Osijek, 14th June 2018

J.Bijelić1,*, A. Stanković1, B. Matasović1, B. Marković1, M. Bijelić2, G. Štefanić3, Ž.

Skoko2, Z. Jagličić4, S. Zellmer5, T. Preller5, G. Garnweitner5 and I. Djerdj1

1Josip Juraj Strossmayer University of Osijek, Department of Chemistry, Cara Hadrijana 8/A, Osijek, Croatia2University of Zagreb, Faculty of Science, Department of Physics, Biljenička 32, Zagreb, Croatia3Rudjer Boskovic Institute, Division of Materials Physics,Biljenička 54, Zagreb, Croatia4University of Ljubljana, Faculty of Civil and Geodetic Engineering, Jamova 2, Ljubljana, Slovenia5Braunschweig University of Technology, Institute for Particle Technology, Volkmaroder Str 5, Braunschweig, Germany

*jelena.bijelic@kemija.unios.hr

Aula of Josip Juraj Strossmayer University of Osijek

ProjectOsijek, 14th June 2018

1st YOUNG SCIENTIST DAY – PhD Conference

• Part of Croatian science foundation project: „Complex multiferroicmaterials prepared by solution chemistry methods (SOLFERROMAT)”

• formal associates• izv. prof. dr. sc. Igor Djerdj, supervisor• izv. prof. dr. sc. Berislav Marković• prof. dr. sc. Zvonko Jagličić• izv. prof. dr. sc. Dajana Gašo-Sokač• doc. dr. sc. Tomislav Balić• doc. dr. sc. Elvira Kovač-Andrić• dr. sc. Anamarija Stanković• dr. sc. Mirjana Bijelić• dr. sc. Goran Štefanić• dr. sc. Davor Ristić• dr. sc. Brunislav Matasović• Jelena Bijelić

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ContentsOsijek, 14th June 2018

1st YOUNG SCIENTIST DAY – PhD Conference

1. Introduction

2. Multiferroicity

3. Perovskite structure

1. Partial substitution on B-site

4. Properties of perovskites

5. Application of perovskites

6. Tellurates and tungstates

7. Synthesis

8. Results

1. XRD data of tellurates

2. XRD data of tungstates

3. Magnetic properties of tellurates

4. Magnetic properties of tungstates

5. EDS-SEM and HRTEM of tungstates

9. Conclusions

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1. IntroductionOsijek, 14th June 2018

1st YOUNG SCIENTIST DAY – PhD Conference

• An ultimate need for reducing the size and expanding

density of data storage devices

• Ferroelectricity and ferromagnetism are essential for

achieving multifunctional properties

• Solution chemistry synthesis

• complex double or single perovskites with A3B2(Te/W)O9 and

A2B(Te/W)O6 (A=earth alkali metal, B=transition metal)

structure type

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2. MultiferroicityOsijek, 14th June 2018

1st YOUNG SCIENTIST DAY – PhD Conference

• Ferromagnetism, ferroelasticity, ferroelectricity (+

ferrimagnetism, antiferromagnetism)

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3. Perovskite structureOsijek, 14th June 2018

1st YOUNG SCIENTIST DAY – PhD Conference

Ideal cubic structure (ideal ionic size ratios) ABO3

Compensation for non-ideal ionic size ratios• Expansion/contraction of octahedra BO6

• Octahedra can tilt

Electronic instabilities• Distortion

• Shifting of cations from their positions

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Corner-sharednetwork ofoctahedra

Voids filledwith Acation

3.1. Partial substitution on B-siteOsijek, 14th June 2018

1st YOUNG SCIENTIST DAY – PhD Conference

• Partial substitution as very common method for tailoring the properties ofperovskites

• AB’B’’O6 substitution of exactly half of the B-site cations• B’ and B’’ can remain disordered• Formation of ordered double perovskite structure

• Orderingsa. Rock-salt (elpasolite structure K2NaAlF6)b. Layered (occasionally)c. Columnar (very rare; only been found in A’A’’B’B’’O6)

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Generation of two unitswithin the single phase

whic operate separately to achieve multifunctional

properties

4. Properties of perovskitesOsijek, 14th June 2018

1st YOUNG SCIENTIST DAY – PhD Conference

• Possible properties• Superconductivity• Magnetic orderings (antiferro-, ferro-, ferri-)• Magnetic frustration (no long-range order)• Catalytic properties• Ferroic atomic displacements• Ionic conductivity

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5. Application of perovskitesOsijek, 14th June 2018

