Fundamental insights on scale-dependent phenomena in barium titanate-based ferroelectrics: critical grain size and effect of nanostructuring (FerroScale)

Project code: PN-III-P4-ID-PCE-2016-0817
Project number: 192 ⁄ 2017
Funded by the Executive Unit for Financing High Education, Research, Development and Innovation, CNCS – UEFISCDI

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BaTiO₃ is the prototype ferroelectric oxide, widely used in microelectronics due to its dielectric, piezo, pyro, ferroelectric and electro-optic properties, which can be tailored by substitutions and by microstructural factors (density, internal stress, morphology: size, shape, texture). In the last years, the miniaturization trend of the elements in microelectronics has imposed the need of developing new BaTiO₃ based ceramics with reduced grain sizes towards few tenths of nanometers, which has opened a new fundamental research topic: the role of the grain size on the functional properties. Grain size is an important parameter to tailor the functional properties in BaTiO₃ because around 1 micrometer some properties are maximized. However, for applications is essential to preserve high values for the material constants while reducing grain size at nanoscale. Understanding why enhanced properties are found at the critical grain size of 1 micrometer and extending to other systems the ways to reproduce such specific conditions to acquire enhanced properties is very challenging. The major goal of the present project is to clarify missing aspects concerning size-dependent phenomena in BT-based ferroelectrics by a novel experimental-modeling multiscale approach (macroscopic, mesoscopic and at nanoscale) and by a multidisciplinary study involving innovative chemistry for preparation, complex nano/microscale characterization, detailed investigation of the functional properties and multiscale complex modeling tools.

Project budget

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"Alexandru Ioan Cuza" University of Iasi, Faculty of Physics
Project Manager: Prof. Univ. dr. Liliana Mitoseriu
CSII dr. Cristina Elena Ciomaga
Asist. Univ. dr. Lavinia-Petronela Curecheriu
CSIII dr. Mirela Airimioaei
CSIII dr. Nadejda Horchidan
Asist. Univ. dr. Leontin Padurariu
Ph. D. Student Ina Turcan (hired from July 2018)
Ph. D. Student Vlad-Alexandru Lukacs (hired from July 2018)

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2017 - Stage I
I. Synthesis of pure and doped BT nanopowders. Modeling domain structures in BT monocrystals (Budget Stage I: 270.000,00lei)
I.1 Synthesis of BT based nanopowders by wet methods and solid state reaction method (Budget: 76.125,00lei).
I.2 Micro/nanostructural and phase analysis of nanopowders (Budget: 36.125,00 lei).
I.3 Sintering of dense BT-based ceramics with different grain size (sintering and testing for optimization parameters) (Budget: 20.000,00lei).
I.4 Micro/nanostructural and phase characterization of BT based ceramic as a function of grain size and composition (Budget: 40.000,00 lei).
I.5 Monte Carlo model for describing domain structures and DWs dynamics in BT single crystals based on thermodynamic theories and ab-initio calculations (Budget: 35.000,00 lei).
I.6 Project management, coordination and dissemination I (Budget: 62.750,00 lei).

2018 - Stage II
II. Experimental and theoretical multiscale study of grain size-dependent properties in BT-based ceramics (Budget Stage II: 278.449,00 lei)
II.1 Sintering of dense BT-based ceramics with different grain sizes (continued) (Budget: 30.000,00 lei).
II.2 Micro/nanostructural and phase characterization of BT based ceramic based on grain size and composition (continued) (Budget: 30.000,00 lei).
II.3 Study of grain size dependence of dielectric and ferroelectric properties at nano / mesoscale: the effects of grain size and composition on the ferroelectric domains structure (spontaneous and field-induced) (Budget: 50.000,00 lei).
II.4 Monitoring of structural changes in BT ceramics depending on grain size (around 1μm) and composition (Budget: 50.000,00 lei)
II.5 Study of grain size dependence of macroscopic low field properties by impedance spectroscopy (this task will continue in 2019) (Budget: 12.149,00 lei).
II.6 Monte Carlo modeling of the domain structure and inter-domain dynamics in BT single-crystal using thermodynamic theories and ab-initio calculations (continued) (Budget: 40.000,00).
II.7 Meso-scale modeling (Monte Carlo with FEM calculations) to describe the grain size effects on low field properties of BT-based polycrystalline ceramics (Budget: 30.000,00 lei).
II.8 Project management, coordination and dissemination II (Budget: 36.300,00 lei).

