Tuesday, August 5, 2014

Cornell - The perfect atom sandwich requires an extra layer

As reported by Cornell: Cornell researchers have discovered that sometimes, layer-by-layer atomic assembly – a powerful technology capable of making new materials for electronics – requires some unconventional “sandwich making” techniques.

The team, led by thin-films expert Darrell Schlom, the Herbert Fisk Johnson Professor of Industrial Chemistry in the Department of Materials Science and Engineering, describes the trick of growing perfect films of oxides called Ruddlesden-Poppers in Nature Communications Aug. 4.
 
The left figure demonstrates why the first double layer of strontium oxide is missing when growing a Ruddlesden-Popper oxide thin film. Titanium atoms (yellow) preferentially bond with oxygen atoms (gray) and sit at the center of a complete octahedron, making it energetically more favorable for titanium to switch positions with the topmost strontium oxide layer (red). Because of this, the first double layer of strontium oxide is always missing, and the extra layer rides the surface. By depositing an extra strontium oxide layer first, the desired first double layer is obtained. (source : Cornell)

These oxides are widely studied for their electronically enticing properties, among them superconductivity, magnetoresistance and ferromagnetism. Their layered structure is like a double Big Mac with alternating double and single layers of meat patties – strontium oxide – and bread – titanium oxide – in the case of the Ruddlesden-Poppers studied.

“Our dream is to control these materials with atomic precision,” Schlom said. “We think that controlling interfaces between Ruddlesden-Poppers will lead to exotic and potentially useful, emergent properties.”

Schlom’s lab makes novel thin films with molecular beam epitaxy, a deposition method that controls the order in which atom-thick layers are assembled layer-by-layer, which Schlom likens to precision spray-painting with atoms.
Full story here and Nature abstract below.
 
Atomically precise interfaces from non-stoichiometric deposition
Y. F. Nie, Y. Zhu, C.-H. Lee, L. F. Kourkoutis, J. A. Mundy, J. Junquera, Ph. Ghosez, D. J. Baek, S. Sung, X. X. Xi, K. M. Shen, D. A. Muller & D. G. Schlom   
Nature Communications 5, Article number: 4530, 04 August 2014
     
Complex oxide heterostructures display some of the most chemically abrupt, atomically precise interfaces, which is advantageous when constructing new interface phases with emergent properties by juxtaposing incompatible ground states. One might assume that atomically precise interfaces result from stoichiometric growth. Here we show that the most precise control is, however, obtained by using deliberate and specific non-stoichiometric growth conditions. For the precise growth of Srn+1TinOn+1 Ruddlesden–Popper (RP) phases, stoichiometric deposition leads to the loss of the first RP rock-salt double layer, but growing with a strontium-rich surface layer restores the bulk stoichiometry and ordering of the subsurface RP structure. Our results dramatically expand the materials that can be prepared in epitaxial heterostructures with precise interface control—from just the n=∞ end members (perovskites) to the entire RP homologous series—enabling the exploration of novel quantum phenomena at a richer variety of oxide interfaces.
 
 

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