1st YOUNG SCIENTIST DAY – PhD Conference

• Electrode and electrolyte materials for fuel cells

• Magnetic memory components

• Dielectrics of piezoelectrics in electronic devices and

sensors

• Catalytic converters in diesel vehicles

• Components for solar cells

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Aqueous Sol−Gel Route toward Selected Quaternary Metal Oxides with Single and Double Perovskite-Type StructureContaining Tellurium

Igor Djerdj, Berislav Marković, Jasminka Popović, Suraj Mal, Tobias Weller, Marko Nuskol, Zvonko Jagličić, Damir Pajić, Christian Suchomski, Pascal Voepel, Roland Marschall, Bojan Kozlevčar and Bernd M. Smarsly

Department of Chemistry, J. J. Strossmayer University of Osijek, Ulica cara Hadrijana 8/a, HR-31000 Osijek, Croatia

Ruđer Boškovic Institute, Bijenicka 54, 10000 Zagreb, Croatia

Institute of Mathematics, Physics and Mechanics, Jadranska 19, 1000 Ljubljana, Slovenia

Institute of Physical Chemistry, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 17, 35392 Giessen, Germany

Department of Physics, Faculty of Science, University of Zagreb, Bijenicka 32, 10000 Zagreb, Croatia

Faculty of Chemistry and Chemical Technology, University of Ljubljana, Vecna pot 113, SI-1000 Ljubljana, Slovenia

Article

pubs.acs.org/crystal

DOI: 10.1021/acs.cgd.5b01558igor.djerdj@kemija.unios.hrBernd.Smarsly@phys.Chemie.uni-giessen.de

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6. Tellurates and tungstatesOsijek, 14th June 2018

1st YOUNG SCIENTIST DAY – PhD Conference 11

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COMPOUND TOLERANCE FACTOR

Sr3Fe2TeO9 1.0031

Sr3Fe2WO9 0.9964

Ba3Fe2TeO9 1.0643

Ba3Fe2WO9 1.0571

Perfect cubicperovskitestructure

t>1 A-site cation istoo large strain

cannot be relieved byoctahedral tiltinghexagonal structure

7. SynthesisOsijek, 14th June 2018

1st YOUNG SCIENTIST DAY – PhD Conference 12

8. ResultsOsijek, 14th June 2018

1st YOUNG SCIENTIST DAY – PhD Conference

• Powder XRD• Magnetic measurements using SQUID magnetometer• EDS-SEM• TEM, HR-TEM

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8.1. XRD data of

telluratesOsijek, 14th June 2018

1st YOUNG SCIENTIST DAY – PhD Conference 14

8.2. XRD data of tungstatesOsijek, 14th June 2018

1st YOUNG SCIENTIST DAY – PhD Conference 15

8.3. Magnetic properties of telluratesOsijek, 14th June 2018

1st YOUNG SCIENTIST DAY – PhD Conference 16

Ferrimagnetic ordering withTc= 667 K (close to SSR value

of 715 K)

Antiferromagnetic ordering below 80 K, at 20K superparamagnetic blocking 16

8.4. Magnetic properties of tungstatesOsijek, 14th June 2018

1st YOUNG SCIENTIST DAY – PhD Conference 17

TC= 220 K

Ferrimagnetic ordering ofSr3Fe2WO9 with no visible TC

(by SSR reported at 373 K).

Superparamagnetic blocking at 50 K (maximum at ZFC curve)

Ferrimagnetic ordering ofBa3Fe2WO9 with TC=220 K (by

SSR reported at 330 K).

Superparamagnetic blocking at 64 K.

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8.5. EDS-SEM and HRTEM of tungstatesOsijek, 14th June 2018

1st YOUNG SCIENTIST DAY – PhD Conference 18

EDS-SEM of Sr3Fe2WO9 (a, b) and Ba3Fe2WO9 (c, d)

HRTEM of Ba3Fe2WO9 (a, b, c) and Ba3Fe2WO9 (d, e, f)

9. ConclusionsOsijek, 14th June 2018

1st YOUNG SCIENTIST DAY – PhD Conference

• Small particle sizes (in nanometer range) despite the

high calcination temepratures

• Structures similar to corresponding tellurates

• Lower calcination temperatures

• Differences in magnetic properties of the same

compounds synthesized by SSR and sol-gel

• High yields (75-85%)

• Ferrimagnetic ordering of synthesized compounds

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Thanks to sponsors!

Supporting publication