Recent scanning tunneling microscopy studies have shown that local nanoscale pairing inhomogenities are correlated with interstitial oxygen dopants in Bi-2212. Combining electrostatic and cluster calculations, in this paper the impact of a dopant on the local Madelung and charge transfer energies, magnetic exchange J, Zhang-Rice mobility, and interactions with the lattice is investigated. It is found that electrostatic modifications locally increases the charge transfer energy and slightly suppresses J. It is further shown that coupling to c-axis phonons is strongly modified near the dopant. The combined effects of electrostatic modifications and coupling to the lattice yield broadened spectral features, reduced charge gap energies, and a sizable local increase of J. This implies a strong local interplay between antiferromagnetism, polarons, and superconducting pairing.
Recent experiments on Bi-based cuprate superconductors have revealed an unexpected enhancement of the pairing correlations near the interstitial oxygen dopant ions. Here we propose a possible mechanism -- based on local screening effects -- by which the oxygen dopants do modify the electronic parameters within the CuO_2 planes and strongly increase the superexchange coupling J. This enhances the spin pairing effects locally and may explain the observed spatial variations of the density of states and the pairing gap.
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 …
We address the question of whether the superconducting transition temperature (Tc) of high-Tc cuprates is enhanced when randomly distributed dopant atoms form an ordered array in the charge reservoir layers. This study is possible for the Sr2CuO3+d superconductor with K2NiF4-type structure in which oxygen atoms only partially occupy the apical sites next to the CuO2 planes and act as hole-dopants. We show that remarkable Tc enhancement up to 95K in this mono CuO2 layered HTS is associated with the apical oxygen ordering, not to the hole concentration change. The result points a route toward fu…
We present a methodology based on \textit{ex-situ} (post-growth) electrochemistry to control the oxygen concentration in thin films of the superconducting oxide La$_2$CuO$_{4+y}$ grown epitaxially on substrates of isostructural LaSrAlO$_4$. The superconducting transition temperature, which depends on the oxygen concentration, can be tuned by adjusting the pH level of the base solution used for the electrochemical reaction. As our main finding, we demonstrate that the dopant oxygens can either occupy the interstitial layer in an orientationally disordered state or organize into a crystalline ph…
We have performed an angular-resolved photoemission study of underdoped, optimally doped and overdoped Bi$_{2}$Sr$_2$CaCu$_2$O$_{8+x}$ samples using a wide photon energy range (15 - 100 eV). We report a small and broad non-dispersive A$_{1g}$ peak in the energy distribution curves whose intensity scales with doping. We attribute it to a local impurity state similar to the one observed recently by scanning tunneling spectroscopy and identified as the oxygen dopants. Detailed analysis of the resonance profile and comparison with the single-layered Bi$_{2}$Sr$_2$CuO$_{6+x}$ suggest a mixing of th…
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…
The highest temperature superconductors are electronically inhomogeneous at the nanoscale, suggesting the existence of a local variable which could be harnessed to enhance the superconducting pairing. Here we report the relationship between local doping and local strain in the cuprate superconductor Bi$_2$Sr$_2$CaCu$_2$O$_{8+x}$. We use scanning tunneling microscopy to discover that the crucial oxygen dopants are periodically distributed, in correlation with local strain. Our picoscale investigation of the intra-unit-cell positions of all oxygen dopants provides essential structural input for …
Despite intensive research a physical explanation of high Tc superconductors remains elusive. One reason for this is that these materials have generally a very complex structure making useless theoretical models for a homogeneous system. Little is known on the control of the critical temperature by the space disposition of defects because of lack of suitable experimental probes. X-ray diffraction and neutron scattering experiments used to investigate y oxygen dopants in YBa2Cu3O 6+y lack of spatial resolution. Here we report the spatial imaging of dopants distribution in-homogeneity in YBa2Cu3…
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…
The modification of the properties of CeO$_2$ through aliovalent doping are investigated within the \emph{ab-initio} density functional theory framework. Lattice parameters, dopant atomic radii, bulk moduli and thermal expansion coefficients of fluorite type Ce$_{1-x}$M$_{x}$O$_{2-y}$ (with M$ = $ Mg, V, Co, Cu, Zn, Nb, Ba, La, Sm, Gd, Yb, and Bi)are presented for dopant concentrations in the range $0.00 \leq x \leq 0.25$. The stability of the dopants is compared and discussed, and the influence of oxygen vacancies is investigated. It is shown that oxygen vacancies tend to increase the lattice…
Scanning tunneling spectroscopy has recently discovered a positive correlation between the magnitude of the superconducting gap and positions of dopant oxygen atoms in Bi-based cuprates. We propose a microscopic mechanism that could be responsible for this effect. In particular, we demonstrate that the dopant-induced spatial variation of the atomic levels always enhances the superexchange interaction.
