Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Synthesis of a metal oxide with a room-temperature photoreversible phase transition

Nature Chemistry volume 2, pages 539–545 (2010)Cite this article

Subjects

Abstract

Photoinduced phase-transition materials, such as chalcogenides, spin-crossover complexes, photochromic organic compounds and charge-transfer materials, are of interest because of their application to optical data storage. Here we report a photoreversible metal–semiconductor phase transition at room temperature with a unique phase of Ti3O5, λ-Ti3O5. λ-Ti3O5 nanocrystals are made by the combination of reverse-micelle and sol–gel techniques. Thermodynamic analysis suggests that the photoinduced phase transition originates from a particular state of λ-Ti3O5 trapped at a thermodynamic local energy minimum. Light irradiation causes reversible switching between this trapped state (λ-Ti3O5) and the other energy-minimum state (β-Ti3O5), both of which are persistent phases. This is the first demonstration of a photorewritable phenomenon at room temperature in a metal oxide. λ-Ti3O5 satisfies the operation conditions required for a practical optical storage system (operational temperature, writing data by short wavelength light and the appropriate threshold laser power).

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on SpringerLink
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Synthesis procedure for λ-Ti3O5 nanocrystals in a SiO2 matrix.
Figure 2: Formation and crystal structure of λ-Ti3O5.
Figure 3: Magnetic and optical properties, and electronic structures of λ-Ti3O5.
Figure 4: Reversible photoinduced phase transition in λ-Ti3O5.
Figure 5: Phase transition between λ-Ti3O5 and β-Ti3O5 induced by one-shot laser pulses.
Figure 6: Mechanism of the photoinduced phase transition in λ-Ti3O5.

Similar content being viewed by others

References

  1. Yamada, N., Ohno, E., Nishiuchi, K., Akahira, N. & Takao, M. Rapid-phase transitions of GeTe–Sb2Te3 pseudobinary amorphous thin films for an optical disk memory. J. Appl. Phys. 69, 2849–2856 (1991).

    Article  CAS  Google Scholar 

  2. Kolobov, A. V. et al. Understanding the phase-change mechanism of rewritable optical media. Nature Mater. 3, 703–708 (2004).

    Article  CAS  Google Scholar 

  3. Gütlich, P., Hauser, A. & Spiering, H. Thermal and optical switching of iron(ii) complexes Angew. Chem. Int. Ed. Engl. 33, 2024–2054 (1994).

    Article  Google Scholar 

  4. Nasu, K. Relaxations of Excited States and Photo-Induced Structural Phase Transitions (Springer, 1997).

    Book  Google Scholar 

  5. Kahn, O. & Martinez, C. J. Spin-transition polymers: from molecular materials toward memory devices. Science 279, 44–48 (1998).

    Article  CAS  Google Scholar 

  6. Decurtins, S., Gütlich, P., Köhler, C.P., Spiering, H. & Hauser, A. Light-induced excited spin state trapping in a transition-metal complex: the hexa-1-propyltetrazole-iron(ii) tetrafluoroborate spin-crossover system Chem. Phys. Lett. 105, 1–4 (1984).

    Article  CAS  Google Scholar 

  7. Létard, J. F. et al. Light induced excited pair spin state in an iron(ii) binuclear spin-crossover compound. J. Am. Chem. Soc. 121, 10630–10631 (1999).

    Article  Google Scholar 

  8. Varret, F. et al. Thermally induced dilution of the photo-induced magnetic state of Prussian Blue analogues. Mol. Cryst. Liq. Cryst. 379, 333–340 (2002).

    Article  CAS  Google Scholar 

  9. Dürr, H. & Bouas-Laurent, H. Photochromism: Molecules and Systems (Elsevier, 1990).

    Google Scholar 

  10. Aktsipetrov, O. A., Fedyanin, A. A., Melnikov, A. V., Mishina, E. D. & Murzina, T. V. Second harmonic generation as a nondestructive readout of optical (photo(electro)chromic and magnetic) memories. Jpn J. Appl. Phys. 37, 122–127 (1998).

    Article  CAS  Google Scholar 

  11. Irie, M., Fukaminato, T., Sasaki, T., Tamai, N. & Kawai, T. Organic chemistry: a digital fluorescent molecular photoswitch. Nature 420, 759–760 (2002).

    Article  CAS  Google Scholar 

  12. Habuchi, S. et al. Reversible single-molecule photoswitching in the GFP-like fluorescent protein Dronpa. Proc. Natl Acad. Sci. USA 102, 9511–9516 (2005).

