Baker, L. Robert
- Chemical Communications, Vol. 54, Issue 34
Highly efficient perovskite solar cells incorporating NiO nanotubes: increased grain size and enhanced charge extraction
journal, January 2017
- Yun, Juyoung; Jun, Jaemoon; Yu, Haejun
- J. Mater. Chem. A, Vol. 5, Issue 41
Photoinduced Structural Dynamics of Molecular Systems Mapped by Time-Resolved X-ray Methods
journal, May 2017
- Chergui, Majed; Collet, Eric
- Chemical Reviews, Vol. 117, Issue 16
Ultrafast Electron Trapping and Defect-Mediated Recombination in NiO Probed by Femtosecond Extreme Ultraviolet Reflection–Absorption Spectroscopy
journal, August 2018
- Biswas, Somnath; Husek, Jakub; Londo, Stephen
- The Journal of Physical Chemistry Letters, Vol. 9, Issue 17
Nickel Oxide Hole Injection/Transport Layers for Efficient Solution-Processed Organic Light-Emitting Diodes
journal, July 2014
- Liu, Shuyi; Liu, Rui; Chen, Ying
- Chemistry of Materials, Vol. 26, Issue 15
Field emission from α-Fe2O3 nanoflakes: Effect of vacuum pressure, gas adsorption and in-situ thermal treatment
journal, February 2014
- Wu, J. Q.; Deng, S. Z.; Xu, N. S.
- Applied Surface Science, Vol. 292
p-Type Dye-Sensitized NiO Solar Cells: A Study by Electrochemical Impedance Spectroscopy
journal, November 2011
- Huang, Zhongjie; Natu, Gayatri; Ji, Zhiqiang
- The Journal of Physical Chemistry C, Vol. 115, Issue 50
Charge-Transfer Processes in Dye-Sensitized NiO Solar Cells
journal, September 2008
- Mori, Shogo; Fukuda, Shunya; Sumikura, Seiichi
- The Journal of Physical Chemistry C, Vol. 112, Issue 41
Solid-State Perovskite-Sensitized p-Type Mesoporous Nickel Oxide Solar Cells
journal, April 2014
- Tian, Haining; Xu, Bo; Chen, Hong
- ChemSusChem, Vol. 7, Issue 8
Ultrafast Exciton Dissociation and Long-Lived Charge Separation in a Photovoltaic Pentacene–MoS 2 van der Waals Heterojunction
journal, December 2016
- Bettis Homan, Stephanie; Sangwan, Vinod K.; Balla, Itamar
- Nano Letters, Vol. 17, Issue 1
Long-range exciton dissociation in organic solar cells
journal, August 2012
- Caruso, D.; Troisi, A.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 34
NiO as an Inorganic Hole-Transporting Layer in Quantum-Dot Light-Emitting Devices
journal, December 2006
- Caruge, Jean-Michel; Halpert, Jonathan E.; Bulović, Vladimir
- Nano Letters, Vol. 6, Issue 12
Attosecond transient-absorption dynamics of xenon core-excited states in a strong driving field
journal, March 2017
- Kobayashi, Yuki; Timmers, Henry; Sabbar, Mazyar
- Physical Review A, Vol. 95, Issue 3
An ultra-thin, un-doped NiO hole transporting layer of highly efficient (16.4%) organic–inorganic hybrid perovskite solar cells
journal, January 2016
- Seo, Seongrok; Park, Ik Jae; Kim, Myungjun
- Nanoscale, Vol. 8, Issue 22
Design of α-Fe2O3 nanorods functionalized tubular NiO nanostructure for discriminating toluene molecules
journal, May 2016
- Wang, Chen; Wang, Tianshuang; Wang, Boqun
- Scientific Reports, Vol. 6, Issue 1
Achieving Surface Sensitivity in Ultrafast XUV Spectroscopy: M 2,3 -Edge Reflection–Absorption of Transition Metal Oxides
journal, July 2017
- Cirri, Anthony; Husek, Jakub; Biswas, Somnath
- The Journal of Physical Chemistry C, Vol. 121, Issue 29
Relationship between Work Function of Hole Collection Electrode and Temperature Dependence of Open-Circuit Voltage in Multilayered Organic Solar Cells
journal, February 2012
- Itoh, Eiji; Shirotori, Toshiki
- Japanese Journal of Applied Physics, Vol. 51, Issue 2S
Review of third and next generation synchrotron light sources
journal, April 2005
- Bilderback, Donald H.; Elleaume, Pascal; Weckert, Edgar
- Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 38, Issue 9
Dissociation of two-dimensional excitons in monolayer WSe2
