Continuous-wave far-infrared ESR spectrometer for high-pressure measurements

We present a newly-developed microwave probe for performing sensitive high-field/multi-frequency electron spin resonance (ESR) measurements under high hydrostatic pressures. The system consists of a BeCu-made pressure-resistant vessel, which accommodates the investigated sample and a diamond microwave coupling window. The probe’s interior is completely filled with a pressure-transmitting fluid. The setup operates in reflection mode and can easily be assembled with a standard oversized microwave circuitry. The probe-head withstands hydrostatic pressures up to 1.6 GPa and interfaces with our home-built quasi-optical high-field ESR facility, operating in a millimeter/submillimeter frequency range of 105–420 GHz and in magnetic fields up to 16 T. The overall performance of the probe was tested, while studying the pressure-induced changes in the spin-relaxation mechanisms of a quasi-1D conducting polymer, KC₆₀. The preliminary measurements revealed that the probe yields similar signal-to-noise ratio to that of commercially available low-frequency ESR spectrometers. Moreover, by observing the conduction electron spin resonance (CESR) linewidth broadening for KC₆₀ in an unprecedented microwave frequency range of 210–420 GHz and in the pressure range of up to 1.6 GPa, we demonstrate that a combination of high-pressure ESR probe and high-field/multi-frequency spectrometer allows us to measure the spin relaxation rates in conducting spin systems, like the quasi-1D conductor, KC₆₀.     

Multipurpose High-Frequency ESR Spectrometer for Condensed Matter Research

We describe a multifrequency quasi-optical electron spin resonance (ESR) spectrometer operating in the 75–225 GHz range and optimized at 222.4 GHz for general use in condensed matter physics and chemistry. The quasi-optical bridge detects the change of millimeter wave polarization at the ESR condition. A controllable reference arm maintains a millimeter wave bias at the detector. The sensitivity of 2 × 10¹⁰ spin/(G Hz^0.5), measured on a dilute Mn:MgO sample in a non-resonant probe head at 222.4 GHz and 300 K, is comparable to that of commercial high-sensitive X-band spectrometers. The spectrometer is robust, easy to use and may be operated by undergraduate students. Its performance is demonstrated by examples from various fields of condensed matter physics.     

Submillimetre EPR spectrometer

A wide-band submillimetre EPR spectrometer is described. A set of tunable backward wave oscillators and quasioptic lens system enables one to operate in the frequency region 79–535 GHz. The sample is placed in a magnetic field of up to 1 T at 4.2 K. The spectrometer is intended for the investigation of EPR spectra of rare-earth ions in solids with zero field splittings of the ground states near the frequency of operation and/or electron systems with ag-factor exceeding 5. The spectrometer’s capabilities are demonstrated with an investigation of the EPR spectra of Dy²⁺ and Dy³⁺ ions in CaF₂. As a result the exact value of the zero field splitting between the ground Γ₈ quartet and the first exited Γ₇ doublet of Dy³⁺ in CaF₂, Δ=257±0.5 GHz, has been measured directly.     

Anomalous spin relaxation and quantum criticality in Mn1 − x Fe x Si solid solutions

We report results of the high frequency (60 GHz) electron spin resonance (ESR) study of the quantum critical metallic system Mn_{1 ? x} Fe _x Si. The ESR is observed for the first time in the concentration range 0 < x < 0.24 at temperatures up to 50 K. The application of the original experimental technique allowed carrying out line shape analysis and finding full set of spectroscopic parameters, including oscillating magnetization, line width and g factor. The strongest effect of iron doping consists in influence on the ESR line width and spin relaxation is marked by both violation of the classical Korringa-type relaxation and scaling behavior. Additionally, the non-Fermi-liquid effects in the temperature dependence of the ESR line width, which may be quantitatively described in the theory of Wölfle and Abrahams, are observed at quantum critical points x* ～ 0.11 and x _c ～ 0.24.     

