Conducting interface in oxide homojunction: Understanding of superior properties in black TiO2

Lu, Xujie; Chen, Aiping; Luo, Yongkang; Lu, Ping; Dai, Yaomin; Enriquez, Erik M.; Dowden, Paul Charles; Xu, Hongwu; Kotula, Paul G.; Azad, Abul Kalam; Yarotski, Dmitry Anatolievitch; Prasankumar, Rohit Prativadi; Taylor, Antoinette Jane; Thompson, Joe David; Jia, Quanxi

doi:10.1021/acs.nanolett.6b02454

Title: Conducting interface in oxide homojunction: Understanding of superior properties in black TiO₂

Journal Article · Wed Sep 14 00:00:00 EDT 2016 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.6b02454· OSTI ID:1331278

Lu, Xujie ^[1]; Chen, Aiping ^[1]; Luo, Yongkang ^[1]; Lu, Ping ^[2]; Dai, Yaomin ^[1]; Enriquez, Erik M. ^[1]; Dowden, Paul Charles ^[1]; Xu, Hongwu ^[1]; Kotula, Paul G. ^[2]; Azad, Abul Kalam ^[1]; Yarotski, Dmitry Anatolievitch ^[1]; Prasankumar, Rohit Prativadi ^[1]; Taylor, Antoinette Jane ^[1]; Thompson, Joe David ^[1]; Jia, Quanxi ^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Black TiO₂ nanoparticles with a crystalline core and amorphous-shell structure exhibit superior optoelectronic properties in comparison with pristine TiO₂. The fundamental mechanisms underlying these enhancements, however, remain unclear, largely due to the inherent complexities and limitations of powder materials. Here, we fabricate TiO₂ homojunction films consisting of an oxygen-deficient amorphous layer on top of a highly crystalline layer, to simulate the structural/functional configuration of black TiO₂ nanoparticles. Metallic conduction is achieved at the crystalline–amorphous homointerface via electronic interface reconstruction, which we show to be the main reason for the enhanced electron transport of black TiO₂. As a result, this work not only achieves an unprecedented understanding of black TiO₂ but also provides a new perspective for investigating carrier generation and transport behavior at oxide interfaces, which are of tremendous fundamental and technological interest.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC52-06NA25396

OSTI ID:: 1331278

Report Number(s):: LA-UR-16-22153

Journal Information:: Nano Letters, Vol. 16, Issue 9; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 80 works

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References (33)

Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected Results Linsebigler, Amy L.; Lu, Guangquan.; Yates, John T. Chemical Reviews, Vol. 95, Issue 3 https://doi.org/10.1021/cr00035a013	journal	May 1995
Mesoporous TiO2 single crystals delivering enhanced mobility and optoelectronic device performance Crossland, Edward J. W.; Noel, Nakita; Sivaram, Varun Nature, Vol. 495, Issue 7440 https://doi.org/10.1038/nature11936	journal	March 2013
Band alignment of rutile and anatase TiO2 Scanlon, David O.; Dunnill, Charles W.; Buckeridge, John Nature Materials, Vol. 12, Issue 9 https://doi.org/10.1038/nmat3697	journal	July 2013
Enhanced Electron Transport in Nb-Doped TiO ₂ Nanoparticles via Pressure-Induced Phase Transitions Lü, Xujie; Yang, Wenge; Quan, Zewei Journal of the American Chemical Society, Vol. 136, Issue 1 https://doi.org/10.1021/ja410810w	journal	December 2013
Water reduction by a p-GaInP2 photoelectrode stabilized by an amorphous TiO2 coating and a molecular cobalt catalyst Gu, Jing; Yan, Yong; Young, James L. Nature Materials, Vol. 15, Issue 4 https://doi.org/10.1038/nmat4511	journal	December 2015
Visible-Light Photocatalysis in Nitrogen-Doped Titanium Oxides Asahi, R. Science, Vol. 293, Issue 5528 https://doi.org/10.1126/science.1061051	journal	July 2001
A General Preparation Strategy for Hybrid TiO2 Hierarchical Spheres and Their Enhanced Solar Energy Utilization Efficiency Lü, Xujie; Huang, Fuqiang; Mou, Xinliang Advanced Materials, Vol. 22, Issue 33 https://doi.org/10.1002/adma.201001008	journal	August 2010
Reversible oxygen scavenging at room temperature using electrochemically reduced titanium oxide nanotubes Close, Thomas; Tulsyan, Gaurav; Diaz, Carlos A. Nature Nanotechnology, Vol. 10, Issue 5 https://doi.org/10.1038/nnano.2015.51	journal	April 2015
Increasing Solar Absorption for Photocatalysis with Black Hydrogenated Titanium Dioxide Nanocrystals Chen, X.; Liu, L.; Yu, P. Y. Science, Vol. 331, Issue 6018 https://doi.org/10.1126/science.1200448	journal	January 2011
Ordered Mesoporous Black TiO ₂ as Highly Efficient Hydrogen Evolution Photocatalyst Zhou, Wei; Li, Wei; Wang, Jian-Qiang Journal of the American Chemical Society, Vol. 136, Issue 26 https://doi.org/10.1021/ja504802q	journal	June 2014
Structure and Formation Mechanism of Black TiO ₂ Nanoparticles Tian, Mengkun; Mahjouri-Samani, Masoud; Eres, Gyula ACS Nano, Vol. 9, Issue 10 https://doi.org/10.1021/acsnano.5b04712	journal	September 2015
Black anatase titania enabling ultra high cycling rates for rechargeable lithium batteries Myung, Seung-Taek; Kikuchi, Masaru; Yoon, Chong Seung Energy & Environmental Science, Vol. 6, Issue 9 https://doi.org/10.1039/c3ee41960f	journal	January 2013
Hydrogenated TiO ₂ Nanotube Arrays for Supercapacitors Lu, Xihong; Wang, Gongming; Zhai, Teng Nano Letters, Vol. 12, Issue 3 https://doi.org/10.1021/nl300173j	journal	February 2012
Black titanium dioxide (TiO ₂ ) nanomaterials Chen, Xiaobo; Liu, Lei; Huang, Fuqiang Chemical Society Reviews, Vol. 44, Issue 7 https://doi.org/10.1039/C4CS00330F	journal	January 2015
Oxygen-Deficient TiO _2−δ Nanoparticles via Hydrogen Reduction for High Rate Capability Lithium Batteries Shin, Ji-Yong; Joo, Jong Hoon; Samuelis, Dominik Chemistry of Materials, Vol. 24, Issue 3 https://doi.org/10.1021/cm2031009	journal	December 2011
Unveiling Two Electron-Transport Modes in Oxygen-Deficient TiO ₂ Nanowires and Their Influence on Photoelectrochemical Operation Chen, Haining; Wei, Zhanhua; Yan, Keyou The Journal of Physical Chemistry Letters, Vol. 5, Issue 16 https://doi.org/10.1021/jz5014505	journal	August 2014
H-Doped Black Titania with Very High Solar Absorption and Excellent Photocatalysis Enhanced by Localized Surface Plasmon Resonance Wang, Zhou; Yang, Chongyin; Lin, Tianquan Advanced Functional Materials, Vol. 23, Issue 43 https://doi.org/10.1002/adfm.201300486	journal	May 2013
Effective nonmetal incorporation in black titania with enhanced solar energy utilization Lin, Tianquan; Yang, Chongyin; Wang, Zhou Energy & Environmental Science, Vol. 7, Issue 3 https://doi.org/10.1039/c3ee42708k	journal	January 2014
Effect of Nature and Location of Defects on Bandgap Narrowing in Black TiO ₂ Nanoparticles Naldoni, Alberto; Allieta, Mattia; Santangelo, Saveria Journal of the American Chemical Society, Vol. 134, Issue 18 https://doi.org/10.1021/ja3012676	journal	April 2012
Core-Shell Nanostructured “Black” Rutile Titania as Excellent Catalyst for Hydrogen Production Enhanced by Sulfur Doping Yang, Chongyin; Wang, Zhou; Lin, Tianquan Journal of the American Chemical Society, Vol. 135, Issue 47 https://doi.org/10.1021/ja4076748	journal	November 2013
Hydrogenation and Disorder in Engineered Black ${TiO}_{2}$ Liu, Lei; Yu, Peter Y.; Chen, Xiaobo Physical Review Letters, Vol. 111, Issue 6 https://doi.org/10.1103/PhysRevLett.111.065505	journal	August 2013
Visible-light photocatalytic, solar thermal and photoelectrochemical properties of aluminium-reduced black titania Wang, Zhou; Yang, Chongyin; Lin, Tianquan Energy & Environmental Science, Vol. 6, Issue 10 https://doi.org/10.1039/c3ee41817k	journal	January 2013
Electrodynamics of Solids Dressel, Martin; Grüner, George Cambridge University Press https://doi.org/10.1017/CBO9780511606168	book	January 2010
A high-mobility electron gas at the LaAlO3/SrTiO3 heterointerface Ohtomo, A.; Hwang, H. Y. Nature, Vol. 427, Issue 6973 https://doi.org/10.1038/nature02308	journal	January 2004
Superconducting Interfaces Between Insulating Oxides Reyren, N.; Thiel, S.; Caviglia, A. D. Science, Vol. 317, Issue 5842 https://doi.org/10.1126/science.1146006	journal	August 2007
High-temperature interface superconductivity between metallic and insulating copper oxides Gozar, A.; Logvenov, G.; Kourkoutis, L. Fitting Nature, Vol. 455, Issue 7214, p. 782-785 https://doi.org/10.1038/nature07293	journal	October 2008
Oxide Interfaces--An Opportunity for Electronics Mannhart, J.; Schlom, D. G. Science, Vol. 327, Issue 5973, p. 1607-1611 https://doi.org/10.1126/science.1181862	journal	March 2010
Emergent phenomena at oxide interfaces Hwang, H. Y.; Iwasa, Y.; Kawasaki, M. Nature Materials, Vol. 11, Issue 2 https://doi.org/10.1038/nmat3223	journal	January 2012
Why some interfaces cannot be sharp Nakagawa, Naoyuki; Hwang, Harold Y.; Muller, David A. Nature Materials, Vol. 5, Issue 3, p. 204-209 https://doi.org/10.1038/nmat1569	journal	January 2006
Atomic-scale imaging of nanoengineered oxygen vacancy profiles in SrTiO3 Muller, David A.; Nakagawa, Naoyuki; Ohtomo, Akira Nature, Vol. 430, Issue 7000 https://doi.org/10.1038/nature02756	journal	August 2004
Minority carrier accumulation at high-low junctions in't Hout, S. R. Solid-State Electronics, Vol. 36, Issue 8 https://doi.org/10.1016/0038-1101(93)90193-T	journal	August 1993
Built-in and induced polarization across LaAlO3/SrTiO3 heterojunctions Singh-Bhalla, Guneeta; Bell, Christopher; Ravichandran, Jayakanth Nature Physics, Vol. 7, Issue 1 https://doi.org/10.1038/nphys1814	journal	October 2010
Electronic reconstruction at an interface between a Mott insulator and a band insulator Okamoto, Satoshi; Millis, Andrew J. Nature, Vol. 428, Issue 6983 https://doi.org/10.1038/nature02450	journal	April 2004

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