journal, April 2018
- Massicotte, Mathieu; Vialla, Fabien; Schmidt, Peter
- Nature Communications, Vol. 9, Issue 1
Site-Selective Passivation of Defects in NiO Solar Photocathodes by Targeted Atomic Deposition
journal, February 2016
- Flynn, Cory J.; McCullough, Shannon M.; Oh, EunBi
- ACS Applied Materials & Interfaces, Vol. 8, Issue 7
Hole Thermalization Dynamics Facilitate Ultrafast Spatial Charge Separation in CuFeO 2 Solar Photocathodes
journal, May 2018
- Husek, Jakub; Cirri, Anthony; Biswas, Somnath
- The Journal of Physical Chemistry C, Vol. 122, Issue 21
Spectroscopic investigation of the hole states in Ni-deficient NiO films
journal, January 2013
- Cho, Deok-Yong; Song, Seul Ji; Kim, Un Ki
- Journal of Materials Chemistry C, Vol. 1, Issue 28
Exciton Ionization, Franz−Keldysh, and Stark Effects in Carbon Nanotubes
journal, March 2007
- Perebeinos, Vasili; Avouris, Phaedon
- Nano Letters, Vol. 7, Issue 3
Structural and Electrical Functionality of NiO Interfacial Films in Bulk Heterojunction Organic Solar Cells
journal, April 2011
- Irwin, Michael D.; Servaites, Jonathan D.; Buchholz, D. Bruce
- Chemistry of Materials, Vol. 23, Issue 8
Visualizing Interfacial Charge Transfer in Ru-Dye-Sensitized TiO 2 Nanoparticles Using X-ray Transient Absorption Spectroscopy
journal, February 2011
- Zhang, Xiaoyi; Smolentsev, Grigory; Guo, Jianchang
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 6
Influence of iron doping on tetravalent nickel content in catalytic oxygen evolving films
journal, January 2017
- Li, Nancy; Bediako, D. Kwabena; Hadt, Ryan G.
- Proceedings of the National Academy of Sciences, Vol. 114, Issue 7
Bilayer Dye Protected Aqueous Photocathodes for Tandem Dye-Sensitized Solar Cells
journal, April 2017
- Click, Kevin A.; Schockman, Bradley M.; Dilenschneider, Justin T.
- The Journal of Physical Chemistry C, Vol. 121, Issue 16
Surface electron dynamics in hematite (α-Fe 2 O 3 ): correlation between ultrafast surface electron trapping and small polaron formation
journal, January 2017
- Husek, Jakub; Cirri, Anthony; Biswas, Somnath
- Chemical Science, Vol. 8, Issue 12
X-ray Transient Absorption and Picosecond IR Spectroscopy of Fulvalene(tetracarbonyl)diruthenium on Photoexcitation
journal, June 2012
- Harpham, Michael R.; Nguyen, Son C.; Hou, Zongrui
- Angewandte Chemie, Vol. 124, Issue 31
Relationship between Work Function of Hole Collection Electrode and Temperature Dependence of Open-Circuit Voltage in Multilayered Organic Solar Cells
journal, February 2012
- Itoh, Eiji; Shirotori, Toshiki
- Japanese Journal of Applied Physics, Vol. 51, Issue 2
Achieving Surface Sensitivity in Ultrafast XUV Spectroscopy: M2,3-edge Reflection-Absorption of Transition Metal Oxides
conference, January 2017
- Baker, L. Robert; Cirri, Anthony; Husek, Jakub
- Laser Science, Frontiers in Optics 2017
Site-Selective Passivation of Defects in NiO Solar Photocathodes by Targeted Atomic Deposition
text, January 2016
- L., Li,; J. R., McBride,; T. J., Meyer,
- The University of North Carolina at Chapel Hill University Libraries
Exciton Ionization, Franz-Keldysh and Stark Effects in Carbon Nanotubes
text, January 2007
- Perebeinos, Vasili; Avouris, Phaedon
- arXiv
Works referencing / citing this record:
Controlling polaron formation at hematite surfaces by molecular functionalization probed by XUV reflection-absorption spectroscopy
journal, September 2019
- Biswas, Somnath; Wallentine, Spencer; Bandaranayake, Savini
- The Journal of Chemical Physics, Vol. 151, Issue 10
Photoinduced valence tautomerism of a cobalt-dioxolene complex revealed with femtosecond M-edge XANES
journal, September 2019
- Ash, Ryan; Zhang, Kaili; Vura-Weis, Josh
- The Journal of Chemical Physics, Vol. 151, Issue 10