Use of an AX3 close-packing description of layered perovskites in understanding the role of various A ions in cuprate superconductors

Ganguly, P. ; Shah, N. (1993) Use of an AX3 close-packing description of layered perovskites in understanding the role of various A ions in cuprate superconductors Physica C: Superconductivity and its Applications, 208 (3-4). pp. 307-322. ISSN 0921-4534

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Official URL: http://linkinghub.elsevier.com/retrieve/pii/092145...

Related URL: http://dx.doi.org/10.1016/0921-4534(93)90202-2

Abstract

The layered perovskite oxide systems have been modelled on the basis of two types of AX3 close-packing found, for example, in the Ll2 and DO22 structure types of Cu3Au and TiAl3, respectively. The former is known to give the ABX3 perovskite structure. It is proposed that the latter gives the AX rock-salt structure upon the loss of XX rows for which the ionic radius ratio rA/rX > 0.73. The lower limit of the tolerance factor is also justified in such a packing scheme based on this geometrical constraint of rA/rX > 0.73 or a minimum rAsim;1.02 Å. An admixture of the two kinds of packing yields the layered perovskite structure. The AX#3 packing (X# includes the anion vacancy) may be modelled in terms of pseudo-spins in the axial next-nearest-neighbor-Ising (ANNNI) model. The pseudo-spins correspond to the two relative orientations of the AX# rows instead of the lengths of the domains as in the usual description of long period intermetallic superlattices using antiphase boundary (APB) structures. Just as the intermetallic compounds, the layered cuprate perovskites in general have the m, 1n Fisher-Selke notation where m is the number of spins in "ferromagnetic" ...AX#.B.X#X#.AX#... (perovskite) domains and n is the number of spins in the "antiferromagnetic" ...AX#.X#X#.X#A...(or rock-salt) domains. Three sites for the A ions may then be distinguished. The 3, 1 notation has the sequence ...APX#.X#X#.B.AFX#.X#X#.B.APX#.X#X#.X#AR.X#X#.ARX#.X# X#..., where AP are large cations such as La3+, Ba2+, Sr2+ in nine-fold coordination; AF are cations with eight-fold coordinations such as Ca2+ and Y3+. TlBa2CaCu2O7 is an example of such a notation. The AR ions with six-fold coordination are ions such as Tl, Bi, Pb etc. It is proposed that the constraints of the close-packing model require the average size of the AR ions to have an average radius of 1.02 Å. This is due to an admixture of various valence states in the AR ions such as Bi, Tl, Pb to provide epitaxial stabilization. The possible role of an admixture of the valence skipping states of the AR ions in enhancing the superconducting transition temperatures is discussed.

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