The role of the domain size and titanium dopant in nanocrystalline hematite thin films for water photolysis

Yan, Danhua; Tao, Jing; Kisslinger, Kim; Cen, Jiajie; Wu, Qiyuan; Orlov, Alexander; Liu, Mingzhao

doi:10.1039/C5NR05894E

The role of the domain size and titanium dopant in nanocrystalline hematite thin films for water photolysis

Journal Article · Tue Oct 13 00:00:00 EDT 2015 · Nanoscale

DOI:https://doi.org/10.1039/C5NR05894E· OSTI ID:1224784

Yan, Danhua ^[1]; Tao, Jing ^[2]; Kisslinger, Kim ^[2]; Cen, Jiajie ^[3]; Wu, Qiyuan ^[3]; Orlov, Alexander ^[3]; Liu, Mingzhao ^[2]

Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., Stony Brook, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Stony Brook Univ., Stony Brook, NY (United States)

In this study, we develop a novel technique for preparing high quality Ti-doped hematite thin films for photoelectrochemical (PEC) water splitting, through sputtering deposition of metallic iron films from an iron target embedded with titanium (dopants) pellets, followed by a thermal oxidation step that turns the metal films into doped hematite. It is found that the hematite domain size can be tuned from ~10 nm to over 100 nm by adjusting the sputtering atmosphere from more oxidative to mostly inert. The better crystallinity at a larger domain size ensures excellent PEC water splitting performance, leading to record high photocurrent from pure planar hematite thin films on FTO substrates. Titanium doping further enhances the PEC performance of hematite photoanodes. The photocurrent is improved by 50%, with a titanium dopant concentration as low as 0.5 atom%. It is also found that the role of the titanium dopant in improving the PEC performance is not apparently related to the films’ electrical conductivity which had been widely believed, but is more likely due to the passivation of surface defects by the titanium dopants.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI ID:: 1224784

Alternate ID(s):: OSTI ID: 1237187

Report Number(s):: BNL--108520-2015-JA; BNL--111762-2016-JA; KC0403020

Journal Information:: Nanoscale, Journal Name: Nanoscale; ISSN NANOHL; ISSN 2040-3364

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (44)

Solar Water Splitting: Progress Using Hematite (α-Fe2O3) Photoelectrodes Sivula, Kevin; Le Formal, Florian; Grätzel, Michael ChemSusChem, Vol. 4, Issue 4 https://doi.org/10.1002/cssc.201000416	journal	March 2011
Ti-doped hematite thin films for efficient water splitting Atabaev, Timur Sh.; Ajmal, Muhammad; Hong, Nguyen Hoa Applied Physics A, Vol. 118, Issue 4 https://doi.org/10.1007/s00339-014-8937-7	journal	December 2014
Optical absorption spectrum of hematite, αFe2O3 near IR to UV Marusak, L. A.; Messier, R.; White, William B. Journal of Physics and Chemistry of Solids, Vol. 41, Issue 9 https://doi.org/10.1016/0022-3697(80)90105-5	journal	January 1980
Dye-sensitized solar cells Grätzel, Michael Journal of Photochemistry and Photobiology C: Photochemistry Reviews, Vol. 4, Issue 2, p. 145-153 https://doi.org/10.1016/S1389-5567(03)00026-1	journal	October 2003
On the improvement of PEC activity of hematite thin films deposited by high-power pulsed magnetron sputtering method Kment, S.; Hubicka, Z.; Krysa, J. Applied Catalysis B: Environmental, Vol. 165 https://doi.org/10.1016/j.apcatb.2014.10.015	journal	April 2015
Evolution of structural properties of iron oxide nano particles during temperature treatment from 250 °C–900 °C: X-ray diffraction and Fe K-shell pre-edge X-ray absorption study Bora, Debajeet K.; Braun, Artur; Erat, Selma Current Applied Physics, Vol. 12, Issue 3 https://doi.org/10.1016/j.cap.2011.11.013	journal	May 2012
Spray pyrolytically deposited nanoporous Ti⁴⁺ doped hematite thin films for efficient photoelectrochemical splitting of water Kumari, Saroj; Singh, Aadesh P. International Journal of Hydrogen Energy, Vol. 35, Issue 9, p. 3985-3990 https://doi.org/10.1016/j.ijhydene.2010.01.101	journal	May 2010
Effects of annealing temperature on the physicochemical, optical and photoelectrochemical properties of nanostructured hematite thin films prepared via electrodeposition method Phuan, Yi Wen; Chong, Meng Nan; Zhu, Tao Materials Research Bulletin, Vol. 69 https://doi.org/10.1016/j.materresbull.2014.12.059	journal	September 2015
Structural, optical and electrical properties of undoped polycrystalline hematite thin films produced using filtered arc deposition Glasscock, J. A.; Barnes, P. R. F.; Plumb, I. C. Thin Solid Films, Vol. 516, Issue 8 https://doi.org/10.1016/j.tsf.2007.05.020	journal	February 2008
Thin-Layer Fe ₂ TiO ₅ on Hematite for Efficient Solar Water Oxidation Deng, Jiujun; Lv, Xiaoxin; Liu, Jinyin ACS Nano, Vol. 9, Issue 5 https://doi.org/10.1021/acsnano.5b01028	journal	April 2015
Improving Hematite-based Photoelectrochemical Water Splitting with Ultrathin TiO ₂ by Atomic Layer Deposition Yang, Xiaogang; Liu, Rui; Du, Chun ACS Applied Materials & Interfaces, Vol. 6, Issue 15 https://doi.org/10.1021/am500948t	journal	July 2014
Photoelectrochemical Performance of Nanostructured Ti- and Sn-Doped α-Fe ₂ O ₃ Photoanodes Hahn, Nathan T.; Mullins, C. Buddie Chemistry of Materials, Vol. 22, Issue 23 https://doi.org/10.1021/cm1026078	journal	December 2010
Pt-Doped α-Fe ₂ O ₃ Thin Films Active for Photoelectrochemical Water Splitting Hu, Yong-Sheng; Kleiman-Shwarsctein, Alan; Forman, Arnold J. Chemistry of Materials, Vol. 20, Issue 12 https://doi.org/10.1021/cm800144q	journal	June 2008
Solar Water Splitting Cells Walter, Michael G.; Warren, Emily L.; McKone, James R. Chemical Reviews, Vol. 110, Issue 11, p. 6446-6473 https://doi.org/10.1021/cr1002326	journal	November 2010
Visible Light Driven Photoelectrochemical Water Oxidation by Zn- and Ti-Doped Hematite Nanostructures Mirbagheri, Naghmehalsadat; Wang, Degao; Peng, Cheng ACS Catalysis, Vol. 4, Issue 6 https://doi.org/10.1021/cs500372v	journal	April 2014
Analysis of iron oxidation at high temperatures Slattery, John C.; Peng, Kuang-Yao; Gadalla, A. M. Industrial & Engineering Chemistry Research, Vol. 34, Issue 10 https://doi.org/10.1021/ie00037a028	journal	October 1995
Translucent Thin Film Fe ₂ O ₃ Photoanodes for Efficient Water Splitting by Sunlight: Nanostructure-Directing Effect of Si-Doping Cesar, Ilkay; Kay, Andreas; Gonzalez Martinez, José A. Journal of the American Chemical Society, Vol. 128, Issue 14 https://doi.org/10.1021/ja060292p	journal	April 2006
New Benchmark for Water Photooxidation by Nanostructured α-Fe ₂ O ₃ Films Kay, Andreas; Cesar, Ilkay; Grätzel, Michael Journal of the American Chemical Society, Vol. 128, Issue 49 https://doi.org/10.1021/ja064380l	journal	December 2006
Nanonet-Based Hematite Heteronanostructures for Efficient Solar Water Splitting Lin, Yongjing; Zhou, Sa; Sheehan, Stafford W. Journal of the American Chemical Society, Vol. 133, Issue 8 https://doi.org/10.1021/ja110741z	journal	March 2011
Photoelectrochemical Oxidation of Water at Transparent Ferric Oxide Film Electrodes Jorand Sartoretti, Chantal; Alexander, Bruce D.; Solarska, Renata The Journal of Physical Chemistry B, Vol. 109, Issue 28 https://doi.org/10.1021/jp051546g	journal	July 2005
Enhancement of Photoelectrochemical Hydrogen Production from Hematite Thin Films by the Introduction of Ti and Si Glasscock, Julie A.; Barnes, Piers R. F.; Plumb, Ian C. The Journal of Physical Chemistry C, Vol. 111, Issue 44 https://doi.org/10.1021/jp074556l	journal	November 2007
Current and Voltage Limiting Processes in Thin Film Hematite Electrodes Klahr, Benjamin M.; Hamann, Thomas W. The Journal of Physical Chemistry C, Vol. 115, Issue 16 https://doi.org/10.1021/jp200197d	journal	March 2011
Enhancing Water Splitting Activity and Chemical Stability of Zinc Oxide Nanowire Photoanodes with Ultrathin Titania Shells Liu, Mingzhao; Nam, Chang-Yong; Black, Charles T. The Journal of Physical Chemistry C, Vol. 117, Issue 26 https://doi.org/10.1021/jp404032p	journal	June 2013
Observation and Alteration of Surface States of Hematite Photoelectrodes Du, Chun; Zhang, Ming; Jang, Ji-Wook The Journal of Physical Chemistry C, Vol. 118, Issue 30 https://doi.org/10.1021/jp5006346	journal	April 2014
Combining Mesoporosity and Ti-Doping in Hematite Films for Water Splitting Toussaint, Caroline; Le Tran, Hoang Long; Colson, Pierre The Journal of Physical Chemistry C, Vol. 119, Issue 4 https://doi.org/10.1021/jp5091476	journal	January 2015
Activation of Hematite Photoanodes for Solar Water Splitting: Effect of FTO Deformation Annamalai, Alagappan; Subramanian, Arunprabaharan; Kang, Unseock The Journal of Physical Chemistry C, Vol. 119, Issue 7 https://doi.org/10.1021/jp512189c	journal	February 2015
Electrodeposition of α-Fe ₂ O ₃ Doped with Mo or Cr as Photoanodes for Photocatalytic Water Splitting Kleiman-Shwarsctein, Alan; Hu, Yong-Sheng; Forman, Arnold J. The Journal of Physical Chemistry C, Vol. 112, Issue 40 https://doi.org/10.1021/jp803775j	journal	September 2008
Influence of Feature Size, Film Thickness, and Silicon Doping on the Performance of Nanostructured Hematite Photoanodes for Solar Water Splitting Cesar, Ilkay; Sivula, Kevin; Kay, Andreas The Journal of Physical Chemistry C, Vol. 113, Issue 2 https://doi.org/10.1021/jp809060p	journal	December 2008
Rapid Screening of Effective Dopants for Fe ₂ O ₃ Photocatalysts with Scanning Electrochemical Microscopy and Investigation of Their Photoelectrochemical Properties Jang, Jum Suk; Lee, Joowook; Ye, Heechang The Journal of Physical Chemistry C, Vol. 113, Issue 16 https://doi.org/10.1021/jp8109429	journal	March 2009
Facile Synthesis of Highly Photoactive α-Fe ₂ O ₃ -Based Films for Water Oxidation Wang, Gongming; Ling, Yichuan; Wheeler, Damon A. Nano Letters, Vol. 11, Issue 8 https://doi.org/10.1021/nl202316j	journal	August 2011
Electrochemical Photolysis of Water at a Semiconductor Electrode Fujishima, Akira; Honda, Kenichi Nature, Vol. 238, Issue 5358, p. 37-38 https://doi.org/10.1038/238037a0	journal	July 1972
