NQR investigations of high-T c superconducting oxides

Nuclear quadrupole resonance (NQR) of⁶³Cu has been performed to study the electronic and magnetic properties of YBa₂Cu₃O_6.1 ceramics, treated in iodine or bromine vapours. An analysis of the NQR shows undistorted CuO₂ planes and the absence of an increase of the oxygen content in chains of Cu(1)-O in halogen treated Y-Ba-Cu-O ceramics.¹³⁹La NQR spin-lattice relaxation measurements in powdered La_2?x CuO_4?y compounds are also reported. The present results indicate that the¹³⁹La nuclear relaxation is dominated by the Cu⁺⁺-Cu⁺⁺ magnetic correlations.     

Variation of Kβ/ Kα X-ray intensity ratio and lineshape with the effects of external magnetic field and chemical combination

In this work, the effects caused by different chemical combination and external magnetic field in several copper and zinc compounds (Cu, CuBr, Cu₂O, CuI, CuCl, Cu₂Te, Cu₅Si, CuSO₄, CuSeO₄.5H₂O, CuCl₂, Cu(NO₃)₂, CuS, CuSe, CuF₂, CuF2.3H₂O, CuBr₂, Cu(ClO₄)₂.6H₂O, Zn, ZnSO₄.5H2O, Zn(C₂H₃O₂)₂, ZnF₂, Zn(NO₃)₂.6H₂O, ZnO, ZnS, ZnSe, ZnTe and ZnF₂.4H₂O) were studied using a Si(Li) detector. The samples were excited by 22.69 keV X-rays from ¹⁰⁹Cd point radioactive source of strength 10 mCi in the external magnetic field of intensities 0.6 T and 1.2 T. The shift, asymmetry, FWHM and Kβ/Kα intensity ratio values were determined. For B = 0, the present experimental results were compared with the experimental and theoretical data in literature. The results have shown that the atomic parameters such as energy shifts, asymmetry indices, FWHM and Kβ/Kα intensity ratios can change when irradiation is conducted in a magnetic field.     

Trimers of bivalent copper impurity ions in CaF<Subscript>2</Subscript> crystals: The structure and mechanism of formation

Crystals of CaF₂: Cu (with a copper impurity content higher than 0.1 at. %) grown by the Czochralski method from a melt in a mixed helium-fluorine atmosphere are investigated using electron paramagnetic resonance (EPR) spectroscopy. It is found that the crystals contain paramagnetic centers whose magnetic properties at low temperatures are identical to those of [CuF₄F₄]^6? (S=1/2) single centers. The magnetic properties of the centers exhibit a qualitative change in the temperature range 77–300 K. These changes are described within a model according to which the center is treated as a cluster composed of three [CuF₄F₄]^6? impurity complexes involved in exchange interactions and interactions occurring in the field of Jahn-Teller lattice distortions.     

Cu chemistry of YBa2Cu3O6+x investigated by nuclear quadrupole resonance

The nuclear quadrupole resonance (NQR) technique has been utilized to characterize the local oxygen coordination of inequivalent Cu sites in YBa₂Cu₃O_6+x(0 ≤ x ≤ 0.91). Essentially, four distinct NQR lines which correspond to 2, 3,4 oxygen coordinated Cu sites in the Cu-O chains and 5 oxygen coordinated Cu sites in the Cu-O planes have been observed. The zero-field NQR frequencies of these are centered at about 30.1, 24.0, 22.0 and 31.5 MHz for ⁶³Cu, respectively. For the antiferromagnetic ordered state (x ≤ 0.3), antiferromagnetic nuclear resonance (AFNR) has been observed at 90 MHz with quadrupole splittings associated with the moment-bearing Cu sites in the Cu-O planes. The relative intensities of these resonance lines depend on the oxygen content, and this gives us a microscopic understanding of the Cu chemistry of this system.     