Spin-lattice relaxation in hyperfine-coupled systems: Applications to interstitial diffusion and molecular dynamics

The solid state diffusion of hydrogen, or of its pseudo-isotope muonium, provides an interesting example of spin-lattice relaxation in a 2-spin, 4-level system. The local field experienced by the interstitial atom fluctuates as it moves, inducing transitions between the coupled electron and nuclear spin states. Rate equations governing the populations of these states may be solved numerically to simulate the different relaxation functions which would be displayed by ESR, ENDOR and μSR spectroscopies and to assist in extracting motional correlation times from the experimental data. Spin relaxation in molecular radicals may be treated similarly, with different selection rules for different mechanisms: this paper treats the spin rotation mechanism and perturbation to anisotropic or isotropic components of the hyperfine interaction, caused by inter or intra-molecular motion. Conventional magnetic resonance monitors the population differences appropriate to particular transitions; only in sufficiently high fields do these distinguish the electronic and nuclear response. Muon spin relaxation is remarkable in separating out the nuclear spin projection whatever the degree of mixing of the spin states,via the asymmetry in the muon radioactive decay. Experimentally it has the advantage that measurements can be made over a wide range of field, from null external field up to thelevel crossing where the relaxation rate exhibits a striking peak.     

Field dependence of the ESR “g-shift” in superconductors

Electron spin resonance (ESR) measurements at 36 GHz (Q-band) in $\text{Gd:}\text{CeRu}{}_2$ show a different g-value in the superconducting phase than previously published data measured at 9 GHz (X-band). This frequency dependent “g-shift” is attributed to the spatial change in local field in the vortex state for different external fields.     

Microwave electric field induced spin transitions of AlAs 2D electrons

We present the first direct electron spin resonance (ESR) on a 2D electron gas in a III–V semiconductor. ESR on a high mobility 2D electron gas in a single AlAs quantum well reveals an electronic g-factor of 1.991 at 9.35 GHz and 1.989 at 34 GHz with a minimal linewidth of 7 Gauss. Both the signal amplitude and its dependence on the position and orientation of the sample in the cavity unambiguously demonstrate that the spin transitions in our experiment are caused by the microwave electric field. We present a model that ascribes the spin transitions to the effective magnetic field acting on the electron spins that arises from (Bychkov–Rashba) spin-orbit interaction and the modulation of the electron wavevector around k_F induced by the microwave electric field.     

Magnetic resonance of intrinsic defects in the spin-Peierls magnet CuGeO3

Magnetic resonance in pure single-crystal CuGeO₃ at frequencies 9–75 GHz in the temperature range 1.2–25 K is investigated. Splitting of the magnetic-resonance line into several spectral components is observed at temperatures below 5 K, where spin-Peierls dimerization suppresses the magnetic susceptibility and the ESR signal intensity. Analysis of the magnetic resonance spectra over a wide frequency range with different directions of the magnetic field at different temperatures makes it possible to identify among these components the ESR signals due to defects, having effective spin S=1/2 and spin S=1, in the spin-Peierls phase. The g factor corresponding to these ESR signals is the same and close to the value characteristic for the ion Cu²⁺. Another magnetic-resonance line is characterized by a strongly anisotropic g factor and an increase (at a threshold in the excitation power) in the susceptibility both at resonance and in the line wings. These signals are tentatively attributed to two possible types of planar defects arising on the walls of domains of the spin-Peierls state with different values of the dimerization phase. Zh. éksp. Teor. Fiz. 114, 1876–1896 (November 1998)     

Hyperfine structure of ESR spectra as a probe for heisenberg exchange couplings in nitroxide triradicals serving as building blocks for molecule-based ferrimagnets

A study on electron spin resonance (ESR) spectroscopic determination of exchange interactions in organic oligoradicals is given. When the intramolecular exchange couplingJ between, unpaired electron spins in nitroxide-based oligoradicals falls within the order of 10 Oe (1 mK or 10^?3 cm^?1 forg=2), which is on the same order as the hyperfine couplingA of magnetic nuclei such as nitrogen atoms of nitroxide radicals, the magnitude ofJ can be determined from the hyperfine splitting pattern of ESR spectra in solutions. This range of the exchange couplingJ is not detectable in conventional magnetic susceptibility measurements. We demonstrate an application of hyperfine ESR spectroscopy as a probe for the exchange coupling to a series of organic oligoradicals, which the authors have recently developed as building blocks for molecule-based magnetic materials.     

