Identifying the acceptor state in NiO hole collection layers: direct observation of exciton dissociation and interfacial hole transfer across a Fe2O3/NiO heterojunction

Biswas, Somnath; Husek, Jakub; Londo, Stephen; Fugate, Elizabeth A.; Baker, L. Robert

doi:10.1039/c8cp04502j

Title: Identifying the acceptor state in NiO hole collection layers: direct observation of exciton dissociation and interfacial hole transfer across a Fe₂O₃/NiO heterojunction

Journal Article · Wed Sep 05 00:00:00 EDT 2018 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c8cp04502j· OSTI ID:1594155

^[1];

^[1]; Londo, Stephen ^[1]; Fugate, Elizabeth A. ^[1];

^[1]

The Ohio State Univ., Columbus, OH (United States)

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.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: The Ohio State Univ., Columbus, OH (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Grant/Contract Number:: SC0014051

OSTI ID:: 1594155

Alternate ID(s):: OSTI ID: 1469409

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 20, Issue 38; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 23 works

Citation information provided by
Web of Science

References (60)

Role of the Charge Transfer State in Organic Donor-Acceptor Solar Cells Deibel, Carsten; Strobel, Thomas; Dyakonov, Vladimir Advanced Materials, Vol. 22, Issue 37 https://doi.org/10.1002/adma.201000376	journal	August 2010
Glotaran : A Java -Based Graphical User Interface for the R Package TIMP Snellenburg, Joris J.; Laptenok, Sergey P.; Seger, Ralf Journal of Statistical Software, Vol. 49, Issue 3 https://doi.org/10.18637/jss.v049.i03	journal	January 2012
Femtosecond tracking of carrier relaxation in germanium with extreme ultraviolet transient reflectivity Kaplan, Christopher J.; Kraus, Peter M.; Ross, Andrew D. Physical Review B, Vol. 97, Issue 20 https://doi.org/10.1103/PhysRevB.97.205202	journal	May 2018
X-ray Transient Absorption and Picosecond IR Spectroscopy of Fulvalene(tetracarbonyl)diruthenium on Photoexcitation Harpham, Michael R.; Nguyen, Son C.; Hou, Zongrui Angewandte Chemie International Edition, Vol. 51, Issue 31 https://doi.org/10.1002/anie.201202952	journal	June 2012
NiO _x Hole Transport Layer for Perovskite Solar Cells with Improved Stability and Reproducibility Islam, Md. Bodiul; Yanagida, Masatoshi; Shirai, Yasuhiro ACS Omega, Vol. 2, Issue 5 https://doi.org/10.1021/acsomega.7b00538	journal	May 2017
Experimental determination of band offsets of NiO-based thin film heterojunctions Kawade, Daisuke; Chichibu, Shigefusa F.; Sugiyama, Mutsumi Journal of Applied Physics, Vol. 116, Issue 16 https://doi.org/10.1063/1.4900737	journal	October 2014
Carrier-Specific Femtosecond XUV Transient Absorption of PbI ₂ Reveals Ultrafast Nonradiative Recombination Lin, Ming-Fu; Verkamp, Max A.; Leveillee, Joshua The Journal of Physical Chemistry C, Vol. 121, Issue 50 https://doi.org/10.1021/acs.jpcc.7b11147	journal	December 2017
Band gaps and electronic structure of transition-metal compounds Zaanen, J.; Sawatzky, G. A.; Allen, J. W. Physical Review Letters, Vol. 55, Issue 4 https://doi.org/10.1103/PhysRevLett.55.418	journal	July 1985
Picosecond X-ray Absorption Spectroscopy of a Photoinduced Iron(II) Spin Crossover Reaction in Solution Khalil, Munira; Marcus, Matthew A.; Smeigh, Amanda L. The Journal of Physical Chemistry A, Vol. 110, Issue 1 https://doi.org/10.1021/jp055002q	journal	January 2006
Charge Separation and Exciton Dynamics at Polymer/ZnO Interface from First-Principles Simulations Wu, Guangfen; Li, Zi; Zhang, Xu The Journal of Physical Chemistry Letters, Vol. 5, Issue 15 https://doi.org/10.1021/jz500980q	journal	July 2014
How fast is interfacial hole transfer? In situ monitoring of carrier dynamics in anatase TiO2 nanoparticles by femtosecond laser spectroscopy Yang, Xiujuan; Tamai, Naoto Physical Chemistry Chemical Physics, Vol. 3, Issue 16 https://doi.org/10.1039/b101721g	journal	January 2001
