It is well known that the microstructures of the transition-metal oxides (refs 1-3), including the high-transition-temperature (high-Tc) copper oxide superconductors (refs 4-7), are complex. This is particularly so when there are oxygen interstitials or vacancies (ref.8), which influence the bulk properties. For example, the oxygen interstitials in the spacer layers separating the superconducting CuO2 planes undergo ordering phenomena in Sr(2)O(1+y)CuO(2) (ref. 9), YBa(2)Cu(3)O(6+y) (ref. 10) and La(2)CuO(4+y) (refs 11-15) that induce enhancements in the transition temperatures with no changes in hole concentrations. It is also known that complex systems often have a scale-invariant structural organization16, but hitherto none had been found in high-Tc materials. Here we report that the ordering of oxygen interstitials in the La(2)O(2+y) spacer layers of La(2)CuO(4+y) high-Tc superconductors is characterized by a fractal distribution up to a maximum limiting size of 400 microns. Intriguingly, these fractal distributions of dopants seem to enhance superconductivity at high temperature.
While recent experiments have found that at optimum doping for the highest critical temperature in HgBa$_2$CuO$_{4+y}$ (Hg1201) the oxygen interstitials (O-i) are not homogeneously distributed but form one-dimensional atomic wires, there are no available information of its electronic structure considering self-organized O-i atomic wires. Here we report the calculated electronic structure of HgBa$_2$CuO$_{4+y}$ where oxygen interstitials form atomic wires along (1,0,0) crystal direction in the Hg layer. We find that at optimum doping for superconductivity the chemical potential is tuned near an…
Novel nanoscale probes are opening new venues for understanding unconventional electronic and magnetic functionalities driven by multiscale lattice complexity in doped high temperature superconducting perovskites. In this work we focus on the multiscale texture at supramolecular level of atomic oxygen interstitials (O-i) stripes in HgBa$_2$CuO$_{4+y}$ at optimal doping for the highest superconducting critical temperature $T_C$=94K. We report compelling evidence for the nematic phase of oxygen-interstitial O-i atomic wires with fractal-like spatial distribution over multiple scales by using sca…
Novel imaging methods show that the mobile dopants in optimum doped La$_2$CuO$_{4+y}$ (LCO) get self-organized, instead of randomly distributed. Rigid-band models fail because of ordering of dopants and supercell calculations are required to obtain the Fermi surface reconstruction. We have performed advanced band calculations for a large supercell La$_{16}$Cu$_8$O$_{32+N}$ where $N$=1 or 2 oxygen interstitials form rows in the spacer La$_{16}$O$_{16+N}$ layers intercalated between the CuO$_2$ layers as determined by scanning nano x-ray diffraction. The additional oc cupied states made by inter…
Superconductivity in anti-PbO-type iron chalcogenides Fe1-xTe1-ySey (x = 0, 0.1, y = 0.1 0.4) depends on the amount (x) of interstitial iron atoms located between the FeTe1-ySey layers. Non-superconducting samples of nominal Fe1.1Te1-ySey convert to superconductors with critical temperatures up to 14 K after annealing at 300°C in an oxygen atmosphere. The process is irreversible upon subsequent hydrogen annealing. Magnetic measurements are consistent with the formation of iron oxides suggesting that oxygen annealing preferably extracts interstitial iron from Fe1-xTe1-ySey which interfere with …
Band structure calculations are presented for large supercells of Ba$_2$CuO$_4$ (BCO) with O-vacancies in planar or apic al positions, and of superoxygenated La$_2$CuO$_4$ (LCO) with oxygen interstitials in the La$_2$O$_2$ layers. It is foun d that apical oxygen vacancies in BCO act as electron dopants and makes the electronic structure similar to that of hole doped LCO. Excess oxygen interstitials forming wires in the La$_2$O$_2$ layers of LCO are shown to yield a much larger density-of-states at the Fermi energy than for the stoichiometric compound related with a segmentation of the Fermi su…
The oxygen dopants are essential in tuning electronic properties of Bi$_2$Sr$_2$Ca$_{n-1}$Cu$_n$O$_{2n+4+δ}$ superconductors. Here we apply the technique of scanning tunneling microscopy and spectroscopy to study the influence of oxygen dopants in an optimally doped Bi$_2$Sr$_{2-x}$La$_x$CuO$_{6+δ}$ and an overdoped Bi$_{2-y}$Pb$_y$Sr$_2$CuO$_{6+δ}$. In both samples, we find that interstitial oxygen atoms on the SrO layers dominate over the other two forms of oxygen dopants, oxygen vacancies on the SrO layers and interstitial oxygen atoms on the BiO layers. The hole doping is estimated from th…
