Advances in single crystal growth and annealing treatment of electron-doped HTSC

High quality electron-doped HTSC single crystals of $\rm Pr_{2-x}Ce_{x}CuO_{4+\delta}$ and $\rm Nd_{2-x}Ce_{x}CuO_{4+\delta}$ have been successfully grown by the container-free traveling solvent floating zone technique. The optimally doped $\rm Pr_{2-x}Ce_{x}CuO_{4+\delta}$ and $\rm Nd_{2-x}Ce_{x}CuO_{4+\delta}$ crystals have transition temperatures $T_{\rm c}$ of $25$\,K and $23.5$\,K, respectively, with a transition width of less than $1$\,K. We found a strong dependence of the optimal growth parameters on the Ce content $x$. We discuss the optimization of the post-growth annealing treatment of the samples, the doping extension of the superconducting dome for both compounds as well as the role of excess oxygen. The absolute oxygen content of the as-grown crystals is determined from thermogravimetric experiments and is found to be $\ge 4.0$. This oxygen surplus is nearly completely removed by a post-growth annealing treatment. The reduction process is reversible as demonstrated by magnetization measurements. In as-grown samples the excess oxygen resides on the apical site O(3). This apical oxygen has nearly no doping effect, but rather influences the evolution of superconductivity by inducing additional disorder in the CuO$_{2}$ layers. The very high crystal quality of $\rm Nd_{2-x}Ce_{x}CuO_{4+\delta}$ is particularly manifest in magnetic quantum oscillations observed on several samples at different doping levels. They provide a unique opportunity of studying the Fermi surface and its dependence on the carrier concentration in the bulk of the crystals.Comment: 19 pages, 7 figures, submitted to Eur. Phys. J.

Raman light scattering study and microstructural analysis of epitaxial films of the electron-doped superconductor La_{2-x}Ce_{x}CuO_{4}

We present a detailed temperature-dependent Raman light scattering study of optical phonons in molecular-beam-epitaxy-grown films of the electron-doped superconductor La_{2-x}Ce_{x}CuO_{4} close to optimal doping (x ~ 0.08, T_c = 29 K and x ~ 0.1, T_c = 27 K). The main focus of this work is a detailed characterization and microstructural analysis of the films. Based on micro-Raman spectroscopy in combination with x-ray diffraction, energy-dispersive x-ray analysis, and scanning electron microscopy, some of the observed phonon modes can be attributed to micron-sized inclusions of Cu_{2}O. In the slightly underdoped film (x ~ 0.08), both the Cu_{2}O modes and others that can be assigned to the La_{2-x}Ce_{x}CuO_{4} matrix show pronounced softening and narrowing upon cooling below T ~ T_c. Based on control measurements on commercial Cu_{2}O powders and on a comparison to prior Raman scattering studies of other high-temperature superconductors, we speculate that proximity effects at La_{2-x}Ce_{x}CuO_{4}/Cu_{2}O interfaces may be responsible for these anomalies. Experiments on the slightly overdoped La_{2-x}Ce_{x}CuO_{4} film (x ~ 0.1) did not reveal comparable phonon anomalies.Comment: 7 pages, 8 figure

Phase decomposition and chemical inhomogeneity in Nd2 xCexCuO4 delta

Extensive x ray and neutron scattering experiments and additional transmission electron microscopy results reveal the partial decomposition of Nd2 x Cex CuO4 delta NCCO in a low oxygen fugacity environment such as that typically realized during the annealing process required to create a superconducting state. Unlike a typical situation in which a disordered secondary phase results in diffuse powder scattering, a serendipitous match between the in plane lattice constant of NCCO and the lattice constant of one of the decomposition products, Nd,Ce 2 O3 , causes the secondary phase to form an oriented, quasi two dimensional epitaxial structure. Consequently, diffraction peaks from the secondary phase appear at rational positions H,K,0 in the reciprocal space of NCCO. Additionally, because of neodymium paramagnetism, the application of a magnetic field increases the low temperature intensity observed at these positions via neutron scattering. Such effects may mimic the formation of a structural superlattice or the strengthening of antiferromagnetic order of NCCO, but the intrinsic mechanism may be identified through careful and systematic experimentation. For typical reduction conditions, the Nd,Ce 2 O3 volume fraction is approximately 1 , and the secondary phase layers exhibit long range order parallel to the NCCO CuO2 sheets and have a typical thickness of approximately 100 . The presence of the secondary phase should also be taken into account in the analysis of other experiments on NCCO, such as transport measurements