Highly Localized Charge Transfer Excitons in Metal Oxide Semiconductors Biswas, Somnath; Husek, Jakub; Londo, Stephen Nano Letters, Vol. 18, Issue 2 https://doi.org/10.1021/acs.nanolett.7b04818	journal	January 2018
Ultrafast carrier thermalization and trapping in silicon-germanium alloy probed by extreme ultraviolet transient absorption spectroscopy Zürch, Michael; Chang, Hung-Tzu; Kraus, Peter M. Structural Dynamics, Vol. 4, Issue 4 https://doi.org/10.1063/1.4985056	journal	July 2017
Nickel Oxide Electrode Interlayer in CH ₃ NH ₃ PbI ₃ Perovskite/PCBM Planar-Heterojunction Hybrid Solar Cells Jeng, Jun-Yuan; Chen, Kuo-Cheng; Chiang, Tsung-Yu Advanced Materials, Vol. 26, Issue 24 https://doi.org/10.1002/adma.201306217	journal	March 2014
Electrochemical Behavior of Reactively Sputtered Iron-Doped Nickel Oxide Miller, Eric L. Journal of The Electrochemical Society, Vol. 144, Issue 9 https://doi.org/10.1149/1.1837961	journal	January 1997
Optical and thermal electron transfer in metal complexes Meyer, Thomas J. Accounts of Chemical Research, Vol. 11, Issue 3 https://doi.org/10.1021/ar50123a003	journal	March 1978
Femtosecond M _2,3 -Edge Spectroscopy of Transition-Metal Oxides: Photoinduced Oxidation State Change in α-Fe ₂ O ₃ Vura-Weis, Josh; Jiang, Chang-Ming; Liu, Chong The Journal of Physical Chemistry Letters, Vol. 4, Issue 21 https://doi.org/10.1021/jz401997d	journal	October 2013
Field-Assisted Exciton Dissociation in Highly Efficient PffBT4T-2OD:Fullerene Organic Solar Cells Weu, Andreas; Hopper, Thomas R.; Lami, Vincent Chemistry of Materials, Vol. 30, Issue 8 https://doi.org/10.1021/acs.chemmater.8b00094	journal	March 2018
Electronic and nuclear contributions to time-resolved optical and X-ray absorption spectra of hematite and insights into photoelectrochemical performance Hayes, Dugan; Hadt, Ryan G.; Emery, Jonathan D. Energy & Environmental Science, Vol. 9, Issue 12 https://doi.org/10.1039/C6EE02266A	journal	January 2016
Tabletop Femtosecond M-edge X-ray Absorption Near-Edge Structure of FeTPPCl: Metalloporphyrin Photophysics from the Perspective of the Metal Ryland, Elizabeth S.; Lin, Ming-Fu; Verkamp, Max A. Journal of the American Chemical Society, Vol. 140, Issue 13 https://doi.org/10.1021/jacs.8b01101	journal	March 2018
Excitation-wavelength-dependent small polaron trapping of photoexcited carriers in α-Fe2O3 Carneiro, Lucas M.; Cushing, Scott K.; Liu, Chong Nature Materials, Vol. 16, Issue 8 https://doi.org/10.1038/nmat4936	journal	July 2017
Influence of interface properties on charge density, band edge shifts and kinetics of the photoelectrochemical process in p-type NiO photocathodes Liu, Qian; Wei, Lifang; Yuan, Shuai RSC Advances, Vol. 5, Issue 88 https://doi.org/10.1039/C5RA13135A	journal	January 2015
Improved Exciton Dissociation at Semiconducting Polymer:ZnO Donor:Acceptor Interfaces via Nitrogen Doping of ZnO Musselman, Kevin P.; Albert-Seifried, Sebastian; Hoye, Robert L. Z. Advanced Functional Materials, Vol. 24, Issue 23 https://doi.org/10.1002/adfm.201303994	journal	March 2014
Inorganic p-type contact materials for perovskite-based solar cells Li, Ming-Hsien; Shen, Po-Shen; Wang, Kuo-Chin Journal of Materials Chemistry A, Vol. 3, Issue 17 https://doi.org/10.1039/C4TA06425A	journal	January 2015
Probing electronic binding potentials with attosecond photoelectron wavepackets Kiesewetter, D.; Jones, R. R.; Camper, A. Nature Physics, Vol. 14, Issue 1 https://doi.org/10.1038/nphys4279	journal	October 2017
New interpretations of XPS spectra of nickel metal and oxides Grosvenor, Andrew P.; Biesinger, Mark C.; Smart, Roger St. C. Surface Science, Vol. 600, Issue 9 https://doi.org/10.1016/j.susc.2006.01.041	journal	May 2006
p-Type semiconducting nickel oxide as an efficiency-enhancing anode interfacial layer in polymer bulk-heterojunction solar cells Irwin, M. D.; Buchholz, D. B.; Hains, A. W. Proceedings of the National Academy of Sciences, Vol. 105, Issue 8, p. 2783-2787 https://doi.org/10.1073/pnas.0711990105	journal	February 2008
Elucidating ultrafast electron dynamics at surfaces using extreme ultraviolet (XUV) reflection–absorption spectroscopy Biswas, Somnath; Husek, Jakub; Baker, L. Robert Chemical Communications, Vol. 54, Issue 34 https://doi.org/10.1039/C8CC01745J	journal	January 2018
Highly efficient perovskite solar cells incorporating NiO nanotubes: increased grain size and enhanced charge extraction Yun, Juyoung; Jun, Jaemoon; Yu, Haejun J. Mater. Chem. A, Vol. 5, Issue 41 https://doi.org/10.1039/C7TA05560A	journal	January 2017
Photoinduced Structural Dynamics of Molecular Systems Mapped by Time-Resolved X-ray Methods Chergui, Majed; Collet, Eric Chemical Reviews, Vol. 117, Issue 16 https://doi.org/10.1021/acs.chemrev.6b00831	journal	May 2017
Ultrafast Electron Trapping and Defect-Mediated Recombination in NiO Probed by Femtosecond Extreme Ultraviolet Reflection–Absorption Spectroscopy Biswas, Somnath; Husek, Jakub; Londo, Stephen The Journal of Physical Chemistry Letters, Vol. 9, Issue 17 https://doi.org/10.1021/acs.jpclett.8b01865	journal	August 2018
Nickel Oxide Hole Injection/Transport Layers for Efficient Solution-Processed Organic Light-Emitting Diodes Liu, Shuyi; Liu, Rui; Chen, Ying Chemistry of Materials, Vol. 26, Issue 15 https://doi.org/10.1021/cm501898y	journal	July 2014
Field emission from α-Fe2O3 nanoflakes: Effect of vacuum pressure, gas adsorption and in-situ thermal treatment Wu, J. Q.; Deng, S. Z.; Xu, N. S. Applied Surface Science, Vol. 292 https://doi.org/10.1016/j.apsusc.2013.11.160	journal	February 2014
p-Type Dye-Sensitized NiO Solar Cells: A Study by Electrochemical Impedance Spectroscopy Huang, Zhongjie; Natu, Gayatri; Ji, Zhiqiang The Journal of Physical Chemistry C, Vol. 115, Issue 50 https://doi.org/10.1021/jp205306g	journal	November 2011
Charge-Transfer Processes in Dye-Sensitized NiO Solar Cells Mori, Shogo; Fukuda, Shunya; Sumikura, Seiichi The Journal of Physical Chemistry C, Vol. 112, Issue 41 https://doi.org/10.1021/jp803919b	journal	September 2008
Solid-State Perovskite-Sensitized p-Type Mesoporous Nickel Oxide Solar Cells Tian, Haining; Xu, Bo; Chen, Hong ChemSusChem, Vol. 7, Issue 8 https://doi.org/10.1002/cssc.201402032	journal	April 2014
Ultrafast Exciton Dissociation and Long-Lived Charge Separation in a Photovoltaic Pentacene–MoS ₂ van der Waals Heterojunction Bettis Homan, Stephanie; Sangwan, Vinod K.; Balla, Itamar Nano Letters, Vol. 17, Issue 1 https://doi.org/10.1021/acs.nanolett.6b03704	journal	December 2016
Long-range exciton dissociation in organic solar cells Caruso, D.; Troisi, A. Proceedings of the National Academy of Sciences, Vol. 109, Issue 34 https://doi.org/10.1073/pnas.1206172109	journal	August 2012
NiO as an Inorganic Hole-Transporting Layer in Quantum-Dot Light-Emitting Devices Caruge, Jean-Michel; Halpert, Jonathan E.; Bulović, Vladimir Nano Letters, Vol. 6, Issue 12 https://doi.org/10.1021/nl0623208	journal	December 2006
Attosecond transient-absorption dynamics of xenon core-excited states in a strong driving field Kobayashi, Yuki; Timmers, Henry; Sabbar, Mazyar Physical Review A, Vol. 95, Issue 3 https://doi.org/10.1103/PhysRevA.95.031401	journal	March 2017
An ultra-thin, un-doped NiO hole transporting layer of highly efficient (16.4%) organic–inorganic hybrid perovskite solar cells Seo, Seongrok; Park, Ik Jae; Kim, Myungjun Nanoscale, Vol. 8, Issue 22 https://doi.org/10.1039/C6NR01601D	journal	January 2016
Design of α-Fe2O3 nanorods functionalized tubular NiO nanostructure for discriminating toluene molecules Wang, Chen; Wang, Tianshuang; Wang, Boqun Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep26432	journal	May 2016
Achieving Surface Sensitivity in Ultrafast XUV Spectroscopy: M _2,3 -Edge Reflection–Absorption of Transition Metal Oxides Cirri, Anthony; Husek, Jakub; Biswas, Somnath The Journal of Physical Chemistry C, Vol. 121, Issue 29 https://doi.org/10.1021/acs.jpcc.7b05127	journal	July 2017
Relationship between Work Function of Hole Collection Electrode and Temperature Dependence of Open-Circuit Voltage in Multilayered Organic Solar Cells Itoh, Eiji; Shirotori, Toshiki Japanese Journal of Applied Physics, Vol. 51, Issue 2S https://doi.org/10.7567/JJAP.51.02BK14	journal	February 2012
Review of third and next generation synchrotron light sources Bilderback, Donald H.; Elleaume, Pascal; Weckert, Edgar Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 38, Issue 9 https://doi.org/10.1088/0953-4075/38/9/022	journal	April 2005
Dissociation of two-dimensional excitons in monolayer WSe2 Massicotte, Mathieu; Vialla, Fabien; Schmidt, Peter Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-03864-y	journal	April 2018
Site-Selective Passivation of Defects in NiO Solar Photocathodes by Targeted Atomic Deposition Flynn, Cory J.; McCullough, Shannon M.; Oh, EunBi ACS Applied Materials & Interfaces, Vol. 8, Issue 7 https://doi.org/10.1021/acsami.6b01090	journal	February 2016
Hole Thermalization Dynamics Facilitate Ultrafast Spatial Charge Separation in CuFeO ₂ Solar Photocathodes Husek, Jakub; Cirri, Anthony; Biswas, Somnath The Journal of Physical Chemistry C, Vol. 122, Issue 21 https://doi.org/10.1021/acs.jpcc.8b02996	journal	May 2018
Spectroscopic investigation of the hole states in Ni-deficient NiO films Cho, Deok-Yong; Song, Seul Ji; Kim, Un Ki Journal of Materials Chemistry C, Vol. 1, Issue 28 https://doi.org/10.1039/c3tc30687a	journal	January 2013
Exciton Ionization, Franz−Keldysh, and Stark Effects in Carbon Nanotubes Perebeinos, Vasili; Avouris, Phaedon Nano Letters, Vol. 7, Issue 3 https://doi.org/10.1021/nl0625022	journal	March 2007
Structural and Electrical Functionality of NiO Interfacial Films in Bulk Heterojunction Organic Solar Cells Irwin, Michael D.; Servaites, Jonathan D.; Buchholz, D. Bruce Chemistry of Materials, Vol. 23, Issue 8 https://doi.org/10.1021/cm200229e	journal	April 2011
Visualizing Interfacial Charge Transfer in Ru-Dye-Sensitized TiO ₂ Nanoparticles Using X-ray Transient Absorption Spectroscopy Zhang, Xiaoyi; Smolentsev, Grigory; Guo, Jianchang The Journal of Physical Chemistry Letters, Vol. 2, Issue 6 https://doi.org/10.1021/jz200122r	journal	February 2011
Influence of iron doping on tetravalent nickel content in catalytic oxygen evolving films Li, Nancy; Bediako, D. Kwabena; Hadt, Ryan G. Proceedings of the National Academy of Sciences, Vol. 114, Issue 7 https://doi.org/10.1073/pnas.1620787114	journal	January 2017
Bilayer Dye Protected Aqueous Photocathodes for Tandem Dye-Sensitized Solar Cells Click, Kevin A.; Schockman, Bradley M.; Dilenschneider, Justin T. The Journal of Physical Chemistry C, Vol. 121, Issue 16 https://doi.org/10.1021/acs.jpcc.7b01911	journal	April 2017
Surface electron dynamics in hematite (α-Fe ₂ O ₃ ): correlation between ultrafast surface electron trapping and small polaron formation Husek, Jakub; Cirri, Anthony; Biswas, Somnath Chemical Science, Vol. 8, Issue 12 https://doi.org/10.1039/C7SC02826A	journal	January 2017
X-ray Transient Absorption and Picosecond IR Spectroscopy of Fulvalene(tetracarbonyl)diruthenium on Photoexcitation Harpham, Michael R.; Nguyen, Son C.; Hou, Zongrui Angewandte Chemie, Vol. 124, Issue 31 https://doi.org/10.1002/ange.201202952	journal	June 2012
Relationship between Work Function of Hole Collection Electrode and Temperature Dependence of Open-Circuit Voltage in Multilayered Organic Solar Cells Itoh, Eiji; Shirotori, Toshiki Japanese Journal of Applied Physics, Vol. 51, Issue 2 https://doi.org/10.1143/jjap.51.02bk14	journal	February 2012
Achieving Surface Sensitivity in Ultrafast XUV Spectroscopy: M2,3-edge Reflection-Absorption of Transition Metal Oxides Baker, L. Robert; Cirri, Anthony; Husek, Jakub Laser Science, Frontiers in Optics 2017 https://doi.org/10.1364/ls.2017.ltu5f.4	conference	January 2017
Site-Selective Passivation of Defects in NiO Solar Photocathodes by Targeted Atomic Deposition L., Li,; J. R., McBride,; T. J., Meyer, The University of North Carolina at Chapel Hill University Libraries https://doi.org/10.17615/mt30-nx40	text	January 2016
Exciton Ionization, Franz-Keldysh and Stark Effects in Carbon Nanotubes Perebeinos, Vasili; Avouris, Phaedon arXiv https://doi.org/10.48550/arxiv.cond-mat/0701729	text	January 2007

