Field-angle-dependent multi-frequency electron spin resonance spectroscopy in submillimeter wave range based on thermal detection.

We report the thermally detected electron spin resonance (ESR) spectroscopy in the frequency range of millimeter and submillimeter waves. Under high vacuum conditions, a cantilever-shaped device detects ESR absorption of a mounted sample as a temperature difference in its beam direction. Despite the simple experimental setup, the spin sensitivity of the order of 1012 spins/G was achieved at 10 K. The developed sample stage is small enough to be used in a 10 T split-pair superconducting magnet with a bore of 25 mm, enabling precise field-angle-dependent ESR measurements at multi-frequencies above 500 GHz. We demonstrate its usefulness by studying the field-angle dependence of the excitation energy of the dimer triplet state in the Shastry-Sutherland magnet SrCu2(BO3)2.

Force-detected high-frequency electron spin resonance spectroscopy using magnet-mounted nanomembrane: Robust detection of thermal magnetization modulation.

In this study, we report a conceptually novel broadband high-frequency electron spin resonance (HFESR) spectroscopic technique. In contrast to the ordinary force-detected electron spin resonance (ESR) technique, which detects the magnetization change due to the saturation effect, this method measures the magnetization change due to the change of the sample temperature at resonance. To demonstrate its principle, we developed a silicon nitride nanomembrane-based force-detected ESR spectrometer, which can be stably operated even at high magnetic fields. Test measurements were performed for samples with different spin relaxation times. We succeeded in obtaining a seamless ESR spectrum in magnetic fields of 15 T and frequencies of 636 GHz without significant spectral distortion. A high spin sensitivity of 1012 spins/G s was obtained, which was independent of the spin relaxation time. These results show that this technique can be used as a practical method in research fields where the HFESR technique is applicable.

Pressure Effect on Zero-Field Splitting Parameter of Hemin: Model Case of Hemoproteins under Pressure.

We experimentally studied the pressure dependence of the zero-field splitting (ZFS) parameter of hemin (iron(III) protoporphyrin IX chloride), which is a model complex of hemoproteins, via high-frequency and high-field electron paramagnetic resonance (HFEPR) under pressure. Owing to the large ZFS, the pressure effect on the electronic structure of iron-porphyrin complexes has not yet been explored using EPR. Therefore, we systematically studied this effect using our newly developed sub-terahertz EPR spectroscopy system in the frequency range of 80-515 GHz, under magnetic fields up to 10 T and pressure up to 2 GPa. We observed a systematic shift of the resonance fields of hemin upon pressure application, from which the axial component of the ZFS parameter was found to increase from D = 6.9 to 7.9 cm-1 at 2 GPa. In contrast to the previous methods used to study proteins under pressure, which mainly focused on conformational changes, our HFEPR technique can obtain more microscopic insights into the electronic structures of metal ions under pressure. In this sense, our technique provides novel opportunities to study the pressure effects on biofunctional active centers of versatile metalloproteins.

Note: Force- and torque-detection of high frequency electron spin resonance using a membrane-type surface-stress sensor.

We developed a practical useful method for force- and torque-detected electron spin resonance (FDESR/TDESR) spectroscopy in the millimeter wave frequency region. This method uses a commercially available membrane-type surface-stress (MSS) sensor. The MSS is composed of a silicon membrane supported by four beams in which piezoresistive paths are integrated for detecting the deformation of the membrane. Although this device has a lower spin sensitivity than a microcantilever, it offers several distinct advantages, including mechanical strength, ease of use, and versatility. These advantages make this device suitable for practical applications that require FDESR/TDESR.

Mechanically detected terahertz electron spin resonance using SOI-based thin piezoresistive microcantilevers.

We developed piezoresistive microcantilevers for mechanically detected electron spin resonance (ESR) in the millimeter-wave region. In this article, fabrication process and device characterization of our self-sensing microcantilevers are presented. High-frequency ESR measurements of a microcrystal of paramagnetic sample is also demonstrated at multiple frequencies up to 160 GHz at liquid helium temperature. Our fabrication is based on relatively simplified processes with silicon-on-insulator (SOI) wafers and spin-on diffusion doping, thus enabling cost-effective and time-saving cantilever fabrication.

Cantilever detected ferromagnetic resonance in thin Fe50Ni50, Co2FeAl0.5Si0.5 and Sr2FeMoO6 films using a double modulation technique.

In this work we introduce a new method, which employs commercial piezo-cantilevers, for a ferromagnetic resonance (FMR) detection from thin, nm-size, films. Our setup has an option to rotate the sample in the magnetic field and it operates up to the high microwave frequencies of 160GHz. Using our cantilever based FMR spectrometer we have investigated a set of samples, namely quasi-bulk and 84nm film Co2FeAl0.5Si0.5 samples, 16nm Fe50Ni50 film and 150nm Sr2FeMoO6 film. Low frequency and room temperature test of our setup using 84nm Co2FeAl0.5Si0.5 film yielded a result identical to a standard X-Band spectrometer, namely a single line with quite small linewidth. Our measurements at low temperatures and high frequencies revealed a quite strong FMR response detected in all samples. The FMR spectra share common features, such as the emergence of the second line with an opposite angular dependence, and a drastic increase of the linewidths with increasing microwave frequency. We believe that these findings are results of the complicated dynamics of the magnetization at low temperatures and high frequencies, which we were able to probe using our cantilever based FMR setup.

High-frequency electron paramagnetic resonance of metal-containing porphyrin compounds using a microcantilever.

In this article, we report a novel technique of high-frequency electron paramagnetic resonance (HFEPR) using a microcantilever. In this method, a sample is mounted on a cantilever, and the field-gradient force associated with EPR absorption is detected as a cantilever bending. By using a micrometer-sized cantilever, this technique can be applied to a very tiny sample on the order of µg. In addition, the use of a piezoresistive cantilever makes the experimental setup easy and compact. In this study, we applied this technique to multi-frequency HFEPR measurements of metal-containing porphyrin compounds, which are an important composing element of metal-containing proteins and coenzymes such as hemoglobin and cyanocobalamin.

Metal-insulator transition of charge-transfer salts based on unsymmetrical donor DMET and metal halide anions (DMET)4(MCl4)(TCE)2 (M = Mn, Co, Cu, Zn; TCE = 1,1,2-trichloroethane).

New charge-transfer salts based on an unsymmetrical donor DMET [dimethyl(ethylenedithio)diselenadithiafulvalene] and metal halide anions (DMET)4MIICl4(TCE)2 (M = Mn, Co, Cu, Zn; TCE = 1,1,2-trichloroethane) have been synthesized and characterized by transport and magnetic measurements. The crystal structures of the DMET salts are isostructural, consisting of a quasi-one-dimensional stack of DMET and insulating layers containing metal halide anions and TCE. Semimetallic band structures are calculated by the tight-binding approximation. Metal-insulator transitions are observed at TMI = 25, 15, 5-20, and 13 K for M = Mn, Co, Cu, and Zn, respectively. The M = Cu salt exhibits anisotropic conduction at ambient pressure, being semiconducting in the intralayer current direction but metallic for the interplane current direction, down to T(MI). The metal-insulator transitions are suppressed under pressure. In the M = Co and Zn salts, large magnetoresistances with hysteresis are observed at low temperatures, on which Shubnikov-de Haas oscillations are superposed above 30 T. In the M = Cu salt, no hysteresis is observed but clear Shubnikov-de Haas oscillations are observed. The magnetoresistance is small and monotonic in the M = Mn salt. Paramagnetic susceptibilities of the spins of the magnetic ions are observed for the M = Mn, Co, and Cu salts with small negative Weiss temperatures of approximately 1 K. In the nonmagnetic M = Zn salt, Pauli-like pi-electron susceptibility that vanishes at TMI is observed. The ground state of the pi-electron system is understood as being a spin density wave state caused by imperfect nesting of the Fermi surfaces. In this pi-electron system, the magnetic ions of the M = Mn, Co, and Cu salts interact differently, exhibiting a variety of transport behaviors.