Improvement of Solid Through Improved Solutions and Gels (2): The Other Methods

  • Tatsuya Shimoda


In Chap.  12, we demonstrated that solid films with good properties can be formed at lower temperatures through modification of the solution composition by adding the third element of amines. Here, in Sect. 13.1 we introduce another option: solution amelioration. That is, solvothermal treatment of the solution was found to be very effective to ameliorate the solution, imparting it with improved processability for solidification. We refer to this treatment as “solvothermal synthesis” of a precursor solution. In this section, we introduce the effects of solvothermal synthesis on the insulating properties of LaZrO films. Detailed structural analyses of the precursor solutions, dried gels, and annealed solids were extensively carried out. The analytical results show a substantial improvement of properties achieved by solvothermal treatment of solutions. We confirmed that the structural modification of metal–organic precursors in solution enhanced the processability of the solution in solidification, resulting in a final solid oxide with good properties and a good crystal structure.

We observed that hybrid clusters with inorganic cores coordinated by organic ligands were the typical metal–organic precursor structures. Structural unification of the cluster core was achieved by the solvothermal treatment. Greater uniformity of clusters facilitates the formation of a higher quality solid. The thus-made solid maintains features similar to those of the core structure of the cluster, even after annealing at high temperatures. These results demonstrate the importance of designing and ameliorating the cluster structure in solution.

As a novel method for producing device-quality oxide semiconducting thin film at temperature as low as 200 °C, solution combustion synthesis (SCS) was developed by Kim MG, Kanatzidis MG, Facchetti A, Marks TJ, Nat Mater 10:382, 2011. In Sect. 13.2, the SCS method is introduced. The self-generated heat of combustion synthesis provides a localized energy supply, eliminating the need for high, externally applied processing temperatures. In addition, the atomically local oxidizer supply can efficiently remove organic impurities without coke formation. Here, a redox-based combustion synthetic approach is applied to indium tin oxide (ITO) thin film using acetylacetone as a fuel and metal nitrate as oxidizer (Tue PT, Inoue S, Takamura Y, Shimoda T, Appl Phys A Mater Sci Process 122(6):1–8, 2016). The structural and electrical properties of SCS-ITO precursor solution and thin films were systematically investigated with changes in tin concentration, indium metal precursors, and annealing conditions such as temperature, time, and ambient. After that, the optimized SCS-ITO thin film was applied for source/drain (S/D) electrodes in a total solution-processed amorphous oxide TFT. The performance and stability of the SCS-ITO TFT were evaluated and compared to those of the TFT with sputtered-ITO S/D electrodes.


LaZrO film Solvothermal synthesis Cluster structure in solution Solution combustion synthesis (SCS) 


