Low-frequency detected EPR: Principles and applications

The experimental works described are performed by the authors over last two decades by means of the LFD EPR technique. The essence of this method is low-frequency detection of the longitudinal spin magnetization while the magnetic resonance is excited by a strong microwave field. The first kind of LFD EPR is the enchanced longitudinal susceptibility effect (ELSE) which has been elaborated and applied to study spin thermodynamics in solids since 1972. Various applications of ELSE are described such as direct measuring of the spin-spin interaction temperatureT _ss in the course of resonance saturation, spin-lattice and cross relaxation, dynamic nuclear polarization etc. Another version of LFD EPR was employed to study electron spin-lattice relaxation of paramagnetic centers in high-temperature superconductors (HTSC). Recent experimental data are presented on the electron spin-lattice relaxation of Cu²⁺ ions in YBa₂Cu₃O_6+x at various temperatures andx values.     

Dynamical magnetic susceptibility in Y-Ba-Cu-O near Tc

The ac susceptibility of ceramic Y-Ba₂Cu₃O_7−x is studied in the range 10²–10⁵ Hz near T_c. Measurements were done in the earth's magnetic field, given the ac field 20 mG. On the basis of the frequency dependences of the real and imaginary parts of the susceptibility the existence of a wide distribution of relaxation times is concluded.     

Spin gap, phase separation and d-wave pairing as revealed by electron spin-lattice relaxation in 123 and 124 YBaCuO systems doped with Gd3+

With an original modulation technique, the Gd³⁺ electron spin-lattice relaxation has been investigated in normal and superconducting states of YBa₂Cu₃O_6+x (123) and YBa₂Cu₄O₈ (124) compounds doped with 1% Gd. In the 123 sample withx = 0.9T _c = 90 K), theT ₁ behavior within 50 <T< 200 K reveals the [1 ? tanh²(Δ/2kT)]/T dependence typical of a spin gap opening with Δ ≈ 240 K. Below 50 K, the exponential slowing down ofT ₁ is limited by the Korringa-like behaviorT ₁ T = const); the same Korringa-like law is found in the 123 sample withx = 0.59 (T _c = 56 K) within the total 4.2–200 K temperature range. This is interpreted in terms of microscopic separation of the normal and superconducting phases allowing for the electron spin cross-relaxation between them. In the 124 sample (T _c = 82 K), the Gd³⁺ relaxation rate below 60 K is found to obey a power lawT _n with an exponentn ≈ 3. Such a behavior (previously reported for nuclear spin relaxation) is indicative of the d-wave superconducting pairing. Additional paramagnetic centers characterized by relatively slow spin-lattice relaxation are found in both 123 and 124 systems. A well-pronounced change in theT ₁ temperature dependence atTT* ≈ 180–200 K is observed for these slowly relaxing centers as well as for the conventional, fast-relaxing Gd³⁺ ions, suggesting microscopic phase separation and a change in the relaxation mechanism due to electronic crossover related with the opening of the spin gap. This hypothesis is supported by some “180 K anomalies” previously reported by other authors.     

Possible nature of the pseudogap anomalies in HTSC

An HTSC model, in which the interaction of valence-band electrons with diatomic negative U centers is assumed to be responsible for the anomalous properties of HTSC compounds, is proposed and used to explain the nature of the pseudogap and pseudogap anomalies (including the giant Nernst effect, the anomalous diamagnetism above T _c, the “transfer” of the optical spectral weight). For YBa₂Cu₃O_{6 + δ}, the pseudogap opening temperature T* and T _c are calculated as functions of the degree of doping δ. The calculated dependences agree quantitatively with the experimental dependences without using scale fitting parameters. The good agreement between the calculated and experimental results can serve as an argument for the proposed HTSC model.     

Accurate determination of the Mössbauer spectrum hyperfine parameters and correlation withT c in YBa2Cu3−x 57Fe x O7−δ (0.01≦x≦0.15)

High statistics room temperature Mössbauer spectra have been performed on ten YBa₂Cu_3?x Fe _x O_7?δ (0.01≦x≦0.15) samples. The different fit solutions (including broadening of the lines) are tested with “χ²” factor analysis. Only two solutions are valid with almost similar parameters. The results on present samples and our previous results on various materials made under different heat treatments show thatT _c is governed byx and the relative population of one of the iron species. These species can be related to highly coordinated irons in the chains.     