Mn5Si3-type structure has been offering an interstitial chemistry. Recent report of enhancement of superconductivity in a Nb-based Mn5Si3-type compound by addition of an interstitial atom motivated us to investigate the effect of oxygen-addition in Mn5Si3-type Zr5Pt3. The superconducting critical temperature of 6.4 K in the parent Zr5Pt3 is monotonously reduced to 3.2 K in Zr5Pt3Ox (x=0.6) with increasing oxygen-content. As x is further increased from 0.6 to 2.5, exceeding the full occupancy of oxygen site (x=1.0), samples become multi-phases composed of Zr5Pt3O0.5-0.6, ZrPt and ZrO2. However,…
Interstitial oxygen order and its competition with superconductivity in La$_2$PrNi$_2$O$_{7+δ}$
Tsinghua University（清华大学）；Institute of Physics, Chinese Academy of Sciences（中国科学院物理研究所）；University of Chinese Academy of Sciences（中国科学院大学）；New Cornerstone Science Laboratory（新 cornerstones 科学实验室）；Hefei National Laboratory（合肥国家实验室）
Multiple functional ionic and electronic orders are observed in high temperature superconducting cuprates. The charge density wave order is one of them and it is spatially localized in spatial regions of the material. It is also known that the oxygen interstitials introduced by chemical intercalation self-organize in different oxygen rich regions corresponding with hole rich regions in the Cu$O_2$ layers left empty by the charge density wave order domains. However, what happens in between these two order is not known, and neither there is a method to control this spatial separation. Here we de…
We have studied the annealing effect in transport properties of High temperature Josephson Junctions (HTc JJ) made by ion irradiation. Low temperature annealing (80 degrees Celsius) increases the JJ transition temperature (TJ) and the Ic.Rn product, where Ic is the critical current and Rn the normal resistance. We found that the spread in JJ characteristics can be lowered by sufficient long annealing times. Using random walk numerical simulations, we showed that the characteristic annealing time and the evolution of the spread in JJ characteristics can be explained by a vacancy-interstitial an…
The cuprate material BSCCO-2212 is believed to be doped by a combination of cation switching and excess oxygen. The interstitial oxygen dopants are of particular interest because scanning tunnelling microscopy (STM) experiments have shown that they are positively correlated with the local value of the superconducting gap, and calculations suggest that the fundamental attraction between electrons is modulated locally. In this work, we use density functional theory to try to ascertain which locations in the crystal are energetically most favorable for the O dopant atoms, and how the surrounding …
The simplest cuprate superconductor La2CuO4+y with mobile oxygen interstitials exhibits a clear phase separation, but only recently a bulk multiscale structural phase separation has been observed by using scanning micro X-ray diffraction. Here we get further information on the structural phase separation, using local probe X-ray absorption near edge structure. The spatial distribution of superconducting units is a key parameter controlling percolative superconductivity in complex matter with dispersed superconducting units. These oxides form super-molecular architectures made of superconductin…
The organization of dopants in high temperature superconductors provides complex topological geometries that controls superconducting properties. This makes the study of dopants spatial distribution of fundamental importance. The mobile oxygen ions, y, in the CuO2 plane of YBa2Cu3O6+y (0.33<y<0.67) form ordered chains which greatly affect the transport properties of the material. Here we visualize and characterize the 2D spatial organization of these oxygen chains using scanning micro X-ray diffraction measurements in transmission mode on a thin single crystal slab with y=0.33 (Tc=7 K) near th…
We have examined the effects of 20 keV electron irradiation on [-Cu(1)-O(1)-]n chain oxygen arrangements in oxygen deficient but otherwise twin-free YBa2Cu3O6+x single crystals. Comparison of polarized Raman spectra of non-irradiated and irradiated areas provides evidence that electron bombardments instigate the collective hopping of oxygen atoms either from an interstitial at O(5) site to a vacant O(1) chain site or by reshuffling the chain segments to extend the average length of chains without changing the overall oxygen content. This oxygen ordering effect, while counter-intuitive, is anal…