Shape of the Cu(2) NQR spectra in YBa2Cu3O7, TmBa2Cu3O7 and TmBa2Cu4O8

We present a study of shape of the Cu(2) NQR spectra in YBa₂Cu₃O₇, TmBa₂Cum₃O₇, and TmBa₂Cu₄O₈ compounds at temperatures of 4.2–300 K. The results of the quantitative analysis lead us to conclude that the shape of the Cu(2) NQR spectra in all the samples studied can be described in the framework of the “motional narrowing” model, which implies that the Cu(2) nucleus possesses two different NQR frequencies between which it can rapidly jump. The difference in frequencies seems to be related to the charge-stripe correlations in CuO₂ planes resulting in a dynamical modulation of the electric field gradients at the Cu(2) nuclei. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 9, 594–598 (10 November 1997)     

Magnetic structure of the Sr<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>4</Subscript>Cl<Subscript>2</Subscript> two-subsystem antiferromagnet according to nuclear quadrupole resonance data

The magnetic structure of the Sr₂Cu₃O₄Cl₂ two-subsystem antiferromagnet is studied by the nuclear quadrupole resonance (NQR) method on the ^{63, 65}Cu and ³⁵Cl nuclei. The resonance spectrum above T _N2 = 40 K is determined by the Zeeman splitting of the levels of the ^{63, 65}Cu nuclei of the copper atoms at the Cu1 site with the first-order quadrupole perturbation. The magnetic field on the copper nuclei is equal to 93 kOe. The spectrum below n is significantly different: it includes a low-frequency part, which is associated with the ordering of the second magnetic subsystem Cu2. The splitting of the NQR lines of ³⁵Cl is observed above and below T _N2. This fact indicates the ferromagnetic ordering of the moments of the Cu1 subsystem, which are located along the c axis of the crystal, and makes it possible to determine the direction of the magnetic field on Cu1 copper as (110).     

Ordering of oxygen in halogen treated 1-2-3 systems as studied by NQR

We have investigated the low-temperature behavior of Cu NQR for iodinated RBa₂Cu₃O _x (R = Y, Gd) compounds. The different influence of Gd spins on the Cu(1) and Cu(2) sites was used to separate the contributions of both sites in the spectra. The distinct NQR lines associated with the different oxygen-coordinated Cu(1) sites have been observed. The NQR spectra of the Cu(1) sites show that the iodine treatment gives rise to the modifications of the oxygen sublattice. From the analysis of the NQR spectra of the Cu(1) sites follows an increase of the average length of the Cu(1)-O chains at treatment.     

Structural and magnetic phase transitions in (Chloroanilinium)2CuX4 (X = Cl, Br)

Successive structural phase transitions of (4-ClC₆H₄NH₃)₂CuCl₄, which occur in a very narrow temperature range were reinvestigated by Fourier transform nuclear quadrupole resonance (FT NQR) measurements. The phase transitions at 275.5 and 277.0 K were confirmed. The effect of the deuteration of the ammonium end on these transitions was studied. The³⁵Cl NQR frequencies of organic cation were observed to decrease by about 4 kHz and the phase transition temperatures to decrease by about 2 K by the deuteration, suggesting that the ?NH₃ ⁺ … Cl hydrogen bond is weakened by the deuteration. The magnetic phase transition temperature of 8.6 K showed no remarkable change within experimental error by the deuteration. It was found that the magnetically ordered state is broken by the radio-frequency magnetic field of about 15–35 Oe usually employed in pulsed NQR. However, in the deuterated compound (4-ClC₆H₄ND₃)₂CuCl₄, the ordered state was found to be stabler for the usual radiofrequency power. By combining with the NQR data of (4-ClC₆H₄NH₃)₂CuBr₄ and (3,5-Cl₂C₆H₃NH₃)₂CuCl₄, the possibility is discussed of tuning the interlayer interaction between the organic cation layer and the inorganic complex anion layer by the halogen substitution in the organic cation as well as by the halogen replacement in the inorganic complex anion.     

First-principles studies on the structural and electronic properties of Li-ion battery cathode material CuF2

The 3d transition metal binary compounds have been extensively investigated for a large multi-electron redox capacity through reversible electrochemical reactions. Here, the structural, electronic and magnetic properties of CuF₂ are studied by the first-principles calculations within both the generalized gradient approximation (GGA) and GGA+U frameworks. Our results show that the antiferromagnetic (AFM) configuration of CuF₂ is more stable than the ferromagnetic (FM) one, which is consistent with experiments. The analysis of the electronic density of states (DOS) shows that CuF₂ is a classic Mott–Hubbard insulator with a large d–d type band gap, which is similar to the case of FeF₃. Moreover, small spin polarizations were found on the sites of fluorin ions, which accords with a fluorin-mediated superexchange mechanism for the Cu–Cu magnetic interaction.     