    Article  CAS  Google Scholar 

  13. Koshihara, S., Tokura, Y., Mitani, T., Saito, G. & Koda, T. Photoinduced valence instability in the organic molecular compound tetrathisfulvalence-p-chloranil (TTF-CA). Phys. Rev. B 42, 6853–6856 (1990).

    Article  CAS  Google Scholar 

  14. Collet, E. et al. Laser-induced ferroelectric structural order in an organic charge-transfer crystal. Science 300, 612–615 (2003).

    Article  CAS  Google Scholar 

  15. Ohkoshi, S. & Hashimoto, K. Photo-magnetic and magneto-optical effects of functionalized metal polycyanides. J. Photochem. Photobiol. C 2, 71–88 (2001).

    Article  CAS  Google Scholar 

  16. Verdaguer, M. Molecular electronics emerges from molecular magnetism. Science 272, 698–699 (1996).

    Article  CAS  Google Scholar 

  17. Ohkoshi, S. et al. Photoinduced magnetic pole inversion in a ferro–ferrimagnet: (Feii0.40Mnii0.60)1.5Criii(CN)6 . Appl. Phys. Lett. 70, 1040–1042 (1997).

    Article  CAS  Google Scholar 

  18. Herrera, J. M. et al. Reversible photoinduced magnetic properties in the heptanuclear complex [Moiv(CN)2(CN–CuL)6]8+: a photomagnetic high-spin molecule. Angew. Chem. Int. Ed. 43, 5468–5471 (2004).

    Article  CAS  Google Scholar 

  19. Dei, A. Photomagnetic effects in polycyanometallate compounds: an intriguing future chemically based technology? Angew. Chem. Int. Ed. 44, 1160–1163 (2005).

    Article  CAS  Google Scholar 

  20. Ohkoshi, S., Ikeda, S., Hozumi, T., Kashiwagi, T. & Hashimoto, K. Photoinduced magnetization with a high Curie temperature and a large coercive field in a cyano-bridged cobalt–tungstate bimetallic assembly. J. Am. Chem. Soc. 128, 5320–5321 (2006).

    Article  CAS  Google Scholar 

  21. Tokoro, H. et al. Visible-light-induced reversible photomagnetism in rubidium manganese hexacyanoferrate. Chem. Mater. 20, 423–428 (2008).

    Article  CAS  Google Scholar 

  22. Miyano, K., Tanaka, T., Tomioka, Y. & Tokura, Y. Photoinduced insulator-to-metal transition in a perovskite manganite. Phys. Rev. Lett. 78, 4257–4260 (1997).

    Article  CAS  Google Scholar 

  23. Fiebig, M., Miyano, K., Tomioka, Y. & Tokura, Y. Visualization of the local insulator–metal transition in Pr0.7Ca0.3MnO3 . Science 280, 1925–1928 (1998).

    Article  CAS  Google Scholar 

  24. Åsbrink, S. & Magnéli, A. Crystal structure studies on trititanium pentoxide, Ti3O5 . Acta Cryst. 12, 575–581 (1959).

    Article  Google Scholar 

  25. Hong, S. H. & Åsbrink, S. The structure of γ-Ti3O5 at 297 K. Acta Cryst. B 38, 2570–2576 (1982).

    Article  Google Scholar 

  26. Onoda, M. Phase transitions of Ti3O5 . J. Solid State Chem. 136, 67–73 (1998).

    Article  CAS  Google Scholar 

  27. Chase, M. W. NIST–JANAF Thermochemical Tables 4th edn (ed. Chase, M.) Journal of Physical and Chemical Reference Data, Monograph No. 9 (American Chemical Society and American Institute of Physics, 1998).

    Google Scholar 

  28. Keys, L. K. & Mulay, L. N. Magnetic susceptibility measurements of rutile and the Magnéli phases of the Ti–O system. Phys. Rev. 154, 453–456 (1967).

    Article  CAS  Google Scholar 

  29. Bartholomew, R. F. & Frankl, D. R. Electrical properties of some titanium oxide. Phys. Rev. 187, 828–833 (1969).

    Article  CAS  Google Scholar 

  30. Mulay, L. N. & Danley, W. J. Cooperative magnetic transition in the titanium–oxygen system: a new approach. J. Appl. Phys. 41, 877–879 (1970).