2019 - Stage III
III. Complex macroscopic investigations of functional properties in BT based ceramic based on size effect and composition (Budget Stage III: 227.251,00 lei)
III.1 Study of GS-dependent low-field macroscopic properties by impedance spectroscopy and sub-switching characteristics (Rayleigh) (Budget: 107.851,00lei).
III.2 High-field non-linear dielectric properties, switching and Preisach-FORC analysis; searching for DW mobility anomalies related to critical GS (Budget: 44.400,00lei).
III.3 Meso-scale modeling (Monte Carlo with FEM calculations) to describe the grain size effects on low field properties of BT-based polycrystalline ceramics (continued) (Budget: 30.000,00 lei).
III.4 Advanced modeling of high-field nonlinear dielectric and switching properties (Preisach-FORC or nucleation-growth models combined with FEM calculations) (Budget: 30.000,00 lei).
III.5 Project management, coordination and dissemination III (Budget: 15.000,00 lei).

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Up-to-date results

2017

2018

2019

Sumary of the major grant achivements

1. An experimental-theoretical study of Ag-BaTiO₃ ceramic composites was realised: (a) an outstanding permittivity increase was obtained by synergical use of Ag inclusions and of critical grain size of BaTiO₃ at 1mm; (b) by FEM modeling it was elucidated the role of inclusion microstructure and connectivity on the dielectric an tunability properties for partial percolation. Results: 2 ISI papers (one published, one under evaluation); communications to international conferences. Novelty at international level; new method for evaluating the role of partial percolation by FEM.
2. Study of structure-properties correlation and elucidating the origin of relaxor state in BaCe_xTi_1-xO₃ by macroscopic experiments (dielectric spectroscopy, ferroelectric hysterezis, calorimetry) combined with local investigations (high energy XRD with pair function distribution analysis, Raman spectroscopy). Results: one ISI paper published in collaboration; communications to international conferences. Novelty of the complex approach of this study at international level; contributions to the phase diagram of this system.
3. It was studied a magnetoelectric ceramic system with composition BaTi_1-xFe_xO_3-x/2(0 ≤ x ≤ 0.02) which was analysed from structural and functional point of view (electric, magnetic). Optimum compositions were tested for being applied as miniaturised resonator antenna. Results: one published ISI paper; communications to international conferences. Inovativity at national level: the compositional optimisation for the proposed application.
4. The effect of porosity on the functional properties of ceramic BaTiO₃ with variable porosities induced by the use of pollen sacrificial template. FEM models were developed to explain the role of porosity for specific pore microstructures. Results: one published ISI paper; communications to international conferences. Novelty at international level concerning the use of pollen grains as sacrificial bio-template.
5. It was demonstrated that ferroelectric and polar order have adirect role on the photoluminiscence in ceramics Eu³⁺- BaZr_xTi_1−xO₃. Results: one published ISI paper (50% reporting); communications to international conferences. Complex study of large impact and novelty at international level realised in collaboration.
6. It was performed a theoretical-experimental study in which the role of phase superposition on the functional properties of BaSn_xTi_1−xO₃ was demonstrated. Results: one ISI paper accepted (published on-line; 50% reporting). High impact study at international level.

 Publications in ISI papers with acknowledgement: 6 published, 1 under evaluation (grant members underlined)

1. Ina Turcan, Vlad Alexandru Lukacs, Lavinia Curecheriu, Leontin Padurariu, Cristina Elena Ciomaga, Mirela Airimioaei, George Stoian, Nicoleta Lupu, Liliana Mitoseriu, Microstructure and dielectric properties of Ag-BaTiO₃ composite ceramics, J. Eur. Ceram. Soc. 38, 5420-5429 (2018) (2018)

https://www.sciencedirect.com/science/article/pii/S0955221918304874

2. Giovanna Canu, Giorgia Confalonieri, Marco Deluca, Lavinia Curecheriu, Maria Teresa Buscaglia, Mihai Asandulesa, Nadejda Horchidan, Monica Dapiaggi, Liliana Mitoseriu, Vincenzo Buscaglia, Structure-property correlations and origin of relaxor behaviour in BaCe_xTi_1-xO₃, Acta Materialia 152 258-268 (2018)

