Skip to main content
SpringerLink
Log in

Domain-engineered BiFeO3 thin-film photoanodes for highly enhanced ferroelectric solar water splitting

  • Research Article
  • Published:
Nano Research Aims and scope Submit manuscript

Abstract

In photoelectrochemical (PEC) water splitting, charge separation and collection by the electric field in the photoactive material are the most important factors for improved conversion efficiency. Hence, ferroelectric oxides, in which electrons are the majority carriers, are considered promising photoanode materials because their high built-in potential, provided by their spontaneous polarization, can significantly enhance the separation and drift of photogenerated carriers. In this regard, the PEC properties of BiFeO3 thin-film photoanodes with different crystallographic orientations and consequent ferroelectric domain structures are investigated. As the crystallographic orientation changes from (001)pc via (110)pc to (111)pc, the ferroelastic domains in epitaxial BiFeO3 thin films become mono-variant and the spontaneous polarization levels increase to 110 μC/cm2. Consequently, the photocurrent density at 0 V vs. Ag/AgCl increases approximately 5.3-fold and the onset potential decreases by 0.180 V in the downward polarization state. It is further demonstrated that ferroelectric switching in the (111)pc BiFeO3 thin-film photoanode leads to an approximate change of 8,000% in the photocurrent density and a 0.330 V shift in the onset potential. This study strongly suggests that domain-engineered ferroelectric materials can be used as effective charge separation and collection layers for efficient solar water-splitting photoanodes.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Chapin, D. M.; Fuller, C. S.; Pearson, G. L. A new silicon p–n junction photocell for converting solar radiation into electrical power. J. Appl. Phys. 1954, 25, 676–677.

    Article  Google Scholar 

  2. O’Regan, B.; Grätzel, M. A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films. Nature 1991, 353, 737–740.

    Article  Google Scholar 

  3. Britt, J.; Ferekides, C. Thin-film CdS/CdTe solar cell with 15.8% efficiency. Appl. Phys. Lett. 1993, 62, 2851–2852.

    Article  Google Scholar 

  4. Chitambar, M.; Wang, Z. J.; Liu, Y. M.; Rockett, A.; Maldonado, S. Dye-sensitized photocathodes: Efficient light-stimulated hole injection into p-GaP under depletion conditions. J. Am. Chem. Soc. 2012, 134, 10670–10681.

    Article  Google Scholar 

  5. Gur, I.; Fromer, N. A.; Geier, M. L.; Alivisatos, A. P. Airstable all-inorganic nanocrystal solar cells processed from solution. Science 2005, 310, 462–465.

    Article  Google Scholar 

  6. Ginley, D.; Green, M. A.; Collins, R. Solar energy conversion toward 1 terawatt. MRS Bull. 2008, 33, 355–364.

    Article  Google Scholar 

  7. An, H.; Han, J. Y.; Kim, B.; Song, J.; Jeong, S. Y.; Franchini, C.; Bark, C. W.; Lee, S. Large enhancement of the photovoltaic effect in ferroelectric complex oxides through bandgap reduction. Sci. Rep. 2016, 6, 28313.

    Article  Google Scholar 

  8. Fridkin, V. M. Bulk photovoltaic effect in noncentrosymmetric crystals. Crystallogr. Rep. 2001, 46, 654–658.

    Article  Google Scholar 

  9. Pantel, D.; Chu, Y.-H.; Martin, L. W.; Ramesh, R.; Hesse, D.; Alexe, M. Switching kinetics in epitaxial BiFeO3 thin films. J. Appl. Phys. 2010, 107, 084111.

    Article  Google Scholar 

  10. Clark, J. S.; Robertson, J. Band gap and Schottky barrier heights of multiferroic BiFeO3. Appl. Phys. Lett. 2007, 90, 132903.

    Article  Google Scholar 

  11. Hauser, A. J.; Zhang, J.; Mier, L.; Ricciardo, R. A.; Woodward, P. M.; Gustafson, T. L.; Brillson, L. J.; Yang, F. Y. Characterization of electronic structure and defect states of thin epitaxial BiFeO3 films by UV–visible absorption and cathodoluminescence spectroscopies. Appl. Phys. Lett. 2008, 92, 222901.

