Ben Brown, Department of Physics,

Multiferroic Crystals
Introduction
This poster presents background information on the BSc project, Multiferroic Crystals. Multiferroic crystals are, as the name suggests, multiferroic. The term multiferroic was first proposed by Schmid to describe materials which display more than one of the primary ferroic properties such as; [1] Ferroelectricity Ferromagnetism Ferroelasticity Ferrotoroidicity The crystalline materials dealt with here only display ferroelectric and ferromagnetic properties. Lutetium iron oxide is part of a family of crystals which share the same structure. This group is known as RFe2O4 (where R is; Y, In, Sc, and Lanthanides from Dy to Lu). The structure of these crystals is shown below.

LuFe2O4

Crystal Growth
Once the final rod has been baked, it is time to use the floating zone technique. This uses an optical floating zone furnace (as shown below) to actually grow the crystal. Rotation of Feed Rod Growth Atmosphere Molten Zone Feed Rod

Ferroelectricity [2]
A material is said to be ferroelectric if it has a spontaneous electric polarisation which can be reversed by the application of an electric field. This is best described by the hysteresis curve below.

P, M
Halogen bulb
This shows the structure of the RFe2O4 crystals. They are comprised of two layers, T and W. The T layer is made of triangular levels of O, R and Fe which are stacked up the c-axis. The W layer is made entirely of iron atoms in a triangular lattice. These are an even mix of Fe2+ and Fe3+ atoms which leads to an average of Fe2.5+. [5]

Focusing Mirrors Crystal Growth Seed Rod Rotation of Seed Rod This diagram shows the components of the optical floating zone furnace. The black arrow show how the focusing mirrors direct light from the halogen bulbs onto the molten zone. (Created from an original image found in [9]) The rod produced from the powder synthesis will now become the feed rod from which the crystal will grow. The seed rod is the same material but should have a crystal structure. The two rods are set rotating in opposite directions in order that the temperature and composition of the molten zone become homogeneous. An atmosphere, commonly CO2/CO, is introduced before the lamps are turned on . Mirrors focus the heat onto the tip of the feed rod so it starts to melt. This must then be maneuvered so that it meets and sticks to the tip of the seed rod. Now, the focal point of the mirrors is moved slowly up the feed rod (at around 1mm per hour) thus melting it further up. This allows the molten zone to solidify onto the seed rod with a crystal structure. The feed rod is sometimes raised very slowly (at 0.3mm per hour) during the growth to ensure the crystal grows very thin and remains a single crystal.

E, B

Ferroelectricity arises as a result of charge ordering within the RFe2O4 structure [6]. This charge ordering is caused by charge frustration in the W layer which occurs when it is not possible to satisfy all the interactions in a system to find a ground state [7, 8]. To carry out experiments and research on this material requires a high quality single crystal so that the entire material is aligned. The image below shows a single crystal as there are no protrusions or separate crystals growing off in different directions.

This hysteresis curve shows how electric polarisation (P) depends on applied electric field (E), and also how the magnetisation (M) depends on the applied magnetic field (B). As the applied field increases, P or M increases from a to b. Once the applied field is removed, P or M rests at c. So P and M cannot be zero once their respective field is applied. [3]

Ferromagnetism
This is very common as it is the mechanism which causes magnetism in the everyday sense. Permanent magnets and the materials attracted to them are so because they are ferromagnetic. This is caused when a material has a spontaneous magnetisation which can be altered by application of a magnetic field. Similarly to ferroelectricity, this is best described by a hysteresis curve as shown above. Materials combining these properties will display a coupling between them. The stronger the coupling, the more potential there is for use of a material as it is this coupling which sets multiferroics aside from other materials. Many materials do not have very strong coupling but LuFe2O4 (lutetium iron oxide) shows promising signs that it may become very useful. One of the most effective uses would be in data storage. Coupling in LuFe2O4 means that data could be written electrically and read magnetically, thus combining the best parts of current data storage methods. [4]

This image shows a single crystal of LuFe2O4. This was grown using the floating zone technique described in the next section.

References
[1] - H. Schmid, Multiferroic Magnetoelectrics, Ferroelectrics 162, 317.
[2] - M. Lines & A. Glass (1979). Principles and applications of ferroelectrics and related materials. Clarendon Press, Oxford. ISBN 0-19-851286-4. [3] - http://www.codecogs.com/reference/physics/magnetism/magnetic_hysteresis.php (Retrieved on 28/11/2012) [4] - W. Erenstein, N. D. Mathur and J. F. Scott, Multiferroic and Magnetoelectric Materials, Nature 442, p. 759-765 [5] - M.A. Subramanian, T. He, J. Chen, N.S. Rogado, T.G. Calvarese and A.W. Sleight, Adv. Mater. 18, 1737-1739 (2006). [6] - J. van der Brink and D.I. Khomskii, J.Phys: Condens. Matter 20, 434217 (2008). [7] - N. Ikeda, J. Phys.: Condens. Matter 20, 434218 (2008). [8] - S. Blundell, Magnetism in Condensed Matter, Oxford Master Series in Condensed Matter Physics. [9] - Christo Guguschev, Jens Gtze, and Matthias Gbbels, American Mineralogist 95, p. 449-455

Powder Synthesis
To grow a single crystal like the one above takes a lot of time. To make a LuF22O4 crystal, exact proportions of Lu2O3 (lutetium oxide) and Fe2O3 (iron oxide) must be weighed out and ground together into a fine powder. This powder is then heated several times in different atmospheres for varying lengths of time. This will eventually produce a polycrystalline rod for use in the crystal growth. A typical method would be; 1. Heat for 12 hours at 1200C in a CO2/CO = 5 atmosphere 2. Grind powder 3. Heat for 24 hours at 1200C in an Ar atmosphere 4. Grind powder and compress into rod 5. Heat for 24 hours at 1250C in a CO2/CO = 5 atmosphere
(CO2/CO = 5 indicates the ratio of carbon dioxide to carbon monoxide in the furnace atmosphere)