We present a detailed room temperature x-ray powder diffraction study on La2-xSrxNiO4+d with 0<=x<=0.12 and 0<=d<=0.13. For x=0.02, 0.04 and 0.06 the oxygen content phase diagrams of the Sr doped samples show a similar sequence of pure phases and miscibility gaps as for pure La2NiO4+d. We find a weak Sr doping dependence of the d-range for the pure LTO, LTT and HTT phases; but overall, the d-ranges of the different phases do not vary strongly for x<=0.06. Drastic changes are observed for x=0.08 and 0.12, where miscibility gaps successively disappear. For x=0.12 all oxygen doped samples are in …
The superconducting properties of high-\tc\ materials are functions of carriers concentration, which is controlled by the concentration of defects including heterovalent cations, interstitial oxygen ions, and oxygen vacancies. Here we combine low-temperature thermal treatment of La$_{2-x}$Sr$_{x}$CuO$_{4}$ epitaxial thin films and confocal Raman spectroscopy to control and investigate oxygen vacancies. We demonstrate that the apical site is the most favorable position to accommodate oxygen vacancies under low-temperature annealing conditions. Additionally we show that in high-quality films of …
The nuclear quadrupole resonance (NQR) spectrum of strontium doped La$_2$CuO$_4$ surprisingly resembles the NQR spectrum of La$_2$CuO$_4$ doped with excess oxygen, both spectra being dominated by a main peak and one principal satellite peak at similar frequencies. Using first-principles cluster calculations this is investigated here by calculating the electric field gradient (EFG) at the central copper site of the cluster after replacing a lanthanum atom in the cluster with a strontium atom or adding an interstitial oxygen to the cluster. In each case the EFG was increased by approximately 10 …
The effect of hydrostatic pressure up to 2 GPa on the superconductiong transitions in La{2-x}Sr{x}CuO{4+delta} is investigated. The ambient and high pressure properties of two series of samples with x=0 and x=0.015 and 0<delta<0.1 are characterized and compared by ac-susceptibility measurements. At ambient pressure both sets of samples fit into the same phase diagram as a function of the total hole concentration, n_h. For n_h<0.085 there is a single superconducting transition (T_{c} approx 30 K) with an unusually large pressure coefficient, dT_c{30}/dp approx 10K/GPa. At higher hole density (n…
There is a growing compelling experimental evidence that a quantum complex matter scenario made of multiple electronic components, and competing quantum phases is needed to grab the key physics of high critical temperature (Tc) superconductivity in layered cuprates. While it is known that defects self-organization controls Tc, the mechanism remains an open issue. Here we focus on the theoretical prediction of the multi-band electronic structure and the formation of broken Fermi surfaces generated by the self-organization of oxygen interstitials O-i atomic wires in the spacer layers in HgBa2CuO…
The segregation of oxygen in the high critical temperature cuprate superconductor $La_2CuO_{4+y}$ has been systematically studied along the years. In a recent set of experiments, Poccia et al related, for the first time, time ordering ($t$) of oxygen interstitials with the corresponding superconducting transition temperature $T_c(t)$. We develop a phenomenological description of the time ordering forming pattern domains and show how it may affect the superconducting interaction. The superconducting self-consistent calculations in a system with electronic granular structure of varying hole dopi…
Oxygen chain fragments are known to appear at the insulator to superconductor transition (SIT) in YBa2Cu3O6+y. However the self organization and the size distribution of oxygen chain fragments is not known. Here we contribute to fill this gap, using scanning micro X ray diffraction which is a novel imaging method based on advances in focusing synchrotron radiation beam. This novel approach allows us to probe both real-space and k-space of a high-quality YBa2Cu3O6.33 single crystals with Tc=7K. We report compelling evidence for nanoscale striped puddles, with Ortho-II structure, made of chain f…
Electronic functionalities in materials from silicon to transition metal oxides are to a large extent controlled by defects and their relative arrangement. Outstanding examples are the oxides of copper, where defect order is correlated with their high superconducting transition temperatures. The oxygen defect order can be highly inhomogeneous, even in "optimal" superconducting samples, which raises the question of the nature of the sample regions where the order does not exist but which nonetheless form the "glue" binding the ordered regions together. Here we use scanning X-ray microdiffractio…