  1. 1.
    M.G. Kim, M.G. Kanatzidis, A. Facchetti, T.J. Marks, Nat. Mater. 10, 382 (2011)CrossRefGoogle Scholar
  2. 2.
    P.T. Tue, S. Inoue, Y. Takamura, T. Shimoda, Appl. Phys. A Mater. Sci. Process. 122(6), 1–8 (2016)CrossRefGoogle Scholar
  3. 3.
    P. Tue, J. Li, T. Miyasako, S. Inoue, T. Shimoda, Low-temperature all-solution-derived amorphous oxide thin-film transistors. IEEE Electron Device Lett. 34, 1536–1538 (2013)CrossRefGoogle Scholar
  4. 4.
    T. Kaneda et al., Rheology printing for metal-oxide patterns and devices. J. Mater. Chem. C 2, 40–49 (2014)CrossRefGoogle Scholar
  5. 5.
    P. Tue et al., High-performance solution-processed ZrInZnO thin-film transistors. IEEE Trans. Electron Devices 60, 320–326 (2013)CrossRefGoogle Scholar
  6. 6.
    J. Murakami, D. Li, S. Hirose, T. Kohara, Shimoda, solution processing of highly conductive ruthenium and ruthenium oxide thin films from rutheniumamine complexes. J. Mater. Chem. C 3, 4490–4499 (2015)CrossRefGoogle Scholar
  7. 7.
    Y. Murakami, J. Li, T. Shimoda, Highly conductive ruthenium oxide thin films by a lowtemperature solution process and green laser annealing. Mater. Lett. 152, 121–124 (2015)CrossRefGoogle Scholar
  8. 8.
    J. Li, P. Zhu, D. Hirose, S. Kohara, T. Shimoda, Hybrid cluster precursors of the LaZrO insulator for transistors: Properties of high temperature processed films and structures of solutions, gels, and solids. Sci. Rep. 6, 29682 (2016)Google Scholar
  9. 9.
    P. Lunkenheimer et al., Origin of apparent colossal dielectric constants. Phys. Rev. B 66, 052105 (2002)CrossRefGoogle Scholar
  10. 10.
    H.-J. Deiseroth, H.K. Müller-Buschbaum, Ein Beitrag zur Pyrochlorstruktur an La2Zr2O7. Z. Anorg. Allg. Chem. 375, 152–156 (1970)CrossRefGoogle Scholar
  11. 11.
    C. Loogn, J. Richardson, M. Ozawa, M. Kimura, Crystal structure and short-range oxygen defects in La-modified and Ndmodified ZrO2. J. Alloys Compounds 207, 174–177 (1994)Google Scholar
  12. 12.
    M. Puchberger et al., Can the clusters Zr6O4(OH)4(OOCR)12 and [Zr6O4(OH)4(OOCR)12]2 be converted into each other? Eur. J. Inorg. Chem. 16, 3283–3293 (2006)CrossRefGoogle Scholar
  13. 13.
    G. Kickelbick et al., Formation of organically surface-modified metal oxo clusters from carboxylic acids and metal alkoxides: A mechanistic study. J. Chem. Soc. Dalton Trans. 20, 3892–3898 (2002)CrossRefGoogle Scholar
  14. 14.
    R. Mos et al., Synthesis, crystal structure and thermal decomposition of Zr6O4(OH)4(CH3CH2COO)12. J. Analytical Appl. Pyrolysis 97, 137–142 (2012)CrossRefGoogle Scholar
  15. 15.
    C. Sanchez, M. In, Molecular design of alkoxide precursors for the synthesis of hybrid organic inorganic gels. J. Non-Cryst. Solids 147, 1–12 (1992)CrossRefGoogle Scholar
  16. 16.
    S. Gross, M. Bauer, EXAFS as powerful analytical tool for the investigation of organic-inorganic hybrid materials. Adv. Funct. Mater. 20, 4026–4047 (2010)CrossRefGoogle Scholar
  17. 17.
    P. Li, I.W. Chen, J.E. Penner-Hahn, X-ray-absorption studies of zirconia polymorphs: I. characteristic structures. Phys. Rev. B 48, 10063 (1993)CrossRefGoogle Scholar
  18. 18.
    P. Zhu, J. Li, P.T. Tue, S. Inoue, T. Shimoda, Hybrid cluster precursors of the LaZrO insulator for transistors: Lowering the processing temperature. Sci. Rep. 8, 5934 (2018). CrossRefGoogle Scholar
  19. 19.
    L. Patiny, A. Borel, ChemCalc: A building block for tomorrow’s chemical infrastructure. J. Chem. Inf. Model. 53, 1223–1228 (2013)CrossRefGoogle Scholar
  20. 20.
    B. Ravel, M.A.T.H.E.N.A. Newville, ARTEMIS, HEPHAESTUS: Data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Radiation 12, 537–541 (2005)CrossRefGoogle Scholar
  21. 21.
    U. Martin, H. Boysen, F. Frey, Neutron powder investigation of tetragonal and cubic stabilized zirconia, TZP and CSZ, at temperatures up to 1400 K. Acta Crystallogr. B 49, 403–413 (1993)CrossRefGoogle Scholar
  22. 22.
    E. Terzini, P. Thilakan, C. Minarini, Mater. Sci. Eng. B 77, 110 (2000)CrossRefGoogle Scholar
  23. 23.
    P.K. Biswas, A. De, K. Ortner, S. Korder, Mater. Lett. 58, 1540 (2000)CrossRefGoogle Scholar
  24. 24.
    J. Liu, D. Wu, S. Zeng, J. Mater. Process. Technol. 209, 3943 (2009)CrossRefGoogle Scholar
  25. 25.
    Q. Wei, H. Zheng, Y. Huang, Sol. Energy Mater. Sol. Cells 68, 383 (2001)CrossRefGoogle Scholar
  26. 26.
    D. Raoufi, A. Kiasatpour, H.R. Fallah, A.S.H. Rozatian, Appl. Surf. Sci. 253, 9085 (2007)CrossRefGoogle Scholar
  27. 27.
    T.S. Sathiaraj, Microelectron. J. 39, 1444 (2008)CrossRefGoogle Scholar
  28. 28.
    P.T. Tue, T. Miyasako, J. Li, H.T.C. Tu, S. Inoue, E. Tokumitsu, T. Shimoda, IEEE Trans. Electron Devices 60, 320 (2013)CrossRefGoogle Scholar
  29. 29.
    T.H. Jeong, S.J. Kim, D.H. Yoon, W.H. Jeong, D.L. Kim, H.S. Lim, H.J. Kim, Jpn. J. Appl. Phys. 50, 070202 (2011)CrossRefGoogle Scholar
  30. 30.
    A. Suresh, J.F. Muth, Appl. Phys. Lett. 92, 033502 (2008)CrossRefGoogle Scholar
  31. 31.
    R.B.M. Crossa, M.M. De Souza, Appl. Phys. Lett. 89, 263513 (2006)CrossRefGoogle Scholar
  32. 32.
    D. Gupta, S. Yoo, C. Lee, Y. Hong, IEEE Trans. Electron Devices 58, 1995 (2011)CrossRefGoogle Scholar

Copyright information

© Springer Nature Singapore Pte Ltd. 2019

Authors and Affiliations

  • Tatsuya Shimoda
    • 1
  1. 1.Japan Advanced Institute of Science and TechnologyNomiJapan

Personalised recommendations