Single-crystal like NMR spectra of CeCu 5 Au powder samples

Single-crystal like nuclear magnetic resonance spin-echo spectra are obtained for powder samples of the antiferromagnet CeCu₅Au in the paramagnetic phase. Line shifts and quadrupolar splittings are analyzed for ⁶³Cu and ⁶⁵Cu. The influence of the extreme magnetic anisotropy of the CeCu_6-xAu_x compounds on nuclear spin relaxation is discussed. Received 19 June 2000     

139La and63Cu-NQR of high-T c oxide superconductors

Nuclear quadrupole resonances (NQR) of¹³⁹La in La_2−xM_xCuO₄ (M=Ba, Sr) and⁶³Cu in YBa₂CU₃O₇ have been investigated with substitution of Cu by magnetic impurities. For La-system, the strong enhancement of the nuclear relaxation rate, 1/T ₁ atT _c ^*≈10 K (suggesting the occurrence of magnetic instability with hole-doping), is suppressed by 3D-antiferromagnetism induced by magnetic impurities. In the superconducting region, fluctuations of Cu moments at low temperatures remain extremely fast as at high temperatures. For Y-system, Fe-ions are substituted for both Cu(1) and Cu(2) sites, But Co-ions are preferentially substituted to Cu1 sites. The peaks in the relaxation rate of Cu indicate the appearance of magnetic ordering without destroying superconductivity for the 0.5%-Fe doped sample.     

Pressure-induced change of the interlayer exchange interaction from ferromagnetic to antiferromagnetic in CS2CuF4 observed by neutron scattering experiments up to 2 GPa

Abstract

Neutron scattering experiments on the two-dimensional Heisenberg ferromagnets Cs₂ CuF₄ and K₂CuF₄ have been performed around 2 ～ 3 GPa over 1·4–15 K. At ambient pressure both the intralayer and the interlayer exchange interactions in these two compounds are ferromagnetic. At about 2 GPa, the interlayer exchange coupling in Cs₂ CuF₄ is found to change from ferromagnetic to antiferromagnetic, while the ferromagnetic intralayer exchange interaction is maintained. Contrary to Cs₂CuF₄, the ferromagnetism in K₂Cuf₄ is not destroyed by pressure up to 9 GPa, that was confirmed in the early study of the magnetic susceptibility measurements.     

Copper NQR study of the La 214 system from an aspect of microscopic environment of copper

The nuclear quadrupole resonance (NQR) has been investigated for Cu in La_2–x A _x CuO _y (A=Sr and Ba). Three Cu NQR lines, A, B and C, have been observed, which correspond to three different Cu sites. From the analysis of these NQR intensities, site assignments are possibly as follows. These lines A, B and C are attributed to CuO₆ octahedral, CuO₅ pyramidal and CuO₄ planar sites, respectively. The apical oxygen O(2) is induced to transfer to the interstitial O(3) site between LaO planes when two or more Sr²⁺ ions are located in its neighboring La sites. The excess holes doped into the CuO₂ plane are provided mainly by O(3) as well as the unpaired Sr²⁺ ion.     

Chlorine-35 nuclear quadrupole resonance and phase transitions in (4ClC6H4NH3)2MnCl4, (4-Cl6H4NH3)2CUCl4, and (4-ClC6H4NH3)2CUBr4

The temperature dependence of the ³⁵Cl NQR frequencies of 4-chloroanilinium cations in (4-ClC₆H₄NH₃)₂MnCl₄, (4-ClC₆H₄NH₃)₂CuCl₄, and (4-ClC₆H₄NH₃)₂CuBr₄ was studied over a wide range of temperature. For the two copper(II) complexes, magnetic susceptibilities were measured below approximately 20 K. The lattice constants of these isomorphous orthorhombic crystals were determined. Magnetic phase transitions to three-dimensionally long-range-ordered states were found at 40, 8, and 13 K for the respective complexes. Additional structural phase transitions were also found at higher temperatures for all of the complexes studied. Magnetic properties in the ordered state and the nature of both types of phase transitions are discussed.     

