Structure and PRoperties of Multiferroic Langmuir Films Based on Barium Titanate and Magnetite Nanoparticles

Purpose. Obtaining multiferroic nanofilms from stabilized magnetite and barium titanate by the Langmuir-Blodgett method, establishing the nanostructural relationship and controlling their properties under the influence of both magnetic and electric fields.

Methods. Deposition of multiferroic magnetite and barium titanate nanofilms by the Langmuir-Blodgett method, probe microscopy, FTIR spectroscopy, Raman light scattering, X-ray phase and X-ray structural analysis, piezo response microscopy and temperature dependence of magnetoresistance.

Results. А highly dispersed stabilized magnetite with a particle size of 25 nm according to atomic force microscopy data was synthesized by chemical condensation method. Stabilized magnetite nanofilms were obtained by the Langmuir-Blodgett method. Their chemical structure was confirmed by FTIR spectroscopy and Raman spectroscopy - lines corresponding to both magnetite and its stabilized shells were observed. Based on X-ray diffractometry data, the lattice period of the cubic syngony of magnetite was calculated to be 8.3566 Å. Composite layered structures made of highly homogeneous films of barium titanate and magnetite were created by the Langmuir-Blodgett method. The monodomainization effect of the investigated films with dimensions corresponding to the superparamagnetic range caused by the expected growth of saturation magnetization in the magnetite film structure as compared to the bulk material was established. The temperature dependence of magnetoresistance was investigated. The studies made it possible to confirm the occurrence of the magnetoelectric effect in these nanocomposite structures, the occurrence of which is caused by the manifestation of a complex of magnetostrictive and piezoelectric properties characteristic of the constituent phases.

Conclusion. In Langmuir-Blodgett multiferroics in the form of composite nanofilm structures of stabilized barium titanate/magnetite nanoparticles the possibility of reversible control of magnetic or electric fields on magnetostrictive and piezoelectric properties by combining both forward and reverse piezo- and magnetostrictive effects was confirmed.

1. Freidman A. L., Horoshii I. N., Kolkov M. I., Terentyev K. Yu. Pryamoi i obratnyi magnitoelektricheskii effekt v ortorombicheskikh monokristallakh Dy1-xHOxMnO3 [Direct and inverse magnetoelectric effects in orthorhombic single crystals Dy1-xHoxMnO3]. Fizika tverdogo tela = Physics of the Solid State, 2021, vol. 63, no. 12, pp. 2119–2125. https://doi.org/10.21883/FTT.2021.12.5163.185

2. Fina I., Dix N., Rebled J.-M., eds. Direct magnetoelectric effect in ferroelectric-ferromagnetic epitaxial heterostructures. Nanoscale, 2013, vol. 5, no. 17, pp. 8037–8044. https://doi.org/10.1039/c3nr01011b

3. Ethier M., Shvartsman V., Salomon S., eds. The direct and the converse magnetoelectric effect in multiferroic cobalt ferrite–barium titanate ceramic composites. Journal of the American Ceramic Society, 2016, vol. 99, no. 11, pp. 3623–3631. https://doi.org/10.1111/JACE.14362

4. Toyoki K., Shiratsuchi Y., Kobane Atsushi, eds. Switching of the perpendicular exchange displacement in the layered structure of Pt/Co/Pt/α-Cr2O3/Pt using the magnetoelectric effect. Journal of Applied Physics, 2015, vol. 117, no. 17, pp. 17D902. https://doi.org/10.1063/1.4906322

5. Hur N., Park S., Sharma P., An J., Guha S., Chong S. Electric polarization reversal and memory in a multiferroic material induced by magnetic fields. Nature, 2004, vol. 429, pp. 392–395.

6. Kleeman V., Borisov P., Shvartsman V. V., Bedanta S. Multiferroic and magnetoelectric materials – developments and prospects. The European Physical Journal Conferences, 2012, vol. 29, p. 00046.

7. Bukharaev A. A., Zvezdin A. K., Pyatakov A. P., Fetisov Yu. K. Streintronika – novoe napravlenie mikro- i nanoelektroniki i nauki o materialakh [Straintronics: a new trend in micro- and nanoelectronics and materials science]. Uspekhi fizicheskikh nauk = Physics-Uspekhi, 2018, vol. 188, pp. 1288–1330. https://doi.org/10.3367/UFNr.2018.01.038279

8. Spaldin N. A., Ramesh R. Achievements in the field of magnetoelectric multiferroics. Natural materials, 2019, vol. 18, no. 3, pp. 203–212.