    Article  CAS  Google Scholar 

  31. Rao, C. N. R., Ramdas, S., Loehman, R. E. & Honing, J. M. Semiconductor–metal transition in Ti3O5 . J. Solid State Chem. 3, 83–88 (1971).

    Article  CAS  Google Scholar 

  32. Zachariasen, W. H. Bond lengths in oxygen and halogen compounds of d and f elements. J. Less-Common Metals 62, 1–7 (1978).

    Article  CAS  Google Scholar 

  33. Kresse, G. & Hafner, J. Ab initio molecular dynamics for open-shell transition metals. Phys. Rev. B 48, 13115–13118 (1993).

    Article  CAS  Google Scholar 

  34. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

    Article  CAS  Google Scholar 

  35. Meinders, E. R., Mijiritskii, A. V., van Pieterson, L. & Wuttig, M. Optical Data Storage: Phase-Change Media and Recording (Springer, 2006).

    Google Scholar 

  36. Wuttig, M. & Yamada, N. Phase-change materials for rewriteable data storage. Nature Mater. 6, 824–832 (2007).

    Article  CAS  Google Scholar 

  37. Slichter, C. P. & Drickamer, H. G. Pressure-induced electronic changes in compounds of iron. J. Chem. Phys. 56, 2142–2160 (1972).

    Article  CAS  Google Scholar 

  38. Izumi, F. & Momma, K. Three-dimensional visualization in powder diffraction. Solid. State Phenom. 130, 15–20 (2007).

    Article  CAS  Google Scholar 

  39. McHale, J. M., Auroux, A., Perrotta, A. J. & Navrotsky, A. Surface energies and thermodynamic phase stability in nanocrystalline aluminas. Science 277, 788–791 (1997).

    Article  CAS  Google Scholar 

  40. Ohkoshi, S., Sakurai, S., Jin, J. & Hashimoto, K. The addition effects of alkaline earth ions in the chemical synthesis of ϵ-Fe2O3 nanocrystals that exhibit a huge coercive field. J. Appl. Phys. 97, 10K312 (2005).

    Article  Google Scholar 

  41. Makiura, R. et al. Size-controlled stabilization of the superionic phase to room temperature in polymer-coated AgI nanoparticles. Nature Mater. 8, 476–480 (2009).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was performed under the management of the Project to Create Photocatalyst Industry for Recycling-oriented Society supported by the New Energy and Industrial Technology Development Organization. We are grateful to T. Nuida and K. Takeda for drawing the colour figures, K. Tomono for measuring the infrared spectra, Y. Kakegawa, H. Tsunakawa and M. Adachi for collecting TEM images, S. Ohtsuka and T. Moroyama for collecting SEM images, and T. Takasaki, Y. Namatame, M. Saigo and M. Yasaka (Rigaku Corporation) for measuring the XRD patterns. We are thankful for a Grant-in-Aid for the Global COE Program, ‘Chemistry Innovation through Cooperation of Science and Engineering’ from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan, and the Center for Nano Lithography & Analysis, The University of Tokyo, supported by MEXT, Japan.

Author information

Authors and Affiliations

  1. Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan

    Shin-ichi Ohkoshi, Yoshihide Tsunobuchi, Tomoyuki Matsuda, Asuka Namai, Fumiyoshi Hakoe & Hiroko Tokoro

  2. Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan

    Kazuhito Hashimoto

Authors
  1. Shin-ichi Ohkoshi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yoshihide Tsunobuchi
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Tomoyuki Matsuda
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Kazuhito Hashimoto
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Asuka Namai
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Fumiyoshi Hakoe
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Hiroko Tokoro
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

S.O. designed and coordinated this study and contributed to all measurements and calculations, and wrote the paper. Y.T. carried out synthesis, DSC and first-principle band calculation. T.M. carried out synthesis. A.N. performed XRD measurements, Rietveld analysis and ICP-MS. F.H. carried out synthesis and TEM, SEM and SQUID measurements. K.H. contributed to the discussion. H.T. carried out synthesis and thermodynamic analysis, and carried out the photoirradiation and pressure-effect experiments. All authors commented on the manuscript.

Corresponding author

Correspondence to Shin-ichi Ohkoshi.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 5281 kb)

Supplementary information

Supplementary Movie S1 (MOV 2101 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Ohkoshi, Si., Tsunobuchi, Y., Matsuda, T. et al. Synthesis of a metal oxide with a room-temperature photoreversible phase transition. Nature Chem 2, 539–545 (2010). https://doi.org/10.1038/nchem.670

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nchem.670

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing