Inhomogeneous state of the electron system in the Sr14 ? x Ca x Cu24O41 superconducting cuprate: 63Cu-17O NMR study

Charge fluctuations in quasi-one-dimensional hole-doped Sr₁₄Cu₂₄O₄₁ (Ca-0) and Sr₂Ca₁₂Cu₂₄O₄₁ (Ca-12) spin-ladder cuprates have been studied with the use of ⁶³Cu-¹⁷O NMR. Spin-echo decay rates ¹⁷(1/T ₂) and ⁶³(1/T ₂) have been measured in the temperature range of T = 10–300 K. The variation of ¹⁷(1/T ₂) and ⁶³(1/T ₂) in the Ca-0 compound is monotonic in the entire temperature range of the NMR study. In the Ca-rich compound, pronounced peaks have been observed in the decay rates ¹⁷(1/T ₂) and ⁶³(1/T ₂) at temperatures of 25 and 50 K, respectively. This result indicates the presence of collective low-frequency (τ_c ∼ T ₂) charge density fluctuations in superconducting Ca-12 with an activation energy of E _A = 100(10) K. The fluctuations gradually slow down as the temperature decreases. The amplitude of the charge density fluctuations is only 0.01–0.02 hole per site. ¹⁷O-⁶³Cu spin-echo double-resonance (SEDOR) experiments in Sr_{14 − x} Ca _x Cu₂₄O₄₁ oxides with x = 0 and 12 have been performed depending on the temperature and orientation of single crystals in a magnetic field. The constants of an indirect heteronuclear ¹⁷O-⁶³Cu interaction of nuclear spins mediated by conduction electrons have been measured. The estimates of the indirect interaction constants for nearest neighbors O1-Cu and O2-Cu, as well as SEDOR experiments with selective excitation of separate sections of ¹⁷O and ⁶³Cu NMR spectra, provide convincing evidence of the microscopically inhomogeneous spatial distribution of spin density developing in a crystal. Original Russian Text ? Yu.V. Piskunov, V.V. Ogloblichev, S.V. Verkhovsky, 2007, published in Pis’ma v Zhurnal éksperimental’noĭ i Teoreticheskoĭ Fiziki, 2007, Vol. 86, No. 11, pp. 850–855.     

Y1-xCaxBa2Cu3-xMxO7-δ (M=Fe,Ni)体系的超导电性

本文报道,通过对Y_1-xCa_xBa₂Cu_3-xMxO_7-δ(M=Fe,Ni)体系样品的晶体结构、氧含量、正常态电阻率与温度的关系,以及超导转变温度等测量,并与YBa₂Cu_3-xMxO_7-δ(M=Fe,Ni)体系进行比较,发现Y_1-xCa_xBa₂Cu_3-xFe_xO_7-δ体系的T_c显著地高于相应x值的YBa₂Cu_3-xFe_xO_7-δ体系,而Y_1-xCa_xBa₂Cu_3-xNi_xO_7-δ体系则相反,T_c低于仅Ni替代的体系,表明Ca和Fe同时替代时两者引起的载流子浓度(n_H)变化相互补偿,抑制了仅Fe替代时引起的n_H和T_c急剧下降;而作Ca和Ni同时替代时主要的不是两者引起载流子浓度变化的相互补偿,Ca和Ni替代效应之间的关联较弱。作者认为,对Y_1-xCa_xBa₂Cu_3-xFe_xO_7-δ体系属于CuO₂平面外的元素替代,这时载流子浓度是决定Tc的主要因素;而对Y_1-xCa_xBa₂Cu_3-xNi_xO_7-δ体系,由于Ni²⁺离子主要占据Cu(Ⅱ)位,它导致磁拆对效应,Ni²⁺离子的拆对效应是引起T_c下降的直接原因。 关键词：     

Effect of 3d metal ion doping on the structure and superconductivity of (Tl0.5Pb0.5)Sr2CaCu2O7

(Tl_0.5Pb_0.5)Sr₂Ca(Cu_2−xM_x)O₇ (M=Co, Ni and Zn) have been synthesized and investigated by means of X-ray diffraction, scanning electron microscope, electrical resistivity and magnetic susceptibility measurements. X-ray diffraction patterns show that all studied samples contain the nearly single ‘1212’ phase. They crystallize in a tetragonal unit cell with a=3.8028-3.8040 Å and c=12.0748-12.1558 Å. In (Tl_0.5Pb_0.5)Sr₂Ca(Cu_2−xM_x)O₇ system (M=Co or Ni), the superconducting critical temperature T_c decreases linearly with both Co and Ni concentrations and the rate of T_c decrease is around −6.5 and −7.0 K/at%, respectively. For (Tl_0.5Pb_0.5)Sr₂Ca (Cu_2−xZn_x)O₇ system, the dependence of T_c on the Zn dopant concentration deviates from a linear behavior and the Zn substitution suppresses T_c much less (−2.5 K/at%) than the Co and Ni substitutions. The suppression in T_c in Co and Ni doped samples are attributed to the magnetic pair-breaking mechanism and the reduction in the carrier concentration. The suppression of T_c in Zn doped samples is not caused by the reduction in carrier concentration which should remain constant, but rather due to nonmagnetic pair-breaking mechanism induced by disorder as well as the filling of the local Cu d_x²−y² state due to the full d band of Zn ions.     

Magnetotransport properties and magnetocaloric effect in La0.67Ca0.33Mn1−xTMxO3 (TM=Cu,Zn) perovskite manganites

The magnetic and transport properties of the perovskites La_0.67Ca_0.33Mn_1-xTM_xO₃ were found to be sufficiently changed with the substitution of Mn-sites by other 3d transition-metal cations (TM=Cu,Zn; x=0.15). The values of T_C, T_M−I, and T_CMR were surveyed when Mn was replaced by Cu and Zn. The magnetic field induced resistivity and magnetic entropy change of these samples showed abrupt changes near T_C (194.2 and 201.5 K for Cu and Zn-doped case respectively) and attained the highest values among the doped cases (up to 20% Cu). The maximum values (obtained at H=4 kOe) of magnetoresistance ratio (CMR) were 27.8%, and 24.5% and of magnetic entropy change (−ΔS_M) were 3.9 and 3.2 J/kg K for Cu and Zn-doped, respectively.     

The effect of transition element doping on the electronic and magnetic properties of La1.4Sr1.6Mn2O7

The effect of transition element (TE=Cr, Fe, Co, Ni, Cu, Zn) doping on the electronic transport and magnetic properties in the bilayer manganite La_1.4Sr_1.6Mn₂O₇ is studied for the same dopant concentration fixed at 2%. Doping does not cause change in structure but different behavior in magnetic and transport properties. Except for Cr, all the other dopings significantly shift the magnetic transition temperature (T_C) to a lower temperature. Associated with such a decrease, the insulator-metal transition temperature (T_IM) decreases and the peak resistivity (ρ_p) at T_IM increases. Cr doping enhances T_C and T_IM as well as decreases ρ_p. Fe doping apparently has a stronger effect than Co and Ni doping. It is also indicated that Cu doping causes an anomalously large increase in ρ_p. These behaviors are compared with those observed in other bilayer manganites such as La_1.2Sr_1.8Mn₂O₇ as well as in La_0.7Ca_0.3Mn_1−xTE_xO₃.     

Synthesis, structural and magnetic properties of spin ladder compound Ca1−xCoxCu2O3

MCu₂O₃ (M=Ca and Co) system has two-leg spin ladder structure similar to that of the prototype SrCu₂O₃ system except that the rungs are buckled with an angle of 123° and 105° for CaCu₂O₃ and CoCu₂O₃ compounds, respectively. We have synthesized powder samples of (Ca_1−xCo_x)Cu₂O₃ (x=0.00-1.00) by the solid state reaction method and their structural and magnetic properties have been investigated. All the synthesized compounds crystallize in orthorhombic structure with space group Pmmn. Lattice parameters of (Ca_1−xCo_x)Cu₂O₃ decrease with the increase in Co content. DC magnetic susceptibility χ(T) results of the end products CaCu₂O₃ and CoCu₂O₃ show antiferromagnetic transition (T_N) at 27 and 215 K, respectively. Co doping into (Ca_1−xCo_x)Cu₂O₃ enhances its T_N systematically with increasing Co concentration. The χ(T) of CoCu₂O₃ shows a broad transition with the peak temperature around 215 K and it was found to be field independent up to 90 kOe. The ambiguity concerning the transition was ruled out by recording the temperature dependent X-ray diffraction pattern on CoCu₂O₃ system, which indicated that there is no structural transition in the investigated temperature range of 115-300 K. Further, specific heat measurement on CoCu₂O₃ confirms the magnetic phase transition by the appearance of a sharp peak at 215 K.     

YBa2Cu1-xCox(Cu1-yZny)2Oz体系的Co,Zn共同掺杂效应

本文报道通过对YBa₂Cu_1-xCo_x(Cu_1-yZn_y)₂O_z(0≤x,y≤0.1)体系晶体结构、氧含量、正常态电阻-温度关系、Hall效应以及超导临界温度等的综合测量,发现随着Co和Zn含量的增加,体系经历了从正交结构的超导金属向四方结构的非超导半导体的转变,超导临界温度T_c和载流子浓度n_h均迅速下降,Co 关键词：     

Silica gel-glasses doped with Cr-containing nanoparticles

Charge fluctuations in quasi-one-dimensional hole-doped Sr₁₄Cu₂₄O₄₁ (Ca-0) and Sr₂Ca₁₂Cu₂₄O₄₁ (Ca-12) spin-ladder cuprates have been studied with the use of ⁶³Cu-¹⁷O NMR. Spin-echo decay rates ¹⁷(1/T ₂) and ⁶³(1/T ₂) have been measured in the temperature range of T = 10–300 K. The variation of ¹⁷(1/T ₂) and ⁶³(1/T ₂) in the Ca-0 compound is monotonic in the entire temperature range of the NMR study. In the Ca-rich compound, pronounced peaks have been observed in the decay rates ¹⁷(1/T ₂) and ⁶³(1/T ₂) at temperatures of 25 and 50 K, respectively. This result indicates the presence of collective low-frequency (τ_c ～ T ₂) charge density fluctuations in superconducting Ca-12 with an activation energy of E _A = 100(10) K. The fluctuations gradually slow down as the temperature decreases. The amplitude of the charge density fluctuations is only 0.01–0.02 hole per site. ¹⁷O-⁶³Cu spin-echo double-resonance (SEDOR) experiments in Sr_{14 ? x} Ca _x Cu₂₄O₄₁ oxides with x = 0 and 12 have been performed depending on the temperature and orientation of single crystals in a magnetic field. The constants of an indirect heteronuclear ¹⁷O-⁶³Cu interaction of nuclear spins mediated by conduction electrons have been measured. The estimates of the indirect interaction constants for nearest neighbors O1-Cu and O2-Cu, as well as SEDOR experiments with selective excitation of separate sections of ¹⁷O and ⁶³Cu NMR spectra, provide convincing evidence of the microscopically inhomogeneous spatial distribution of spin density developing in a crystal.     

Magnetic properties and magnetic structures of Sr3−xCaxRu2O7

We have measured magnetization curves and powder neutron diffraction of double-layered Ruddlesden-Popper type ruthenate Sr_3−xCa_xRu₂O₇ (x=1.5, 2.0 and 3.0). The field dependence of the magnetization revealed that the transition field of metamagnetic transition along the b-axis shifted to lower fields and that the transition became broad with increasing Sr content. The slope of the magnetization curve also increased with increasing Sr content below the metamagnetic transition. These results indicate that an itinerant component is partly introduced by the Sr substitution. From the magnetic reflection, on cooling below T_N, an additional reflection was observed at (0 0 1) for each x, and the amplitude increased with decreasing temperature. The observed diffraction patterns are very similar to those of Ca₃Ru₂O₇. We conclude that the magnetic structure of the antiferromagnetic ordered phase is basically the same structure with that of Ca₃Ru₂O₇.     

Anomalous Zn- and Ni-substitution effects on superconductivity in the superconducting weak ferromagnets RuSr2RCu2O8 (R = Gd,Eu)

The effect of magnetic Ni and non-magnetic Zn impurities on superconducting transition temperature T_c in RuSr₂R(Cu_1?x(Ni, Zn)_x)₂O₈ with R = Gd or Eu (Ni- and Zn-substituted Ru1212Gd(Eu)) was extensively studied. It is found that the suppression rate dT_c/dx of RuSr₂R(Cu_1?x(Ni, Zn)_x)₂O₈ is comparable to that of underdoped YBa₂(Cu_1?x(Ni, Zn)_x)₃O_7?δ. The suppression of superconductivity in Ni-substituted Ru1212Eu samples is more significant than that in Zn-substituted ones, indicative of Ni being a more effective pair-breaker than Zn. In strong contrast, the magnetic Ni impurity atoms have a weaker effect on superconductivity than non-magnetic Zn atoms in Ru1212Gd, similar to what was observed in the high-T_c cuprates. These intriguing findings strongly suggest that the impurity-induced local disturbance of the 3d-spin correlation at Cu sites around Ni/Zn is distinctly different between Ru1212Gd and Ru1212Eu.     

Sr和Ba替代对Eu掺杂Ca2.955Si2O7的结构和发光特性的影响研究

利用固相反应法制备了Sr和Ba替代的Ca_2.955-xM_xSi₂O₇: 0.045Eu²⁺ (M= Sr, Ba, x= 0.1-0.5)系列荧光粉, 利用较大离子半径的Sr和Ba元素替代Eu掺杂Ca_2.955-xM_xSi₂O₇ 中的Ca元素,研究Sr和Ba替代对样品结构和发光特性的影响. X射线衍射测试结果表明,少量Sr和Ba替代不会改变基质的晶体结构, 样品仍然为单斜晶系.未替代前, Ca_2.955Si₂O₇: 0.045Eu²⁺ 样品的发射峰在574 nm左右,随着Sr含量的增加,样品的发射峰发生蓝移; 而Ba含量在x= 0.1-0.4时不会引起发射峰位置的移动, 但x= 0.5样品的发射峰发生蓝移.同等含量的Sr和Ba部分替代样品中的Ca元素, Ba替代样品的光谱强度较强.     

89Y NMR probe of Zn induced local magnetism in YBa2(Cu1-yZny) 3O6+x

We present detailed data and analysis of the effects of Zn substitution on the planar Cu site in YBa₂Cu₃O_6+x (YBCO_6+x) as evidenced from our ⁸⁹Y NMR measurements on oriented powders. For x << 1x \ll 1 we find additional NMR lines which are associated with the Zn substitution. From our data on the intensities and temperature dependence of the shift, width, and spin-lattice relaxation rate of these resonances, we conclude that the spinless Zn 3d ¹⁰ state induces local moments on the near-neighbour (nn) Cu atoms. Additionally, we conjecture that the local moments actually extend to the farther Cu atoms with the magnetization alternating in sign at subsequent nn sites. We show that this analysis is compatible with ESR data taken on dilute Gd doped (on the Y site) and on neutron scattering data reported recently on Zn substituted YBCO_{6 + x}. For optimally doped compounds ⁸⁹Y nn resonances are not detected, but a large T-dependent contribution to the ⁸⁹Y NMR linewidth is evidenced and is also attributed to the occurence of a weak induced local moment near the Zn. These results are compatible with macroscopic magnetic measurements performed on YBCO_{6 + x} samples prepared specifically in order to minimize the content of impurity phases. We find significant differences between the present results on the underdoped YBCO_{6 + x} samples and ²⁷Al NMR data taken on Al³⁺ substituted on the Cu site in optimally doped La₂CuO₄. Further experimental work is needed to clarify the detailed evolution of the impurity induced magnetism with hole content in the cuprates.     

Improved quantification of alite and belite in anhydrous Portland cements by Si MAS NMR: Effects of paramagnetic ions

The applicability, reliability, and repeatability of ²⁹Si MAS NMR for determination of the quantities of alite (Ca₃SiO₅) and belite (Ca₂SiO₄) in anhydrous Portland cement was investigated in detail for 11 commercial Portland cements and the results compared with phase quantifications based on powder X-ray diffraction combined with Rietveld analysis and with Taylor–Bogue calculations. The effects from paramagnetic ions (Fe³⁺) on the spinning sideband intensities, originating from dipolar couplings between ²⁹Si and the spins of the paramagnetic electrons, were considered and analyzed in spectra recorded at four magnetic fields (4.7–14.1 T) and this has led to an improved quantification of alite and belite from ²⁹Si MAS NMR spectra recorded at “high” spinning speeds of ν_R=12.0–13.0 kHz using 4 or 5 mm rotors. Furthermore, the impact of Fe³⁺ ions on the spin-lattice relaxation was studied by inversion-recovery experiments and it was found that the relaxation is overwhelmingly dominated by the Fe³⁺ ions incorporated as guest-ions in alite and belite rather than the Fe³⁺ sites present in the intimately mixed ferrite phase (Ca₂Al_xFe_2−xO₅).     