Gap fluctuations, Cooper pairs with finite center-of-mass momentum, and suppression of superconductivity in inhomogeneous systems with dopant superpuddles agglomerates
A new theoretical model is presented to study the nanoscale electronic inhomogeneity in high-$T_c$ cuprates. In this model, we argue that the randomly distributed out-of-plane interstitial oxygen dopants induces locally the off-diagonal (i.e., hopping integral) disorder. This disorder modulates the superexchange interaction resulting from a large-$U$ Hubbard model, which in turns changes the local pairing interaction. The microscopic self-consistent calculations shows that the large gap regions are registered to the locations of dopants. Large gap regions exhibit small and broader coherence pe…
The effect of Co-Ga paired substitution on the superconducting properties of YBa2Cu3O7-d (Y-123) has been investigated by X-ray diffraction, ac susceptibility,dc resistivity and oxygen content measurements. We report in this paper the results of our studies on the paired substitution of a magnetic and non-magnetic ion at Cu site in Y-123, while keeping the total dopant concentration fixed. The simultaneous substitution of Co and Ga at Cu site shows variation in the transition temperature (Tc), oxygen content and hole concentration as a function of change in the balance of magnetic (Co) and non…
Emergency of superconductivity at the instabilities of antiferromagnetism (AFM), spin/charge density waves has been widely recognized in unconventional superconductors. In copper-oxide superconductors, spin fluctuations play a predominant role in electron pairing with electron dopants yet composite orders veil the nature of superconductivity for hole-doped family. However, in electron-doped ones the ending point of AFM is still in controversy for different probes or its sensitivity to oxygen content. Here, by carefully tuning the oxygen content, a systematic study of Hall signal and magnetores…
Fluorite CeO$_2$ doped with group IV elements is studied within the DFT and DFT+U framework. Concentration dependent formation energies are calculated for Ce$_{1-x}$Z$_x$O$_2$ (Z= C, Si, Ge, Sn, Pb, Ti, Zr, Hf) with $0\leq x \leq 0.25$ and a roughly decreasing trend with ionic radius is observed. The influence of the valence and near valence electronic configuration is discussed, indicating the importance of filled $d$ and $f$ shells near the Fermi level for all properties investigated. A clearly different behavior of group IVa and IVb dopants is observed: the former are more suitable for surf…
Recent low-temperature scanning tunnelling spectroscopy experiments on the surface of BSCCO-2212 have revealed a strong positive correlation between the position of localized resonances at -960 meV identified with interstitial oxygen dopants and the size of the local spectral gap. We review efforts to understand these correlations within a model where the dopants modulate the pair interaction on an atomic scale. We provide further evidence for this model by comparing the correlations between the dopants and the local density of states with experimental results.
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…
Statistical thermodynamical and kinetically-limited models are applied to study the origin and evolution of space charges and band-bending effects at low angle [001] tilt grain boundaries in YBa$_2$Cu$_3$O$_7$ and the effects of Ca doping upon them. Atomistic simulations, using shell models of interatomic forces, are used to calculate the energetics of various relevant point defects. The intrinsic space charge profiles at ideal surfaces are calculated for two limits of oxygen contents, i.e. YBa$_2$Cu$_3$O$_6$ and YBa$_2$Cu$_3$O$_7$. At one limit, O$_6$, the system is an insulator, while at O$_…
The oxygen dopant concentration dependence of the "quasiparticle" feature at 600-750 cm-1 of the infrared spectrum of Bi2Sr2CaCu2O8+delta (BSCCO), lying near and above the top of the host phonon spectrum at 600 cm-1, is strongly correlated with superconductivity. Using parameter-free topological methods, theory assigns this feature to split apical oxygen interstitials. It explains both the qualitative similarities and the quantitative differences between "quasiparticle" features identified in infrared and phtoemission data, as well as identifying new features in the infrared spectra.
To understand the link between doping and electronic properties in high temperature superconductors, we report first-principles calculations on the oxygen doping effect for the single layer cuprate HgBa$_2$CuO$_{4+δ}$. The doping effect is studied both by supercell and single cell virtual crystal type approaches. We find ionic behavior of the dopant atom up to an optimal doping concentration of $δ=0.22$. The excess oxygen attracts electrons from the CuO$_2$ plane leading to an increase of the hole concentration in this building block. The maximum amount of holes is reached when the oxygen $p$-…
Many theoretical models of high temperature superconductivity focus only on the doping dependence of the CuO2 plane electronic structure. But such models are manifestly insufficient to explain the strong variations in superconducting critical temperature Tc among cuprates which have identical hole-density but are crystallographically different outside the CuO2 plane. A key challenge, therefore, has been to identify a predominant out-of-plane influence controlling the superconductivity - with much attention focusing on the distance $d_A$ between the apical oxygen and the planar copper atom. Her…
We describe two different nuclear quadrupole resonance (NQR) based techniques, designed to measure the local asymmetry of the internal electric field gradient, and the tilt angle of the main NQR principal axis z from the crystallographic axis c. These techniques use the dependence of the NQR signal on the duration of the radio frequency (rf) pulse and on the direction of the rf field H1 with respect to the crystal axis. The techniques are applied to oriented powder of YBa$_{2}$Cu$%_{3}$O$_{y}$ fully enriched with 63Cu. Measurements were performed at different frequencies, corresponding to diff…
The parent compounds of the copper oxide high-Tc superconductors are unusual insulators. Superconductivity arises when they are properly doped away from stoichiometry1. In Bi2Sr2CaCu2O8+x, superconductivity results from doping with excess oxygen atoms, which introduce positive charge carriers (holes) into the CuO2 planes, where superconductivity is believed to originate. The role of these oxygen dopants is not well understood, other than the fact that they provide charge carriers. However, it is not even clear how these charges distribute in the CuO2 planes. Accordingly, many models of high-Tc…
We report temporal changes in Raman-scattering spectra of detwinned YBa$_2$Cu$_3$O$_{6+x}$ single crystals under exposure to red laser light polarized along the crystallographic $a$-axis. A recent publication by Bakr et al. (Phys. Rev. B 88 214517 (2013)) identified new Raman-active modes that appear upon cooling below $T \sim 200$ K, and attributed these modes to charge ordering phenomena observed in x-ray scattering and nuclear magnetic resonance experiments on the same materials. Here we report that the intensities of these modes depend not only on temperature and oxygen content, but also o…