Viscous flow of magnetic vortices and rapid relaxation of magnetization in YBaCuO ceramics

The viscous flow of magnetic vortices in granular YBaCuO ceramics of various granule sizes is investigated using the microwave absorption method (f=80 MHz) in the range of varying magnetic fields H=±1500 Oe and of temperatures T=77 to 95 K. The conditions for the formation and melting of the vortex lattice, as well as the transition of the high-temperature superconductor (HTSC) state from the irreversibility region to the region of the viscous flow of magnetic vortices, are considered. The rapid magnetic relaxation times in the range τ=72 to 111 ms are determined from the magnetization relaxation in the HTSC materials under investigation depending on the granule size d, which varies from 1 to 30 μm. The experimental results on the variation of the relaxation time τ from 77 to 120 ms in a ceramic exposed to fast neutrons with various fluences (Φ=10¹⁶ to 10¹⁹ cm⁻²) are considered. The depinning process is analyzed; it occurs in the form of a thermally assisted flux flow in the range of low activation energies. __________ Translated from Fizika Tverdogo Tela, Vol. 43, No. 6, 2001, pp. 968–973. Original Russian Text Copyright ? 2001 by Chashchin.     

Relaxation processes in glasses of the Ge-As-S system

The internal friction in Ge _x As_{40 ? x} S₆₀ glasses is investigated in the temperature range 100 K-T _g at infralow frequencies (10^?3?10^?1 Hz). It is shown that the concentration dependence of the internal friction of these materials changes as a result of the transformation of the dominant kinetic unit in dissipative processes of the relaxation and nonrelaxation types. It is established tha the change in the mechanism of internal friction in the Ge _x As_{40 ? x} S₆₀ glasses leads to a jump in the activation energy of the α relaxation and to a local minimum in the frequency factor τ₀.     

The classification of superconductors using muon spin rotation

In this paper we explore the role of muon spin rotation (μSR) techniques in the characterization and classification of superconducting materials. In particular we focus upon the Uemura classification scheme which considers the correlation between the superconducting transition temperature,T _c, and the effective Fermi temperature,T _F, determined from μSR measurements of the penetration depth. Within this scheme strongly correlated “exotic” superconductors, i.e, hightT _C cuprates, heavy fermions, Chevrel phases and the organic superconductors, form a common but distinct group, characterized by a universal scaling ofT _C withT _F such that 1/100 <T _C/T _F<1/10. For conventional BCS superconductorsT _C/T _F<1/1000. The results of new μSR measurements of the penetration depth in superconducting Y(Ni_1?x Co _x )₂B₂C and YB₆ are also presented. In Y(Ni_1?x Co _x )₂B₂C the decrease ofT _C with increasing Co concentration is linked to a marked decrease in the carrier density from 2.9·10²⁸ m^?3 atx=0 to 0.6·10²⁸ m^?3, atx=0.1, while the carrier mass enhancement remains almost constant at approximately 10. For YB₆ we find evidence of a modest enhancement of the carrier mass (m ^*/m=3), and a relatively low carrier density of 0.24·10²⁸ m^?3. These results are discussed within the Uemura classification scheme. It is found that neither Y(Ni_1?x Co _x )₂B₂C withT _c/T _F>>1/250 nor YB₆ withT _C/T _F>>1/340 can be definitively classified as either “exttic” or “conventional”, but instead the compounds display behavior which interpolates between the two regimes.     

EPR and magnetic susceptibility studies of xCuO·(1−x)[2B2O3·Li2O] glasses

The results of EPR and magnetic susceptibility studies on xCuO·(1?x)? [2B₂O₃·Li₂O] glasses with $\text{0?x?30 mol \%}$, are reported. The modification of EPR spectra with the increasing of CuO content are explained supposing that these are the result of the superposition of two EPR signals, one showing the hyperfine structure typical for isolated Cu²⁺ ions and other consisting from a broad line centered at g ～ 2 typical for the clustered Cu²⁺ ions. The values of the EPR parameters prove that the coordination of isolated Cu²⁺ -complexes remains approximately the same and show that Cu²⁺ ions are situated in axially distorted octahedral vicinities. EPR measurements have shown that the Cu²⁺ ions are present mostly as the isolated species when $\text{x?5 mol \%}$. Beside the dipole-dipole coupling between Cu²⁺ ions, the magnetic measurements suggest that for x>10 mol % superexchange interactions appear, too. From Curie constant is established that in this glass system the copper ions are in Cu²⁺ and Cu⁺ valence states. Also, the amounts of the copper ions in bivalent state are determined.     

On the possibility of developing the non-contact delivery system for cryogenic thermonuclear target transport to the IFE reactor

It is proposed to use the HTSC quantum levitation phenomenon in magnetic fields of various configurations to develop the systems of contact-free positioning and transport of cryogenic fuel targets (CFTs) to the focus of a high-power laser installation or the IFE reactor. The results are presented of a large cycle of experimental studies using YBa₂Cu₃O_7?x superconducting ceramics and permanent magnet guideways based on various combinations of permanentmagnets to develop “CFT-MAGLEV” delivery systems.     

Magnetic resonance in amorphous FexNi80-xP14B6: II. Spin glass alloys

We report EPR measurements on amorphous Fe_xNi_80-xP₁₄B₆ alloys for concentrations less than that required for ferromagnetism. Measurements were made at microwave frequencies between 10 and 35 GHz and at temperatures between 2 and 150 K. We find i) at high temperatures the alloys are simple paramagnets with ? ≈ 2.14 and a relaxation rate (linewidth) increasing linearly with temperature, ii) the linewidth increases at low T and follows an empirical form proposed earlier, iii) as the temperature is decreased, the susceptibility (measured by reference to the line intensities) increases, iv) in order to account for the frequency dependence of the resonance field we must introduce an anisotropy energy with uniaxial symmetry; the “hard axis” being normal to the sample plane. The associated anisotropy constant K' appears at several times the spin glass transition temperature T_SG, v) at still lower temperatures ( < 2T_SG) another type of anisotropy field appears. The corresponding anisotropy energy is similar to that introduced to explain data on the reentrant alloys of this system and the archetypal spin glasses CuMn and AgMn and the anisotropy constant K has the same type of temperature dependence. However, the frequency dependence of K is different.     

On Hahn-echo measurements of short 29Si T2 times in some silica-based materials

The Hahn-echo ²⁹Si NMR experiments performed for determinations of T₂ times in static supermicroporous materials SiO₂–Al₂O₃–MnO and SiO₂–MnO have shown the large loss in the echo intensity, observed at shortest echo delays. The relaxation patterns “intensity—τ”, where the echo-intensity initially increases with increasing τ values and then it “normally” reduces due to spin–spin relaxation, are formally treated and discussed.     

Effect of Zn2+ and Cu2+ on free radical properties of melanin fromCladosporium cladosporioides

Effect of metal ions on free radical properties of natural melanin produced by soil fungiCladosporium cladosporioides was studied. The electron paramagnetic resonance (EPR) spectrum of the studied melanin consists mainly of a single line of eumelanin, and only a very weak signal of pheomelanin was observed. o-Semiquinone free radicals form paramagnetic centers in melanin. Diamagnetic Zn²⁺ ions produce an increase in the free radical concentration in melanin. Quenching of melanin EPR lines was obtained for melanin and paramagnetic Cu²⁺ ion complexes. Slow spin-lattice relaxation processes are characteristic for the free radicals in melanin samples and fast spin-lattice relaxation was observed for Cu²⁺ ions. The EPR lines of copper ions saturate at higher microwave powers than the EPR lines of melanin.     

120 K superconductivity and the zero-field absorption in the BiCaSrCu2Ox system

Onset transition temperature (123±1) K was observed in the BiCaSrCu₂O_x bulk materials prepared by means of conventional ceramic technique. The resistance and AC susceptibility measurements show that there are two highT _c phases. EPR measurement shows that belowT _c (R=0), an intense line at zero field was observed. It is either associated with the glass feature or the spin triplet transition of Cu²⁺–Cu²⁺ pair via exchange interaction.The Project Supported by National Natural Science Foundation of China     

EPR of Yb3+ ions in Ba1−xLaxF2+x mixed crystals

Electron paramagnetic resonance (EPR) spectra of impurity Yb³⁺ ions (about 0.1 at.%) in mixed crystals BaF₂(1-x) plus LaF₃(x) have been investigated for different values of the concentrationx at a frequency of about 9.5 GHz by both continuous-wave (CW) EPR and electron spin echo methods. A spectrum of trigonal symmetry with a complex hyperfine structure is observed in “pure” BaF₂:Yb³⁺ (x=0). Upon admixture of small amounts of LaF₃ (x=0.001), additional EPR lines arise with intensities increasing with the increase ofx up to 0.005. These lines are attributed to trigonal centers including two rare-earth ions and two compensating fluorine ions. A further increase ofx results in a decrease of the total EPR spectrum intensity, and atx≥0.05 the CW resonance becomes practically unobservable. This may be due to the formation of rare-earth ion clusters with paramagnetic Yb³⁺ ions occurring in domains with a disordered structure of surroundings resulting in very broad EPR lines, which cannot be registered by CW EPR. Indeed, very broad (not less than 1 KG) EPR lines were observed by the electron spin echo method for concentrationsx<-0.02.     