Local Magnetic Fields in Some Bismuth-Based Diamagnets

Evidence that local ordered magnetic fields from 30 to 250 G exist in bismuth-based diamagnetic compounds comprising neither d- nor f-elements was given by ²⁰⁹Bi NQR spectroscopy and supported by SQUID measurements of α-Bi₂O₃. The NQR experiments involved a study of the zero-field line shapes, analysis of the Zeeman-perturbed patterns, and examination of the zero-field spin-echo envelopes in single crystals and powders. The results of the experiments followed by computer modeling of the observed spectra were interpreted assuming that ordered magnetic fields are located at the bismuth sites in α-Bi₂O₃, Bi₃O₄Br, Bi₂Al₄O₉, Bi₄Ge₃O₁₂, Bi₂Ge₃O₉ and perhaps in Bi₃B₅O₁₂. A survey of the related ²⁰⁹Bi NQR data is here presented.     

X-ray Lα emission and LIII absorption spectra of copper compounds

The X-ray Lα _{1, 2} emission spectra and L_III absorption spectra in Cu, Cu₂O, CuCl, Cu₂S, CuO, CuCl₂, CuS, CuF₂ and Cu(en)₂Cl₂ are investigated. It is shown that the emission spectra of divalent copper compounds are considerably distorted due to a sharp absorption peak near the L_III edge. The nature of this peak is discussed and a relation is made with satellite peaks in X-ray photoelectron spectra.     

A reexamination of19F NMR in selected solids,the conductor Ag2F and Reference Insulators for studies of YBa2Cu3O7-type superconductors

NMR signals of¹⁹F have been measured in the polycrystalline inorganic conductor Ag₂F and in the polycrystalline insulators AgF, YOF, EuOF, YF₃, CuF₂, BaF₂ and KF to compare them to the signals found in the so-called «1-2-3-type» compounds with claimed formulas RBa₂Cu₃O_7-xF_x (R=Y and Eu). No evidence for a Knight-shifted, built-in fluorine-signal was found in the 1-2-3-type superconductors, whereas Ag₂F shows a clearly downfield shifted¹⁹F peak with reference to AgF.     

Ba nuclear resonance in YBa2Cu2Oy

The first observations of NMR and NQR of both isotopes¹³⁵Ba and¹³⁴Ba in isotopically enriched samples of YBa₂Cu₃O_y with oxygen concentrations y=6.0, 6.2, and 7.0 are described. The pure NQR frequencies and asymmetry parameter are in good agreement with theoretical predictions. The temperature dependence of the NQR frequency of Ba for y=7 is qualitatively similar to that for Cu(2) but much stronger. The temperature dependence of the longitudinal and transverse relaxation times opens new questions.     

Resonance Frequency and NMR Relaxation Times in Two Inequivalent <Superscript>133</Superscript>Cs in Cs<Subscript>2</Subscript>CuBr<Subscript>4</Subscript> and Cs<Subscript>2</Subscript>ZnBr<Subscript>4</Subscript> Single Crystals

The resonance frequencies and relaxation mechanisms of Cs₂CuBr₄ and Cs₂ZnBr₄ were examined by static nuclear magnetic resonance (NMR) method. Here, the two inequivalent Cs(1) and Cs(2) sites surrounded by Br ions were distinguished. The saturation recovery traces for ¹³³Cs nuclei in Cs₂CuBr₄ with the paramagnetic ions, and those in Cs₂ZnBr₄ without the paramagnetic ions were each fitted by four exponential functions. From these results, the spin–lattice relaxation times T₁ in the laboratory frame of ¹³³Cs nuclei in the two crystals were obtained, and Cs(1) surrounded by 11 bromide ions has a longer relaxation time than Cs(2) surrounded by 9 bromide ions.     

NQR investigations of the high-Tc superconductor Ba2YCU3O7

NQR measurements of ^63,65Cu in both the normal and superconducting state are reported for the Cu1 and Cu2 sites in Ba₂YCu₃O₇. An anomalous behaviour in the vicinity and below T_c is observed: after a steep decrease at T_c the quadrupole frequency increases with decreasing temperature.