ELECTROSTATIC ENERGY STORAGE IN ANTIFERROELECTRIC LIKE PEROVSKITE Tunisian Chemical Society 8th International Solid State Chemistry Conference -17-20 December 2017 – Royal Thalassa Monastir Hotel, Skanes-Monastir, Tunisia ELECTROSTATIC ENERGY STORAGE IN ANTIFERROELECTRIC LIKE PEROVSKITE PRESENTED BY ZANNEN Moneim Co-authors : A. Lahmar, Z. Kutnjak, J. Belhadi , H. Khemakhem, M. El Marssi ISSCC2017

Outline ISSCC2017 Introduction Applications Choice of N0.5Bi0.5TiO3 (NBT) Experimental procedure Results and discussions Conclusions ISSCC2017

Introduction ISSCC2017

Perovskite structure (ABO3) Why the Perovskite? The flexibility of the possible ionic substitutions. The simplicity of their crystallographic structure. The remarkable versatility of the perovskite structure (the A- and B Sites can accommodate nearly every element of the periodic table) leads to a huge range of properties.[1] [1]Schlom, D. G.; Chen, L.-Q.; Pan, X.; Schmehl, A.; Zurbuchen, M.A. “A Thin Film Approach to Engineering Functionality into Oxides”. J.Am. Ceram. Soc. 2008, 91, 2429−245 ISSCC2017

Ferroelectricity/antiferroelectricity antiferroelectric materials have a double hysterisis P-E loop. Ferroelectric materials have permanent dipoles A ferroeletric is generally defined as one of which exhibits hysterisis loop. ISSCC2017

Ferroelectricity vs Perovskite The ferroelectricity in perovskite materials is due to B-cation center off antiferroelectric materials have a double hysterisis P-E loop. ISSCC2017

Applications ISSCC2017

Applications Microelectronic components Multilayer capacitors Electromechanical transducers Infrared detectors Ferroelectric-Perovskite materials presents a large wide domain of applications ISSCC2017

Energy Storage [2] Xihong Hao , «A review on the dielectric materials for high energy-storage application », jOURNAL OF ADVANCED DIELECTRICS, Vol. 3, No. 1 (2013) 1330001 ISSCC2017

Calculations [3] [3] X.H. Hao, Y. Wang, L. Zhang, L.W. Zhang, S.L. An, Appl. Phys. Lett. 102 (2013) 163903. ISSCC2017

Choice of Ba0.5Na0.5TiO3 (NBT) ISSCC2017

Most Studied Material PZT (Pb(ZrxTi1−x)O3 ) PLZT (Pb1−xLax(ZryTi1−y)1−x/4O3) PMN (Pb(Mg1/3Nb2/3O3)- PT(PbTiO3) Lead (Pb) release into the environment at time of processing and remain for a long time in the environment and accumulates in living tissues which damages the brain and nervous system. It could introduce to the ecosystem and cause “acid rain”. Restoring and recycling of lead-based materials is an extensive environmental issues. ISSCC2017

Why Ba0.5Na0.5TiO3 (NBT)? ISSCC2017 [4] Jürgen Rödel, Wook Jo, Klaus T. P. Seifert, Eva-Maria Anton, and Torsten Granzow, J. Am. Ceram. Soc., 92 [6] 1153–1177 (2009). ISSCC2017

Why Ba0.5Na0.5TiO3 (NBT)? Lead free compound. Ferroelectric at room temperature. Large Remnant polarization. Pr  38 C.cm-2 Bi3+ ions are isoelectronic configuration with Pb2+ , both showing a lone pair effect. High coercive electrical field Ec  73 kV.mm−1 High conductivity ISSCC2017

Rare earth elements doped-NBT Na1/2 Bi1/2 TiO3 Ln3+ Na1/2 (Bi1-xLnx)1/2TiO3 Ln3+: Ho3+, Er3+ Reduction of conductivity due to Bismuth volatilization. Optical activities of rare earth elements. Multifunctional Materials. ISSCC2017

Experimental procedure ISSCC2017

Experimental procedure Ferroelectric measurement XRD SEM Ceramics/Films Ferroelectric measurement Photoluminescence ISSCC2017

Results and Discussions ISSCC2017

Results and discussions Pure Perovskite structure with R3c space group ISSCC2017

Results and discussions Reduction of grain size with dopant elements NBT ceramic NBT-Er ceramic NBT-Ho ceramic NBT thin film NBT-Er thin film NBT-Ho thin film. Reduction of grain size with dopant elements No evidence change ISSCC2017

Results and discussions Saturated P-E hysteresis loops for doped-NBT ISSCC2017

Results and discussions Antiferroelectric-like character ISSCC2017

Results and discussions Material nature composition Pmax (C. cm-2) E (Kv/cm) W1 (J.cm-3) W2 η (%) Ceramics NBT 31.23 80 0.19 0.37 33.92 NBT- Er 26.41 95 0.18 0.11 62.06 NBT-Ho 21.06 0.13 0.09 59.09 Films NBT (film) 61.03 500 12.31 10.87 53.1 NBT- Er (film) 40.25 9.26 6.98 57 NBT-Ho (film) 42.16 9.43 7.7 55.04 Interesting values of energy storage density for thin films ISSCC2017

Results and discussions Many applications such as reprographics, holography, medical diagnostics, etc. ISSCC2017

Conclusions Pure Perovskite structure without any symmetry change for doped samples. The microstructure analysis of both ceramics and thin films showed high microstructure density for all specimens. The stored and delivered energies were found to depend on the form and the composition of the sample. Such type of material, already compatible with electronic application and thermally stable, can be used in the electric or hybrid vehicles and in parallel with the battery to supply a maximal power. The trivalent holmium Ho3+ and Erbium Er3+emissions opens a great potential for application in photonics or optoelectronic devices. ISSCC2017

THANKS