Conduction-electron spin resonance in aluminium by means of a reflection spectrometer at 60 GHz

Conduction-electron spin resonance in thin aluminium platelets, coated with a plastic surface layer, has been studied in a reflection spectrometer at 60 GHz. It is shown that the data on linewidth and g-factor fall in line with recent measurements at 21 GHz by the present authors and partly also with earlier measurements at 1.27 GHz 9.27 GHz, 35 GHz and 79 GHz by others.     

Precise - and -factor measurements of Ba+ isotopes

Laser-microwave double and triple resonance experiments were performed on clouds of Ba⁺ ions confined in a Penning ion trap to induce and detect electronic and nuclear spin flip transitions. Collisions with buffer gas molecules in the trap was used to reduce the lifetime of a long lived metastable state of the ions, in which population trapping might occur, and to cool the ions to the ambient temperature. Loss of ions from the trap by collisions were prevented by coupling the magnetron and reduced cyclotron motions by an additional r.f. field at the sum frequency of the two motions. Electronic Zeeman transitions in ¹³⁸Ba⁺ and ¹³⁵Ba⁺ were observed at a full width of about 3 kHz at a transition frequency of 80 GHz. The uncertainty of the line center was . From the magnetic field calibration by the cyclotron resonance of electrons stored in the same trap the g_J-factor for both isotopes could be determined to . From radiofrequency induced transitions of ¹³⁵Ba⁺ the nuclear g-factor could be determined . Both measurements improve earlier results by about one order of magnitude. Received: 9 July 1998 / Accepted: 14 July 1998     

Dependence of electron spin g-factor on magnetic field in quantum wells

The dependence of electron spin g-factor on magnetic field has been investigated in GaAs/AlGaAs quantum wells. We have estimated the electron g-factor from spin precession frequency in time-resolved photoluminescence measurements under a magnetic field in different configurations; the magnetic field perpendicular (g_⊥) and parallel (g_∥) to the quantum confinement direction. When the angle between the magnetic field and the confinement direction is 45°, we have found that g-factor varies depending on the direction of magnetic field and the circular polarization type of excitation light (σ⁺ or σ^?). These dependences of g-factor exhibit main features of Overhauser effect that nuclear spins react back on electron spin precession. The value of g_⊥ and g_∥ corrected for the nuclear effects agree well with the results of four-band k·p perturbation calculations.     

Absorption coefficients of sulfur dioxide microwave rotational lines

New calculations of the absorption coefficients of the rotational transitions of ³²S¹⁶O₂ are given for all energy levels up to J = 50 and frequencies less than 200 GHz. A spectrometer incorporating a semiconfocal Fabry-Perot resonant cavity and operating in the vicinity of 70 GHz is described. The calculated absorption coefficients are compared to measured values obtained with this spectrometer and to existing measurements over the frequency range 26–40 GHz. The results obtained are in general agreement to within 5–10%. A detailed knowledge of the absorption coefficient behavior as a function of frequency is of particular interest in the development of high-sensitivity SO₂ monitors, and in investigations of the kinetics of fast chemical reactions.     

High-Field Phenomena of Qubits

Electron and nuclear spins are very promising candidates to serve as quantum bits (qubits) for proposed quantum computers, as the spin degrees of freedom are relatively isolated from their surroundings and can be coherently manipulated, e.g., through pulsed electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR). For solid-state spin systems, impurities in crystals based on carbon and silicon in various forms have been suggested as qubits, and very long relaxation rates have been observed in such systems. We have investigated a variety of these systems at high magnetic fields in our multifrequency pulsed EPR/ENDOR (electron nuclear double resonance) spectrometer. A high magnetic field leads to large electron spin polarizations at helium temperatures, giving rise to various phenomena that are of interest with respect to quantum computing. For example, it allows the initialization of both the electron spin as well as hyperfine-coupled nuclear spins in a well-defined state by combining millimeter and radio-frequency radiation. It can increase the T ₂ relaxation times by eliminating decoherence due to dipolar interaction and lead to new mechanisms for the coherent electrical readout of electron spins. We will show some examples of these and other effects in Si:P, SiC:N and nitrogen-related centers in diamond.     