Cited By (2)

Controlling polaron formation at hematite surfaces by molecular functionalization probed by XUV reflection-absorption spectroscopy Biswas, Somnath; Wallentine, Spencer; Bandaranayake, Savini The Journal of Chemical Physics, Vol. 151, Issue 10 https://doi.org/10.1063/1.5115163	journal	September 2019
Photoinduced valence tautomerism of a cobalt-dioxolene complex revealed with femtosecond M-edge XANES Ash, Ryan; Zhang, Kaili; Vura-Weis, Josh The Journal of Chemical Physics, Vol. 151, Issue 10 https://doi.org/10.1063/1.5115227	journal	September 2019

Similar Records

Elucidating ultrafast electron dynamics at surfaces using extreme ultraviolet (XUV) reflection–absorption spectroscopy

Journal Article · Fri Apr 06 00:00:00 EDT 2018 · ChemComm · OSTI ID:1594155

Biswas, Somnath; Husek, Jakub; Baker, L. Robert

Highly Localized Charge Transfer Excitons in Metal Oxide Semiconductors

Journal Article · Thu Jan 25 00:00:00 EST 2018 · Nano Letters · OSTI ID:1594155

Biswas, Somnath; Husek, Jakub; Londo, Stephen; +1 more

Small Polarons and Surface Defects in Metal Oxide Photocatalysts Studied Using XUV Reflection–Absorption Spectroscopy

Journal Article · Tue Sep 29 00:00:00 EDT 2020 · Journal of Physical Chemistry. C · OSTI ID:1594155

Bandaranayake, Savini; Hruska, Emily; Londo, Stephen; +2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Identifying the acceptor state in NiO hole collection layers: direct observation of exciton dissociation and interfacial hole transfer across a Fe2O3/NiO heterojunction

Citation Formats

References (60)

Cited By (2)

Similar Records

Related Subjects

Title: Identifying the acceptor state in NiO hole collection layers: direct observation of exciton dissociation and interfacial hole transfer across a Fe₂O₃/NiO heterojunction