9. Kalgin A. V. Pryamoi magnitoelektricheskii effekt v dvukhsloinykh kerami- cheskikh kompozitakh na osnove ferrimagnetika Mn0.4Zn0.6Fe2O4 i segnetoelektrika PbZr0.53Ti0.47O3 [Direct magnetoelectric effect in bilayered ceramic composites based on Mn0. 4Zn0.6Fe2O4 ferrimagnet and PbZr0.53Ti0.47O3 ferroelectric]. Fizika tverdogo tela = Physics of the Solid State, 2021, vol. 63, no. 7, pp. 888–893.

10. Peng Zhou, Zhigiand Zheng, Yajun Qi, eds. Magnetoelectric effect Ni1-xZnxFe2O4/PZT in thinfilm heterostructures. Physics Letters A., 2022, vol. 426, p. 127897. https://doi.org/10.21016/j.phusleta.2021.127897

11. Filippov D. A., Laletin V. M., Galichyan T. A. Magnitoelektricheskii effekt v dvukhsloinoi magnitostriktsionno-p'ezoelektricheskoi strukture [Magnetoelectric effect in a magnetostrictive-piezoelectric bilayer structure]. Fizika tverdogo tela = Physics of the Solid State, 2013, vol. 55, no. 9, pp. 1728–1733.

12. Filippov D. A., Laletin V. M., Poddubnaya N. N. Nizkochastotnyi magnitoelektricheskii effekt v dvukhsloinoi magnitostriktsionno-p'ezoelektricheskoi strukture [Low-frequency magnetoelectric effect in a two-layer magnetostrictive piezoelectric structure]. Mezhdunarodnyi nauchno-issledovatel'skii zhurnal = International Scientific Research Journal, 2021, no. 3-1 (105), pp. 6-12. https://doi.org/10.23670/IRJ.2021.1053.001

13. Shirokov V. B., Kalinchuk V., Shakhovoy R. A., Yuryuk Yu. I. Material constants of barium titanate thin films. Physics of the Solid State, 2015, vol. 57, no. 8, pp. 1535–1540. https://doi.org/10.1134/S106378341508.0302

14. Budiavanti S., Soejijono B., Mudzakir I. Influence of layer number and sintering on ferroelectric behaviour of barium titanate films prepared with sol-gel method. Physical Journal: A series of conferences. IOP Publishing, 2018, vol. 985, no. 1, p. 012034.

15. Kumbhar S. S., Mahadik M., Chugule P. K., eds. Structural and electrical properties of barium titanate (BaTiO3) thin films obtained by spray pyrolysis method. Materials SciencePoland, 2015, vol. 33, no. 4, pp. 852–861. https://doi.org/10.1515/msp-2015-0107

16. Balashev V. V., Vikulov V. A., Dmitrov A. A., eds. Evolyutsiya strukturnykh i magnitotransportnykh svoistv plenok magnetita v zavisimosti ot temperatury ikh sinteza na poverkhnosti SiO2/Si (001) [Evolution and structural magnetotransport properties of magnetite films depending on the temperature of their synthesis on the surface of SiO2/Si (001)]. Fizika metallov i metallovedenie = Physics of Metals and Metallology, 2017, vol. 118, no. 7, pp. 679–685. https://doi.org/10.7868/S0015323017050023

17. Malikov I. V., Bererin V. A., Fomin L., Chernykh A. V. Epitaxial Fe3O4 films grown on R-plane sapphire by pulsed laser deposition. Inorganic materials, 2020, vol. 56, no. 2, pp. 164–171. https://doi.org/10.1134/S0020168520020120

18. Kuzmenko A. P., Chukhaeva I. V., Abakumov P. V. Features of the formation and Structure of Barium Titanate Langmuir Films [Features of the formation and structure of Barium titanate langmuir films]. Technical Physics = Technical physics, 2019, vol. 64, no. 8, pp. 1168–1177.

19. Kuzmenko A. P., Chukhaeva I. V., Abakumov P. V. [Electrical properties of Langmuir – Blodgett films of stabilized barium titanate]. Nauchnye tendentsii: Voprosy tochnykh i tekhnicheskikh nauk. Sbornik nauchnykh trudov po materialam XI Mezhdunarodnoi nauchnoi konferentsii [Scientific trends: Issues of exact and technical sciences. Collection of scientific papers based on the materials of the XI International Scientific Conference]. St. Petersburg, Obshchestvennaya nauka Publ., 2017, pp. 9–12. (In Russ.)

20. Koo Yu. S., K. M. Song, Hur N., Jung J. Y. Stain-induced magnetoelectric coupling in BaTiO3/Fe3O4 core/shell nanoparticles. Applied Physics Letters, 2009, vol. 94, pp. 032903-1 – 032903-3. https://doi.org/10.1063/1.3073751