    Article  Google Scholar 

  12. Yi, H. T.; Choi, T.; Choi, S. G.; Oh, S. G.; Cheong, S. W. Mechanism of the switchable photovoltaic effect in ferroelectric BiFeO3. Adv. Mater. 2011, 23, 3403–3407.

    Article  Google Scholar 

  13. Neaton, J. B.; Ederer, C.; Waghmare, U. V.; Spaldin, N. A.; Rabe, K. M. First-principles study of spontaneous polarization in multiferroic BiFeO3. Phys. Rev. B 2005, 71, 014113.

    Article  Google Scholar 

  14. Wang, Y. Y. A giant polarization value in bismuth ferrite thin films. J. Alloys Compd. 2011, 509, L362–L364.

    Article  Google Scholar 

  15. Kim, T. H.; Baek, S. H.; Yang, S. M.; Kim, Y. S.; Jeon, B. C.; Lee, D.; Chung, J.-S.; Eom, C. B.; Yoon, J.-G.; Noh, T. W. Polarity-dependent kinetics of ferroelectric switching in epitaxial BiFeO3(111) capacitors. Appl. Phys. Lett. 2011, 99, 012905.

    Article  Google Scholar 

  16. Wu, J. G.; Wang, J. Orientation dependence of ferroelectric behavior of BiFeO3 thin films. J. Appl. Phys. 2009, 106, 104111.

    Article  Google Scholar 

  17. Béa, H.; Bibes, M.; Zhu, X.-H.; Fusil1, S.; Bouzehouane, K.; Petit, S.; Kreisel, J.; Barthélémy, A. Crystallographic, magnetic, and ferroelectric structures of bulklike BiFeO3 thin films. Appl. Phys. Lett. 2008, 93, 072901.

    Article  Google Scholar 

  18. Li, J. F.; Wang, J. L.; Wuttig, M.; Ramesh, R.; Wang, N. G.; Ruette, B.; Pyatakov, A. P.; Zvezdin, A. K.; Viehland, D. Dramatically enhanced polarization in (001), (101), and (111) BiFeO3 thin films due to epitiaxial-induced transitions. Appl. Phys. Lett. 2004, 84, 5261–5263.

    Article  Google Scholar 

  19. Wang, J.; Neaton, J. B.; Zheng, H.; Nagarajan, V.; Ogale, S. B.; Liu, B.; Viehland, D.; Vaithyanathan, V.; Schlom, D. G.; Waghmare, U. V. et al. Epitaxial BiFeO3 multiferroic thin film heterostructures. Science 2003, 299, 1719–1722.

    Article  Google Scholar 

  20. Singh, S. K.; Kim, Y. K.; Funakubo, H.; Ishiwara, H. Epitaxial BiFeO3 thin films fabricated by chemical solution deposition. Appl. Phys. Lett. 2006, 88, 162904.

    Article  Google Scholar 

  21. Chen, Z. H.; He, L.; Zhang, F.; Jiang, J.; Meng, J. W.; Zhao, B. Y.; Jiang, A. Q. The conduction mechanism of large on/off ferroelectric diode currents in epitaxial (111) BiFeO3 thin film. J. Appl. Phys. 2013, 113, 184106.

    Article  Google Scholar 

  22. Zhu, J.; Luo, W. B.; Li, Y. R. Growth and properties of BiFeO3 thin films deposited on LaNiO3-buffered SrTiO3 (001) and (111) substrates by PLD. Appl. Surf. Sci. 2008, 255, 3466–3469.

    Article  Google Scholar 

  23. Sone, K.; Naganuma, H.; Miyazaki, T.; Nakajima, T.; Okamura, S. Crystal structures and electrical properties of epitaxial BiFeO3 thin films with (001), (110), and (111) orientations. Jpn. J. Appl. Phys. 2010, 49, 09MB03.

    Article  Google Scholar 

  24. Kubel, F.; Schmid, H. Structure of a ferroelectric and ferroelastic monodomain crystal of the perovskite BiFeO3. Acta Cryst. B 1990, 46, 698–702.