Multifrequency electron spin resonance study of the charge-ordered manganite Nd<Subscript>0.5</Subscript>Ca<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript>

We performed multifrequency electron spin resonance (ESR) on the antiferromagnetic (T_N = 160 K) and charge-ordered (T _co = 250 K) insulating manganite Nd_0.5Ca_0.5MnO₃. Temperature (4–300 K) and frequency (9.4–285 GHz) dependence of the linewidth, intensity and position of the ESR line were studied. In the paramagnetic state we observe a single Lorentzian absorption line. For a given frequency, the ESR line position is temperature independent (close tog = 1.99). A strong linewidth broadening is observed below T_co. This indicates that there is no magnetic order in the temperature rangeT _cos>T >T _N but strong antiferromagnetic fluctuations are present. Below T_N, due to high-frequency and high-field ESR (up to 12 T) measurements, we were able to observe unexpected lines within the antiferromagnetic gap revealing the presence of a phase separation.     

Microwave frequency modulation in continuous-wave far-infrared ESR utilizing a quasi-optical reflection bridge

We report the development of the frequency-modulation (FM) method for measuring electron spin resonance (ESR) absorption in the 210- to 420GHz frequency range. We demonstrate that using a high-frequency ESR spectrometer without resonating microwave components enables us to overcome technical difficulties associated with the FM method due to nonlinear microwave-elements, without sacrificing spectrometer performance. FM was achieved by modulating the reference oscillator of a 13GHz Phase-Locked Dielectric Resonator Oscillator, and amplifying and frequency-multiplying the resulting millimeter-wave radiation up to 210, 315 and 420GHz. ESR spectra were obtained in reflection mode by a lock-in detection at the fundamental modulation frequency, and also at the second and third harmonic. Sensitivity of the setup was verified by conduction electron spin resonance measurement in KC60.     

The application of submetallic phosphorus-doped Si as ESR marker

With the aim of applying it in high-accuracy electron spin resonance spectral analysis, some “marker” qualities of P-doped Si have been investigated. K-band data of submetallic Si:P powders doped to (1.7 ± 0.1) × 10¹⁸ CM⁻³ in the temperature range T = 1.6−300 K are presented. If this material is used in accurate ESR calibration work, full attention should be paid to the reported g versus T variations over the whole T range covered. Comparison to other data at T less than 4.2 K indicates an essentially different behavior of g and ΔB_pp versus T when studied in either low or high magnetic field regimes. Hence, when calibrating spectra, the ESR marker data obtained in the same observational frequency band as the one of interest should be used.     

ESR spectrometer with a wide frequency range using a gyrotron as a radiation power source

The development of a high frequency electron spin resonance (ESR) spectrometer with a wide frequency range using a gyrotron as the radiation power source is described.GYROTRON FU-E, optimized for use in an ESR spectrometer in the millimeter wave range, was developed in Fukui University. In order to test the normal operation of the spectrometer, the ESR of two standard samples, single crystal and polycrystalline DPPH, has been measured, in the pulsed mode over the frequency range from 65 GHz to 135 GHz.     

脉冲强磁场高频电子自旋共振装置的研制

国内第一套脉冲强磁场高频电子自旋共振(ESR)装置由武汉国家脉冲强磁场科学中心研制成功.该装置的频率范围为210-370 GHz,样品温度范围为2-300 K, 磁场强度为0-50 T.在脉冲强磁场ESR装置上进行了红宝石ESR实验,获得了Cr³⁺ 离子的ESR谱.