Zero-field muon-spin-rotation study of hole antiferromagnetism in low-carrier-density Y1−xCaxBa2Cu3O6

We have studied magnetic correlations in the low-carrier-doping regime of Y_1−xCa_xBa₂Cu₃O₆. Samples with carrier densities p_sh=0.015–0.035 (x=0.03–0.07) were studied in the temperature range 2.6–200 K using the zero-field time differential muon spin rotation (ZF TD μSR) technique. An oscillating signal, of 4.1 MHz (∼300 G) in the low-temperature limit (T→0 K), indicative of antiferromagnetism, was found in each sample. This frequency diminished slightly with increasing Ca concentration. Two distinct regimes of frequency as a function of temperature are separated by a kink, which is interpreted as an independent ordering of the spins of the doped holes. The doped-hole spin-freezing temperature is doping dependent and occurs in the range 20.8–33 K. Even in the low-carrier-density regime, the long-range antiferromagnetic ordering is still strongly frustrated by the spin-glass mechanism through calcium doping. Apparent transitions between the 3D frozen-hole antiferromagnetic state and the spin-glassy state with diffusing holes were observed. Clearly the same magnetic interaction mechanisms are operating in both low-carrier-density (Y,Ca)-123 and (La,Sr)₂CuO₄.     

从对Cu的取代看YBa2Cu3O7-y中Cu-O平面和Cu—O链的作用

通过测量YBa₂Cu_3-xM_xO_7-y(M=Zn,Ni,x=0,0.025,0.05,0.075,0.1,0.15,0.2,0.3)系列样品的晶体结构、正常态电子输运性质、超导电性以及O含量,给出了Zn择优取代Cu(2)的更直接证据;同时,观察到掺Zn系统中的由正交相Ⅰ到正交相Ⅱ的结构相变以及Ni取代Cu带来的电子局域化效应。研究结果表明,具有正二价态的Zn对Cu(2)具有择优取代性,而具有正二价和正三价的Ni并不具有明显的择优取代。对Cu(2)的取代引起超导临界温度的显著变化,但对正常态电子输运性质的影响不明显;对Cu(1)的取代更显著地影响了晶体结构和正常态电子输运性质,同时对T_c产生抑制,我们认为,YBa₂Cu₃0₇中的高温超导电性以及正常态输运性质是由CU-O平面和Cu-0链共同承担,而Cu-O平面和Cu-0链之间的耦合强度决定着该系统的超导电性的强弱。 关键词：     

Superconductivity induced phonon anomalies in the Raman spectra of Zn and Ni doped YBa2Cu3O7

Here we present Raman spectra of YBa₂(Cu_1–x Zn _x )₃O₇ and YBa₂(Cu_1–x Ni _x )₃O₇ as a function of temperature and Zn or Ni content. The temperature dependence of two modes at 340 and 440 cm^–1 is analyzed. Similarly to the infrared measurements it is found that Zn substantially suppresses the superconductivity induced phonon softening whereas, Ni does not affect much that effect. Moreover, the superconductivity induced phonon stiffening of the 440 cm^–1 mode completely disappeared with the Zn doping. We find this behaviour might support the model where Zn acts effectively as a magnetic pair breaker.     

Characterization of multiferroic LiTMxCu2−xO2 (TM=Ni and Zn) single crystals

We investigate a series of single crystalline samples of LiT_MxCu_2−xO₂ (T_M=Ni and Zn) grown by floating-zone technique. As-grown crystals showed a clear X-ray diffraction pattern of pure(single) phase. These crystals exhibit varied magnetic and electrical properties owing to successful incorporation of Ni and Zn dopants.     

新块材超导体Pr1-xCaxBa2Cu3O7-δ(0.4≤x≤0.6)的高压合成与超导电性

采用高温高压合成方法，合成出了Pr_1-xCa_xBa₂Cu₃O_7-δ(0.4≤x≤0.6) 系列块材超导体，在缺氧的Pr_0.5Ca_0.5Ba₂Cu₃O_7-δ四方123结构样品中得到了T_c为98K.实验结果表明Pr在123结构中的价态为大于3+的混合价态，因而空穴填充和杂化导致的载流子局域化是Pr抑制123相超导电性的关键因素. 关键词：     

Photoemission investigation of the high temperature superconductors La2−x Sr x CuO4

Photoemission spectra of the La_2–x Sr _x CuO₄ system which recently has been demonstrated of being capable to produce high temperature (T _c >35 K) superconducting compounds are reported. The photoemission spectra of the basic system (La₂CuO₄) and of samples which contain up to 20% Sr are not significantly different. The density of states at the Fermi energy is small (smaller than that of metallic Cu) and the samples show a possible small shift of the Cu 2p lines towards the trivalent position with increasing tendency to superconductivity. From the Sr 3d spectra a considerable amount of oxygen defects coordinated to the Sr ions is estimated.