    Article  Google Scholar 

  25. Baek, S.-H.; Folkman, C. M.; Park, J.-W.; Lee, S.; Bark, C.-W.; Tybell, T.; Eom, C.-B. The nature of polarization fatigue in BiFeO3. Adv. Mater. 2011, 23, 1621–1625.

    Article  Google Scholar 

  26. Das, R. R.; Kim, D. M.; Baek, S. H.; Eom, C. B.; Zavaliche, F.; Yang, S. Y.; Ramesh, R.; Chen, Y. B.; Pan, X. Q.; Ke, X. et al. Synthesis and ferroelectric properties of epitaxial BiFeO3 thin films grown by sputtering. Appl. Phys. Lett. 2006, 88, 242904.

    Article  Google Scholar 

  27. Streiffer, S. K.; Parker, C. B.; Romanov, A. E.; Lefevre, M. J.; Zhao, L.; Speck, J. S.; Pompe, W.; Foster, C. M.; Bai, G. R. Domain patterns in epitaxial rhombohedral ferroelectric films. I. Geometry and experiments. J. Appl. Phys. 1998, 83, 2742–2753.

    Article  Google Scholar 

  28. Taylor, D. V.; Damjanovic, D. Evidence of domain wall contribution to the dielectric permittivity in PZT thin films at sub-switching fields. J. Appl. Phys. 1997, 82, 1973–1975.

    Article  Google Scholar 

  29. Jang, H. W.; Ortiz, D.; Baek, S. H.; Folkman, C. M.; Das, R. R.; Shafer, P.; Chen, Y. B.; Nelson, C. T.; Pan, X. Q.; Ramesh, R. et al. Domain engineering for enhanced ferroelectric properties of epitaxial (001) BiFeO thin films. Adv. Mater. 2009, 21, 817–823.

    Article  Google Scholar 

  30. Cruz, M. P.; Chu, Y.-H.; Zhang, J. X.; Yang, P. L.; Zavaliche, F.; He, Q.; Shafer, P.; Chen, L. Q.; Ramesh, R. Strain control of domain-wall stability in epitaxial BiFeO3 (110) films. Phys. Rev. Lett. 2007, 99, 217601.

    Article  Google Scholar 

  31. Liu, Q.; Zhou, Y.; You, L.; Wang, J. L.; Shen, M. R.; Fang, L. Enhanced ferroelectric photoelectrochemical properties of polycrystalline BiFeO3 film by decorating with Ag nanoparticles. Appl. Phys. Lett. 2016, 108, 022902.

    Article  Google Scholar 

  32. Ji, W.; Yao, K.; Lim, Y. F.; Liang, Y. C.; Suwardi, A. Epitaxial ferroelectric BiFeO3 thin films for unassisted photocatalytic water splitting. Appl. Phys. Lett. 2013, 103, 062901.

    Article  Google Scholar 

  33. Rong, N. N.; Chu, M. S.; Tang, Y. L.; Zhang, C.; Cui, X.; He, H. C.; Zhang, Y. H.; Xiao, P. Improved photoelectrocatalytic properties of Ti-doped BiFeO3 films for water oxidation. J. Mater. Sci. 2016, 51, 5712–5723.

    Article  Google Scholar 

  34. Moniz, S. J. A.; Quesada-Cabrera, R.; Blackman, C. S.; Tang, J. W.; Southern, P.; Weaver, P. M.; Carmalt, C. J. A simple, low-cost CVD route to thin films of BiFeO3 for efficient water photo-oxidation. J. Mater. Chem. A 2014, 2, 2922–2927.

    Article  Google Scholar 

  35. Cao, D. W.; Wang, Z. J.; Nasori; Wen, L. Y.; Mi, Y.; Lei, Y. Switchable charge-transfer in the photoelectrochemical energy-conversion process of ferroelectric BiFeO3 photoelectrodes. Angew. Chem., Int. Ed. 2014, 53, 11027–11031.

    Article  Google Scholar 

  36. Rojac, T.; Bencan, A.; Drazic, G.; Sakamoto, N.; Ursic, H.; Jancar, B.; Tavcar, G.; Makarovic, M.; Walker, J.; Malic, B. et al. Domain-wall conduction in ferroelectric BiFeO3 controlled by accumulation of charged defects. Nat. Mater. 2017, 16, 322–327.

