Growing crystals for your PhD, – The trials and tribulations Part 1

Will Brant tells us about growing Sr1-xTi1-2xNb2xO3 crystals for his PhD

For this post (and the next) I decided to do something a little different and talk about stories from my PhD which are in line with a crystal growing theme. Growing nice large crystals is not easy; there are so many factors which can influence the outcome of the growth of one specific type of crystal that some may consider it an art form. I found this out the hard way through my forays into trying to grow two seemingly similar, but ultimately very different, oxide materials. That is, Sr0.8Ti0.6Nb0.4O3 and Sr3TiNb4O15 (or Sr0.6Ti0.2Nb0.8O3).

The first of the two crystals I attempted to grow, Sr0.8Ti0.6Nb0.4O3, is a defect perovskite structure derived from the cubic perovskite SrTiO3. To get to Sr0.8Ti0.6Nb0.4O3 from SrTiO3 the TiO+4 cations are incrementally substituted with Nb+5 cations. In order to balance the difference in charge between titanium and niobium, vacancies are produced on the strontium position. (see structure below)

Figure 1

Sr0.8Ti0.6Nb0.4O3 was originally created in an attempt to produce new kinds of A-site deficient perovskites for lithium ion conduction applications. While Sr0.8Ti0.6Nb0.4O3 itself is not a very good lithium ion conductor it did exhibit some interesting short range structural distortions.[1] By growing a large single crystal, these distortions could be studied in greater detail.

My crystal growing method of choice was the floating zone furnace. To grow a crystal using this method, the ends of two sintered powder rods of a near-pure target material are melted using the focused heat from high power lamps. These molten regions are brought into contact with one another to produce a molten zone suspended between the two powdered rods. As the rods are moved vertically the molten zone travels through the polycrystalline powder. As the melt leaves the hot region crystals begin to form as the material cools. Over time, if all goes well, the growth of one of these crystals will predominate and a large, high quality single crystal will result.

The floating zone furnace.

The floating zone furnace.

The process began by preparing a pure Sr0.8Ti0.6Nb0.4O3 powder. This took around two to three weeks of repeated grinding and sintering. Once a rod of the polycrystalline material was prepared the growth could begin. By begin in this sense I mean about four trial growths were attempted to establish the best conditions. The hard work and long hours finally paid off however, as by the fifth attempt a stable growth had begun! However, this came to a grinding halt as a bubble began to form inside the melt. The bubble become larger and larger as the growth continued before finally bursting sending molten material flying out from the melt zone.

So what went wrong? Ironically, the presence of a few vacancies, while not in sufficient quantity to allow for lithium diffusion, encouraged entirely different, unintentional ion diffusion. That is, of oxygen ions! At high temperatures and slightly reducing conditions, oxygen is removed from the material. This gas became trapped in the melt gradually accumulating to the point where eventually a bubble of O2 burst and ruined everything.

It was time for round 6: remove as much oxygen as possible before attempting crystal growth. Given that oxygen rapidly left the material at high temperatures, this involved heating both the powder and then the sintered rod up to 1350 °C for extended periods of time. This time around, no bubbles formed and it appeared as though the melt and crystal growth were actually stable.



What did I get for my effort? A large lump of super dense highly fused polycrystalline ceramic. So, not a crystal. The lump was so large and dense that I couldn’t actually break it into smaller pieces despite my enthusiastic efforts to do so (RIP mortar and pestle). This lump of perovskite now sits in my desk. By this point I had decided to abandon trying to grow Sr0.8Ti0.6Nb0.4O3 crystals because another material was proving to be much more successful, Sr3TiNb4O15

To be continued…..


Perfect for the cold and ‘flu season: Eucalyptus Oil

What does is look like? eucalyptolThe structure of Eucalyptol. The carbon atoms are grey, the oxygen atom is red and the hydrogen atoms are white. Images generated using POV-Ray (The Persistence of Vision Ray-Tracer; and complied with VideoMach (

What is it?

This is the crystal structure of Eucalyptol also known as 1,8-cineole. Eucalyptol is the major component in Eucalyptus oil and is obtained from the leaves of Eucalyptus trees, many of which are indigenous to Australia. The leaves of these plants, which are toxic to many animals, are the primary food source of Koalas. Eucalyptus oil is a potent antiseptic and is also routinely used to relieve the symptoms of influenza and colds acting as a decongestant when inhaled.

Eucalyptol is a monoterpene and is therefore closely related to many other strongly smelling natural products such as Limonene which has a strong orange smell. Eucalyptol is classed as a bicyclic molecule as it is formed from two fused six membered rings. Unlike many other terpenes, this molecule has internal mirror symmetry with the symmetry axis passing through the oxygen atom.

Where did it come from?

Despite research into Eucalyptol being performed for more than 100 years, its crystal structure was not obtained until 2001. To obtain the structure, single crystals had to be grown in-situ on the diffractometer at -5 °C (just below its freezing point) using a floating-zone technique. This method of crystallisation is normally used for the purification of high-melting point solids such as silicon and ruby! The crystal structure was reported in: “Crystal Structure of Eucalyptol at 265 K”, A. D. Bond, J. E. Davies, Aust. J. Chem., 2001, 54, 683-684 and is deposited in the CCDC Refcode: MOFPAY