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Ce-doping and reduction annealing effects on electronic states in Pr$_{2-x}$Ce$_{x}$CuO$_4$ studied by Cu ${K}$-edge X-ray absorption spectroscopy

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 Added by Shun Asano
 Publication date 2018
  fields Physics
and research's language is English




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We investigated Ce-substitution and reduction annealing effects on the electronic states at copper sites by Cu ${K}$-edge x-ray absorption near-edge structure measurements in Pr$_{2-x}$Ce$_x$CuO$_{4+alpha-delta}$ (PCCO) with varying $x$ and $delta$ (the amount of oxygen loss during annealing) values. Absorption near-edge spectra were modified by Ce-substitution and reduction annealing in a similar manner with increasing $x$ and $delta$. Considering electron doping by Ce-substitution, this similarity indicates an increase of electron number at the copper sites due to annealing $n_{rm AN}$. Thus, the total number of electrons is determined by the amount of Ce and oxygen ions. Furthermore, quantitative analyses of the spectra clarified that the number of Cu$^+$ sites, corresponding to the induced electron number by Ce-substitution $n_{rm Ce}$ increases linearly with $x$ in the as-sintered PCCO ($delta=0$), whereas $n_{rm AN}$ is not exactly equal to twice of $delta$, which is expected from charge neutrality. For each $x$-fixed sample, $n_{rm AN}$ tends to exceed 2$delta$ with increasing $delta$, suggesting the emergence of two types of carrier due to annealing.



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In order to realize superconductivity in cuprates with the T-type structure, not only chemical substitution (Ce doping) but also post-growth reduction annealing is necessary. In the case of thin films, however, well-designed reduction annealing alone without Ce doping can induce superconductivity in the T-type cuprates. In order to unveil the origin of superconductivity in the Ce-undoped T-type cuprates, we have performed bulk-sensitive hard x-ray photoemission and soft x-ray absorption spectroscopies on superconducting and non-superconducting Nd$_{2-x}$Ce$_x$CuO$_4$ ($x=$ 0, 0.15, and 0.19) thin films. By post-growth annealing, core-level spectra exhibited dramatic changes, which we attributed to the enhancement of core-hole screening in the CuO$_2$ plane and the shift of chemical potential along with changes in the band filling. The result suggests that the superconducting Nd$_2$CuO$_4$ film is doped with electrons and that the electronic states are similar to those of Ce-doped superconductors.
We report a Cu K- and L$_3$-edge resonant inelastic x-ray scattering study of charge and spin excitations of bulk Nd$_{2-x}$Ce$_x$CuO$_4$, with focus on post-growth annealing effects. For the parent compound Nd$_2$CuO$_4$ ($x = 0$), a clear charge-transfer gap is observed in the as-grown state, whereas the charge excitation spectra indicate that electrons are doped in the annealed state. This is consistent with the observation that annealed thin-film and polycrystalline samples of RE$_2$CuO$_4$ (RE = rare earth) can become metallic and superconducting at sufficiently high electron concentrations without Ce doping. For $x = 0.16$, a Ce concentration for which it is known that oxygen reduction destroys long-range antiferromagnetic order and induces superconductivity, we find that the high-energy spin excitations of non-superconducting as-grown and superconducting annealed crystals are nearly identical. This finding is in stark contrast to the significant changes in the low-energy spin excitations previously observed via neutron scattering.
We report muon-spin rotation/relaxation (muSR) measurements on single crystals of the electron-doped high-T_c superconductor Pr$_{2-x}$Ce$_x$CuO$_4$. In zero external magnetic field, superconductivity is found to coexist with Cu spins that are static on the muSR time scale. In an applied field, we observe a Knight shift that is primarily due to the magnetic moment induced on the Pr ions. Below the superconducting transition temperature T_c, an additional source of static magnetic order appears throughout the sample. This finding is consistent with antiferromagnetic ordering of the Cu spins in the presence of vortices. We also find that the temperature dependence of the in-plane magnetic penetration depth in the vortex state resembles that of the hole-doped cuprates at temperatures above ~ 0.2 T_c.
We measured the far infrared reflectivity of two superconducting Pr(2-x)Ce(x)CuO(4) films above and below Tc. The reflectivity in the superconducting state increases and the optical conductivity drops at low energies, in agreement with the opening of a (possibly) anisotropic superconducting gap. The maximum energy of the gap scales roughly with Tc as 2 Delta_{max} / kB Tc ~ 4.7. We determined absolute values of the penetration depth at 5 K as lambda_{ab} = (3300 +/- 700) A for x = 0.15 and lambda_{ab} = (2000 +/- 300) A for x = 0.17. A spectral weight analysis shows that the Ferrell-Glover-Tinkham sum rule is satisfied at conventional low energy scales ~ 4 Delta_{max}.
We use neutron scattering to study the influence of a magnetic field on spin structures of Nd$_2$CuO$_4$. On cooling from room temperature, Nd$_2$CuO$_4$ goes through a series of antiferromagnetic (AF) phase transitions with different noncollinear spin structures. While a c-axis aligned magnetic field does not alter the basic zero-field noncollinear spin structures, a field parallel to the CuO$_2$ plane can transform the noncollinear structure to a collinear one (spin-flop transition), induce magnetic disorder along the c-axis, and cause hysteresis in the AF phase transitions. By comparing these results directly to the magnetoresistance (MR) measurements of Nd$_{1.975}$Ce$_{0.025}$CuO$_4$, which has essentially the same AF structures as Nd$_2$CuO$_4$, we find that a magnetic-field-induced spin-flop transition, AF phase hysteresis, and spin c-axis disorder all affect the transport properties of the material. Our results thus provide direct evidence for the existence of a strong spin-charge coupling in electron-doped copper oxides.
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