    Article  Google Scholar 

  37. Huang, Y.-L.; Chang, W. S.; Van, C. N.; Liu, H.-J.; Tsai, K.-A.; Chen, J.-W.; Kuo, H.-H.; Tzeng, W.-Y.; Chen, Y.-C.; Wu, C.-L. et al. Tunable photoelectrochemical performance of Au/BiFeO3 heterostructure. Nanoscale 2016, 8, 15795–15801.

    Article  Google Scholar 

  38. Chen, S. Y.; Wang, L.-W. Thermodynamic oxidation and reduction potentials of photocatalytic semiconductors in aqueous solution. Chem. Mater. 2012, 24, 3659–3666.

    Article  Google Scholar 

  39. Choi, T.; Lee, S.; Choi, Y. J.; Kiryukhin, V.; Cheong, S. W. Switchable ferroelectric diode and photovoltaic effect in BiFeO3. Science 2009, 324, 63–66.

    Article  Google Scholar 

  40. Chen, J.; Lu, H. D.; Liu, H. J.; Chu, Y.-H.; Dunn, S.; Ostrikov, K. K.; Gruverman, A.; Valanoor, N. Interface control of surface photochemical reactivity in ultrathin epitaxial ferroelectric films. Appl. Phys. Lett. 2013, 102, 182904.

    Article  Google Scholar 

  41. Fang, L.; You, L.; Zhou, Y.; Ren, P.; Lim, Z. S.; Wang, J. L. Switchable photovoltaic response from polarization modulated interfaces in BiFeO3 thin films. Appl. Phys. Lett. 2014, 104, 142903.

    Article  Google Scholar 

  42. Rioult, M.; Datta, S.; Stanescu, D.; Stanescu, S.; Belkhou, R.; Maccherozzi, F.; Magnan, H.; Barbier, A. Tailoring the photocurrent in BaTiO3/Nb:SrTiO3 photoanodes by controlled ferroelectric polarization. Appl. Phys. Lett. 2015, 107, 103901.

    Article  Google Scholar 

  43. Yun, K. Y.; Noda, M.; Okuyama, M.; Saeki, H.; Tabata, H.; Saito, K. Structural and multiferroic properties of BiFeO3 thin films at room temperature. J. Appl. Phys. 2004, 96, 3399–3403.

    Article  Google Scholar 

  44. Xu, G. Y.; Hiraka, H.; Shirane, G.; Li, J. F.; Wang, J. L.; Viehland, D. Low symmetry phase in (001) BiFeO3 epitaxial constrained thin films. Appl. Phys. Lett. 2005, 86, 182905.

    Article  Google Scholar 

  45. Béa, H.; Bibes, M.; Fusil, S.; Bouzehouane, K.; Jacquet, E.; Rode, K.; Bencok, P.; Barthélémy, A. Investigation on the origin of the magnetic moment of BiFeO3 thin films by advanced X-ray characterizations. Phys. Rev. B 2006, 74, 020101(R).

    Article  Google Scholar 

  46. Chu, Y.-H.; Zhao, T.; Cruz, M. P.; Zhan, Q.; Yang, P. L.; Martin, L. W.; Huijben, M.; Yang, C. H.; Zavaliche, F.; Zheng, H. et al. Ferroelectric size effects in multiferroic BiFeO3 thin films. Appl. Phys. Lett. 2007, 90, 252906.

    Article  Google Scholar 

  47. Lewis, N. S. A quantitative investigation of the open-circuit photovoltage at the semiconductor/liquid interface. J. Electrochem. Soc. 1984, 131, 2496–2503.

    Article  Google Scholar 

  48. Walter, M. G.; Warren, E. L.; McKone, J. R.; Boettcher, S. W.; Mi, Q. X.; Santori, E. A.; Lewis, N. S. Solar water splitting cells. Chem. Rev. 2010, 110, 6446–6473.

