Growth of Vanadyl Pyrophosphate Single Crystals

The present work communicates about the first successful attempt at growing of sizeable single crystals of vanadyl pyrophosphate (VO)₂P₂O₇ (VOPO) — a low dimensional antiferromagnet. The growth of VOPO is complicated by two features of this compound. The first is a strong sensitivity of the oxydation state of vanadium (and stability of VOPO) to the oxygen content in the growth atmosphere. The second is a tendency of the VOPO-melt to glass formation during the cooling due to its high viscosity. Therefore the growth has to be carried out with a very low growth rate and in an atmosphere with exactly controllable oxygen content. The best results were achieved with a combination of Czochralski and Kyropoulos techniques, i.e. pulling of crystals with simultaneous cooling of the melt. Crystals of VOPO with sizes up to 10 × 5 × 3 mm³ have been grown. The growth from the melt is accompanied by growth from gaseous phase also (sublimation). Since the VOPO phase has a homogeneity range in oxygen content, attention was paid to the composition of the grown crystals. Growth experiments combined with TGA and XRD measurements show, that the oxygen content and thus the oxidation state of vanadium in the crystals can be adjusted accurately.