The average structure of superconducting La2CuO4.032 has been determined by single-crystal neutron diffraction data. The excess oxygen is located between two adjacent LaO layers. Its presence distorts the apical-oxygen sublattice in such a way that a short OO bond is formed (1.64Å). By scanning several hkl reflections, we have confirmed that a phase separation occurs below room temperature. The peaks of one phase are in agreement with the space group Cmca and the unit cell proposed by Jorgensen et al. and Cox et al.. However, a monoclinic unit cell is needed to index the second phase reflections. © 1989.

A two-phase refinement of a crystal for the compound La2CuO4+δ (δ=0.032), based on the neutron diffraction data collected at 15 K with the D9 diffractometer at ILL, using {double barred pipe}=0.48 A ̊, has been carried out. One phase (30%) consists of stoichiometric La2CuO4 domains, while the other (70%) of oxygen-rich La2CuO4.048 domains. The percentages of each phase, which have been refined together with the other parameters (scale factor, positional parameters, thermal factors and occupancy factors of the oxygen atoms), agree very well with the value determined from χAC measurements. The La2CuO4.048 structure is essentially the same as the average structure reported in ref. [1], the only difference being the oxygen content which is found to be δ= δ 0.70. The extra oxygen, O(4), is found to be in between two LaO layers in a similar position as the oxygen atoms located between two Nd layers in the N2CuO4 structure. The insertion of extra oxygen causes the displacement of some of the oxygen O(1) towards the O(3) positions. Different models are proposed for the distortion induced by this insertion according to the experimental value, 3.3 [6], found for the ratio of the amount of O(3) to that of O(4). If this ratio is assumed to be 3 and the O(3) atoms are localized about the insertion, then the formation of a short O(4)-O(3) bond would occur. The models not requiring the formation of the short bond correspond to ratios of 2 or 4. In the latter case there would be four displaced O(1), but due to the rigidity of the oxygen octahedra only two O(3) would be bonded to O(4), the other two being the apically opposite oxygen atoms of the same octahedra. © 1990.

The crystal structure of superconducting (37.5 K) La2CuO4.032 has been refined from single-crystal neutron-diffraction data at room temperature and 15 K. At both temperatures it exhibits the orthorhombic symmetry Cmca. The extra oxygen O4 atoms occupy the special positions ( 1 4y 1 4 with y=0.243 at 15 K). They are located between two successive LaO layers and are surrounded by distorted cubes built up of two interpenetrated tetrahedra, one comprising four La atoms and the other four O1 atoms (the apical oxygen atoms of the CuO6octahedra). The O4 insertion causes a 0.75 Å displacement of 4.8% of the O1 atoms towards new O3 positions (x=0.030(5), y=0.182(2), z=0.100(5)). From the refined values of the occupancy factors at 15 K, it is deduced that for each extra O4 three O1 are displaced to O3 with one short O3-O4 distance of 1.64(3) Å. This value indicates the formation of a strong O-O covalent bond of peroxide type with a formal 2-valence. Since the La and Cu sublattices have been found to be fully occupied and the doping does not change the oxygen charge, the La, Cu and O sublattices have the formal valences 6+, 2+, and 8-, respectively. However, the increase in La coordination and the consequent La-O distance readjustment indicate, when compared to the undoped compound structure, that a charge transfer occurs in La2CuO4.032, with the excess positive charge going either to the La or to the O sublattice. In the latter case it would correspond to the formation of holes in the O 2p band. © 1989.

The structure of superconducting La>2CuO>4.032 has been determined by single-crystal neutron diffraction data. The excess oxygen, O4, is located between two adjacent LaO1 layers. The presence of O4 distorts the apical-oxygen O1 sublattice in such that each O4 forms a short bond (1.64 Ɨ) with one O1, which indicates the formation of a strong covalent bond between these two atoms. The Cu and O2 sublattices as well as that of La are not affected by O4, however, 1.6% of the La cations increase their coordination from 9 to 10. © 1989 IOP Publishing Ltd.