    Article  Google Scholar 

  49. Wang, G. M.; Ling, Y. C.; Wheeler, D. A.; George, K. E. N.; Horsley, K.; Heske, C.; Zhang, J. Z.; Li, Y. Facile synthesis of highly photoactive α-Fe2O3-based films for water oxidation. Nano Lett. 2011, 11, 3503–3509.

    Article  Google Scholar 

  50. Wang, Z. J.; Cao, D. W.; Wen, L. Y.; Xu, R.; Obergfell, M.; Mi, Y.; Zhan, Z. B.; Nasori, N.; Demsar, J.; Lei, Y. Manipulation of charge transfer and transport in plasmonicferroelectric hybrids for photoelectrochemical applications. Nat. Commun. 2016, 7, 10348.

    Article  Google Scholar 

  51. Liao, L. B.; Zhang, Q. H.; Su, Z. H.; Zhao, Z. Z.; Wang, Y. N.; Li, Y.; Lu, X. X.; Wei, D. G.; Feng, G. Y.; Yu, Q. K. et al. Efficient solar water-splitting using a nanocrystalline CoO photocatalyst. Nat. Nanotechnol. 2014, 9, 69–73.

    Article  Google Scholar 

  52. Xu, H.-M.; Wang, H. C.; Shi, J.; Lin, Y. H.; Nan, C. W. Photoelectrochemical performance observed in Mn-doped BiFeO3 heterostructured thin films. Nanomaterials 2016, 6, 215.

    Article  Google Scholar 

  53. Pintilie, L.; Alexe, M. Metal-ferroelectric-metal heterostructures with Schottky contacts. I. Influence of the ferroelectric properties. J. Appl. Phys. 2005, 98, 124103.

    Article  Google Scholar 

  54. Yang, S. Y.; Seidel, J.; Byrnes, S. J.; Shafer, P.; Yang, C.-H.; Rossell, M. D.; Yu, P.; Chu, Y.-H.; Scott, J. F.; Ager, J. W. et al. Above-bandgap voltages from ferroelectric photovoltaic devices. Nat. Nanotechnol. 2010, 5, 143–147.

    Article  Google Scholar 

Download references

Acknowledgements

The authors gratefully acknowledge the financial support from the Basic Science Research Program (No. NRF-2014R1A1A2053552) and the Future Material Discovery Program (No. NRF-2016M3D1A1027666) through the National Research Foundation of Korea, and the International Energy Joint R&D Program through the Korea Institute of Energy Technology Evaluation and Planning (No. 20168510011350), and by the GIST (Gwangju Institute of Science and Technology) Research Institute (GRI) Project through a grant provided by GIST in 2016.

Author information

Authors and Affiliations

  1. School of Materials Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju, 61005, Republic of Korea

    Jaesun Song, Jongmin Lee, Jaeseong Cha, Sang Yun Jeong, Hyunji An, Wan Sik Kim, Yen-Sook Jung, Jiyoon Park, Gun Young Jung, Dong-Yu Kim, Ji Young Jo & Sanghan Lee

  2. Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul, 08826, Republic of Korea

    Taemin Ludvic Kim & Ho Won Jang

  3. Department of Physics, Chonbuk National University, Jeonju, 54896, Republic of Korea

    Sam Yeon Cho & Sang Don Bu

Authors
  1. Jaesun Song
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Taemin Ludvic Kim
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jongmin Lee
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Sam Yeon Cho
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jaeseong Cha
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Sang Yun Jeong
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Hyunji An
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Wan Sik Kim
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Yen-Sook Jung
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Jiyoon Park
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Gun Young Jung
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Dong-Yu Kim
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Ji Young Jo
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Sang Don Bu
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Ho Won Jang
    View author publications

    You can also search for this author in PubMed Google Scholar

  16. Sanghan Lee
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Ho Won Jang or Sanghan Lee.

Electronic supplementary material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Song, J., Kim, T.L., Lee, J. et al. Domain-engineered BiFeO3 thin-film photoanodes for highly enhanced ferroelectric solar water splitting. Nano Res. 11, 642–655 (2018). https://doi.org/10.1007/s12274-017-1669-1

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-017-1669-1

Keywords

Search

Navigation