Photoelectrochemical cells Grätzel, Michael Nature, Vol. 414, Issue 6861 https://doi.org/10.1038/35104607	journal	November 2001
Single-crystalline, wormlike hematite photoanodes for efficient solar water splitting Kim, Jae Young; Magesh, Ganesan; Youn, Duck Hyun Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep02681	journal	September 2013
Highly photoactive Ti-doped α-Fe ₂ O ₃ thin film electrodes: resurrection of the dead layer Zandi, Omid; Klahr, Benjamin M.; Hamann, Thomas W. Energy Environ. Sci., Vol. 6, Issue 2 https://doi.org/10.1039/C2EE23620F	journal	January 2013
Hematite photoelectrodes for water splitting: evaluation of the role of film thickness by impedance spectroscopy Lopes, Tânia; Andrade, Luísa; Le Formal, Florian Physical Chemistry Chemical Physics, Vol. 16, Issue 31 https://doi.org/10.1039/C3CP55473B	journal	January 2014
The influence of the film thickness of nanostructured α-Fe2O3 on water photooxidation Souza, Flavio Leandro; Lopes, Kirian Pimenta; Longo, Elson Physical Chemistry Chemical Physics, Vol. 11, Issue 8 https://doi.org/10.1039/b811946e	journal	January 2009
Carrier dynamics in α‐Fe2O3 (0001) thin films and single crystals probed by femtosecond transient absorption and reflectivity Joly, Alan G.; Williams, Joshua R.; Chambers, Scott A. Journal of Applied Physics, Vol. 99, Issue 5 https://doi.org/10.1063/1.2177426	journal	March 2006
Grain boundary recombination: Theory and experiment in silicon Seager, C. H. Journal of Applied Physics, Vol. 52, Issue 6 https://doi.org/10.1063/1.329202	journal	June 1981
Enhanced photoelectrochemical activity for Cu and Ti doped hematite: The first principles calculations Meng, X. Y.; Qin, G. W.; Li, S. Applied Physics Letters, Vol. 98, Issue 11 https://doi.org/10.1063/1.3567766	journal	March 2011
Synthesis and characterization of titanium-alloyed hematite thin films for photoelectrochemical water splitting Tang, Houwen; Matin, M. A.; Wang, Heli Journal of Applied Physics, Vol. 110, Issue 12 https://doi.org/10.1063/1.3671414	journal	December 2011
Magnetron sputtering of transparent conductive zinc oxide: relation between the sputtering parameters and the electronic properties Ellmer, Klaus Journal of Physics D: Applied Physics, Vol. 33, Issue 4 https://doi.org/10.1088/0022-3727/33/4/201	journal	February 2000
Electrical Properties of Silicon Containing Arsenic and Boron Morin, F. J.; Maita, J. P. Physical Review, Vol. 96, Issue 1 https://doi.org/10.1103/PhysRev.96.28	journal	October 1954
Electronic processes at grain boundaries in polycrystalline semiconductors under optical illumination Card, H. C.; Yang, E. S. IEEE Transactions on Electron Devices, Vol. 24, Issue 4 https://doi.org/10.1109/T-ED.1977.18747	journal	April 1977
Photoelectrochemical Characterization of Sprayed α - Fe 2 O 3 Thin Films: Influence of Si Doping and SnO 2 Interfacial Layer Liang, Yongqi; Enache, Cristina S.; van de Krol, Roel International Journal of Photoenergy, Vol. 2008 https://doi.org/10.1155/2008/739864	journal	January 2008

Similar Records

Effects of annealing temperature on the physicochemical, optical and photoelectrochemical properties of nanostructured hematite thin films prepared via electrodeposition method

Journal Article · Tue Sep 15 00:00:00 EDT 2015 · Materials Research Bulletin · OSTI ID:22475872

Synthesis and Characterization of Titanium-Alloyed Hematite Thin Films for Photoelectrochemical Water Splitting

Journal Article · Wed Dec 14 23:00:00 EST 2011 · Journal of Applied Physics · OSTI ID:1046316

Related Subjects

77 NANOSCIENCE AND NANOTECHNOLOGY
Center for Functional Nanomaterials
graded doping
indirect band gap semiconductor
photoelectrochemical water splitting
strontium titanate

The role of the domain size and titanium dopant in nanocrystalline hematite thin films for water photolysis

Citation Formats

References (44)

Similar Records

Related Subjects