Structure and dielectric response of (1–<Emphasis Type="Italic">x</Emphasis>)NaNO<Subscript>2</Subscript> + <Emphasis Type="Italic">x</Emphasis>BaTiO<Subscript>3</Subscript> composites at <Emphasis Type="Italic">x</Emphasis> = 0.05 and 0.1

The (1–x)NaNO₂ + xBaTiO₃ composites of two compositions (x = 0.05 and 0.1) have been studied by powder neutron diffraction and broadband dielectric spectroscopy (frequency region 10^–1–10⁷ Hz). The temperature dependences of the ferroelectric order parameter of NaNO₂ in the composites and pure NaNO₂ have been measured. The frequency dependences of the real and imaginary parts of the permittivities of the composites and pure NaNO₂ have been analyzed in the temperature range 25–187°C. The anomaly of the dielectric response observed at T ~ 147°C is assumed to be related to the processes of accumulation and “resolution” of charges at the BaTiO₃ particle boundaries.     

Electron spin-lattice relaxation anomaly and the local pseudo freeze-out of impurity dynamics in H-bonded ferroelectrics

The strong decrease in the electron spin-lattice relaxation rate at the ferroelectric transition temperature T_c and the simultaneous increase in the transverse spin-spin relaxation rate can be both understood in terms of the local “spontaneous freeze-out” model of impurity dynamics recently proposed to explain the spontaneous dynamic symmetry breaking observed far above T_c in the EPR spectra of H-bonded ferroelectrics doped with paramagnetic impurities.     

Studies on the superconductivity for the “111” type iron arsenide superconductor

The “111” type Li _x FeAs (x ranges from 0.8 to 1.2) with Cu₂Sb type tetragonal structure was synthesized with T _c 18 K. The isostructure NaFeAs was further studied, which shows superconductivity with T _c up to 26 K. The effect of pressure on superconductivity was investigated.     

Mössbauer studies of magnetic behavior of 3d-doped REBa2Cu3−x Fe x O7+δ (RE=Y,Er, Dy,Gd)

A Mössbauer study has been made on⁵⁷Fe ions substituted into the Cu(1) site of REBa₂Cu_3?x Fe _x O_7+δ (RE=Y, Er, Dy, Gd;x=0.15, 0.30). At low temperature, the iron atoms antiferromagnetically order with a transition temperature which is dependent on the Fe concentration. The temperature dependence of the magnetic subspectra representing Fe ions with various local oxygen environments in YBa₂Cu_3?x Fe _x O_7+δ and ErBa₂Cu_3?x Fe _x O_7+δ fit a 2D-Ising model with a ratio of the anisotropic exchange between the two directions on the order of 0.5–1.0(10^?3) for the Y-compounds and on the order of 1 for the Er-compounds. The magnitude of the local dopant magnetization is related to a short-range chemical order which determines the magnetic chain size and defines the correlation lengths. For the Y-compound, the order is quasi-1D with strong intrachain but very weak interchain coupling. For the Er-compounds, the magnetic coupling is Ising 2D. The strong fluctuation behavior expected in low dimensional systems above and belowT _N is observed via characteristic relaxation in the Mössbauer linewidth nearT _N. For both the Dy- and Gd-compounds, the magnetic order is 3D. The magnitude of the rare-earth magnetic moments appears to affect the character of the magnetic interaction in the Cu(1)-site. However, a Mössbauer effect measurement at¹⁵⁵Gd nuclei in GdBa₂Cu_2.85Fe_0.15O_7+δ (T _N(Fe)～14 K) shows paramagnetic behavior at 4.9 K.     

EPR and dielectric properties of Pb5Ge3O11 crystals with off-center Cu2+ ions

The electron paramagnetic resonance (EPR) and dielectric properties of Pb₅Ge₃O₁₁ crystals activated by copper ion are investigated. It is shown that Cu²⁺ ions replace Pb²⁺ in trigonal symmetry positions and occupy three off-center positions displaced from a crystal lattice site in a plane perpendicular to the polar axis C. The temperature variation of EPR spectra and dielectric properties indicates the presence of thermally activated jumps of Cu²⁺ ions between off-center positions. The EPR and dielectric data are used to determine the activation energy W=0.24 eV and the eigenfrequency τ ₀ ^?1 ～ 10¹² Hz of local dynamics of Cu²⁺ ions.