https://www.sciencedirect.com/science/article/pii/S135964541830315X

3. Felicia Gheorghiu, Cristina Elena Ciomaga, Mantas Simenas, Mirela Airimioaei, Shan Qiao, Sorin Tascu, Vidmantas Kalendra, Juras Banys, Ovidiu G. Avadanei, Liliana Mitoseriu, Preparation and functional characterization of magnetoelectric Ba(Ti_1-xFe_x)O_3-x/2 ceramics. Application for a miniaturized resonator antenna, Ceram.Intern. 44, 20862-20870 (2018):

https://www.sciencedirect.com/science/article/pii/S0272884218321497

4. Vlad Alexandru Lukacs, Roxana Stanculescu, Lavinia Curecheriu, Cristina Elena Ciomaga, Nadejda Horchidan, Cipriana Cioclea, Liliana Mitoseriu, Structural and functional properties of BaTiO₃ porous ceramics produced by using pollen as sacrificial template, Ceramics International 46, 523-530 (2020); https://doi.org/10.1016/j.ceramint.2019.08.292

5. G. Canu, G. Bottaro, M.T. Buscaglia, C. Costa, O. Condurache, L. Curecheriu, L. Mitoseriu, V. Buscaglia, L. Armelao, Ferroelectric order driven Eu³⁺ photoluminescence in BaZr_xTi_1−xO₃ Perovskite, Sci. Reports 9, 6441 (2019); https://doi.org/10.1038/s41598-019-42897-1 (raportare 50%) 
6. N. Horchidan, L. Padurariu, C.E. Ciomaga, L. Curecheriu, M. Airimioaei, F. Doroftei, F. Tufescu, L. Mitoseriu, Room temperature phase superposition as origin of enhanced functional properties in BaTiO₃ - based ceramics, J. Eur. Ceram. Soc., 10.1016/j.jeurceramsoc.2019.11.088 (raportare 50%)

7. V.A. Lukacs, I. Turcan, L. Padurariu, L. Curecheriu, A. Cernescu, G. Stoian, C.E. Ciomaga, F. Tufescu, N. Lupu, L. Mitoseriu, Nonlinear dielectric properties of BaTiO₃ - silver composites: the role of microstructure, J. Alloys and Compounds (in evaluare, revizii minore).

 Presentations to international conferences: 1 invited, 5 oral, 10 poster:

1. Lavinia Curecheriu, Ina Turcan, Vlad Alexandru Lukacs, Leontin Padurariu, Cristina Elena Ciomaga, George Stoian, Nicoleta Lupu, Liliana Mitoseriu, Preparation and dielectric properties of Ag-BaTiO₃ composite ceramics, ICC7, Congresso Brasileiro de Ceramica, June 17-21, 2018, Foz do Iguacu, Brazil (poster).
2. Liliana Mitoseriu, Leontin Padurariu, Lavinia Curecheriu, Cristina Ciomaga, Ina Turcan, Local field engineering for tailoring electrical properties in ferroelectric-metallic particles composites, Electroceramics XVI - Hasselt, Belgium, 9-12th July 2018 (Invited talk).
3. Mirela Airimioaei, Alexandru Lukacs, Liliana Mitoseriu, Biotemplate-mediated synthesis of one-dimensional oxides, Electroceramics XVI - Hasselt, Belgium, 9-12th July 2018 (poster).
4. Alexandru Lukacs, Mirela Airimioaei, Lavinia Curecheriu, Cristina Ciomaga, Liliana Mitoseriu, Grain size effect on dielectric properties of submicron ranged BaTiO₃ ceramics, Electroceramics XVI - Hasselt, Belgium - 9th-12th July 2018 (poster).
5. Ina Turcan, Vlad Alexandru Lukacs, Lavinia Curecheriu and Liliana Mitoseriu, Enhanced permittivity in BaTiO₃ composites as result of silver addition and critical grain size ~1µm, European Conference on Applications of Polar Dielectrics ECAPD Moscow, Russia June 25-28, 2018 (oral).
6. Vlad Alexandru Lukacs, Ina Turcan, Mirela Airimioaei, Lavinia Curecheriu, Liliana Mitoseriu, Grain size effect on dielectric properties of submicron ranged BaTiO₃ ceramics, European Conference on Applications of Polar Dielectrics ECAPD Moscow, Russia June 25-28, 2018 (poster).
7. Cristina E. Ciomaga, Cipriana Padurariu, Lavinia P. Curecheriu, Nadejda Horchidan, Leontin Padurariu and Liliana Mitoseriu, Structural investigation and functional properties on porous BaTiO₃ ceramics, CIEC 16 – Torino, Italy 9-11 Septembre 2018 (poster).
8. Ina Turcan, Vlad Alexandru Lukacs, Lavinia Curecheriu, Leontin Padurariu, Cristina Elena Ciomaga, Liliana Mitoseriu, Exploiting the critical grain size and silver inclusions for enhancing permittivity in BaTiO₃ ceramics, CIEC 16 – Torino, Italy 9-11 Septembre 2018 (oral).
9. Nadejda Horchidan, Cristina Ciomaga, Liliana Mitoseriu, Study of dielectric & ferroelectric properties of BaGe_xTi_1-xO₃ (x³1)ceramics, CIEC 16 – Torino, Italy 9-11 Sept. 2018 (poster).
10. Cristina Elena Ciomaga, Cipriana Padurariu, Lavinia Petronela Curecheriu, Nadejda Horchidan, Leontin Padurariu, Liliana Mitoseriu, Structural investigation and functional properties on porous BaTiO₃ ceramics, CIEC 16 – Torino, Italy 9-11 Septembre 2018 (poster).
11. Leontin Padurariu, Liliana Mitoseriu, Exploiting local field inhomogeneity in ferroelectric based composites: towards improved functional properties, CIEC 16 – Torino, Italy 9-11 Septembre 2018 (poster).
12. A. Lukacs, M. Airimioaei, L.P. Curecheriu, C.E. Ciomaga, A. Bencan, M. Avakian, J. Jones, G. Stoian, N. Lupu and L. Mitoseriu, Grain size effects on the structural instability and functional properties of BaTiO₃ ceramics, F²Cp² Conference Lausanne, Switzerland, 14-19 July 2019 (oral)
13. Turcan, V.A. Lukacs, A. Cernescu, L. Curecheriu, L. Padurariu, C.E. Ciomaga, G. Stoian, N. Lupu, L. Mitoseriu, The role of composition on the dielectric and ferroelectric properties of Ag-BaTiO₃ composites F²Cp² Conference Lausanne, Switzerland, 14-19 July 2019 (1/2 raportare poster)
14. Ina Turcan, Lavinia Curecheriu, Leontin Padurariu, Liliana Mitoseriu, Ag-BaTiO₃ composite ceramics with multiple percolative behavior, 13^th Conference for Young Scientists in Ceramics, Dept. of Materials Eng., Faculty of Technology, Univ. Novi Sad, Serbia (October 16-19, 2019) (oral)
15. V. Lukacs, Lavinia P. Curecheriu, Jacob L. Jones, Liliana Mitoseriu, Scale dependent phenomena in BaTiO₃-based ceramics, 13^th Conference for Young Scientists in Ceramics, Dept. of Materials Eng., Faculty of Technology, Univ. Novi Sad, Serbia (October 16-19, 2019) (oral)
16. Horchidan, L. Padurariu, C.E. Ciomaga, L. Curecheriu, M. Airimioaei, F. Tufescu, L. Mitoseriu, Room temperature phase superp. as origin of enhanced funct. prop. in BaTiO₃ - based ceramics, 30^th Asian Advanced Materials Congress, 31 october-4 november 2019, Singapore (poster)

Presentations to national conferences: 1 oral, 1 poster

1. Vlad-Alexandru Lukacs, Mirela Airimioaei, Lavinia Curecheriu, Ina Turcan, Liliana Mitoseriu, Grain size influence on dielectric properties of dense BaTiO₃ ceramics, Conferinţa Naţională Fizica şi Tehnologiile Educaţionale Moderne, Facultatea de Fizică, Universitatea “Al. I. Cuza“ din Iaşi, România, 19 mai 2018 (oral) – I^st Prize
2. Ina Turcan, Vlad-Alexandru Lukacs, Lavinia Curecheriu, Leontin Padurariu, Cristina Elena Ciomaga and Liliana Mitoseriu, Effect of Silver filler on the sintering behavior and dielectric properties of BaTiO₃, Conferinţa Naţională Fizica şi Tehnologiile Educaţionale Moderne, Facultatea de Fizică, Universitatea “Al. I. Cuza“ din Iaşi, România, 19 mai 2018 (poster).

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