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THz electron spin resonance (ESR) measurements of the spinel compound GeCo2O4, which consists of the Co2+ pyrochlore structure, were performed. The temperature dependence measurements revealed new antiferromagnetic phases, AF1 and AF2, below TN. Moreover, a wide magnetic field range of ESR study using a single crystal at 1.8 K also revealed various field-induced phases due to the competition between the spin–lattice coupling and the spin frustration. Critical field resonances were observed at 5.0 T, 8.6 T, and 11.0 T for B//[111] and 5.1 T, 7.7 T, 11.2 T, and 13.0 T for B//[110] at 1.8 K. Although it became difficult to observe ESR above 86 K, the g-values of Co2+ ions were estimated to be g[111] = 3.34 and g[110] = 3.27 for [111] and [110], respectively, from the observed ESR mode above the saturation field at 1.8 K. Detailed frequency-field diagrams of the ESR modes at 1.8 K suggested the existence of spin–lattice coupling energy of 250 GHz (= 1.03 meV = 12 K) at the critical field resonances. The spin gap mode in the frequency-field diagram at 1.8 K showed excitation energies of E[111] = 1004 GHz (= 4.15 meV = 48 K) and E[110] = 1044 GHz (= 4.32 meV = 50 K) for [111] and [110], respectively. These results will be discussed in connection with the di-tetramer model suggested previously.

Cerium hexaboride attracts attention of solid-state community for almost 50 years. Nowadays, this material is considered as a unique example of a system with orbital ordering resulting in formation of low-temperature magnetic phase with quadrupolar order, the so-called antiferroquadrupole phase. In crystal electric field 4f 1 state of Ce3+ splits into Γ7 doublet and Γ8 quartet, the latter is believed to be the ground state, as long as just Γ8 allows quadrupolar effects. An additional tool for studying rich physics of CeB6 appeared since the discovery in this material the ESR, which is specific to antiferroquadrupole (AFQ) phase and is missing in the paramagnetic phase. In the present review, we have brought together electron spin resonance and inelastic neutron scattering data, which allowed obtaining most detailed structure of the magnetic resonance modes in the AFQ phase in a wide-frequency range up to 0.6 THz. It is shown that apart paramagnetic resonance main mode with homogeneous precession of the magnetization, there are antiferromagnetic resonance modes as well, some of them existing in the AFQ phase. Analysis of the g factors demonstrates that available theories based on Γ8 ground state are facing difficulties with accounting experimental data, thus providing a challenge for developing of a theory correctly describing dynamic magnetic properties of this interesting material.

As THz electron spin resonance (ESR) measurement has several advantages of high spectral resolution, ESR measurement beyond the zero-field splitting or the magnetic phase transition, it is a powerful means to study novel magnetic systems. Focusing on these advantages, we have been developing this THz ESR, and we are now extending to the multi-extreme THz ESR. Here the multi-extreme corresponds to the high magnetic field, the high pressure, the low temperature and the micro-mechanically detected highly sensitive THz ESR. Recent new developments and applications, especially focusing on the high pressure THz ESR, will be shown.

We systematically studied the zero-field splitting (ZFS) parameters of Fe(III) protoporphyrin IX chloride, or hemin, using the terahertz electron paramagnetic resonance (EPR) spectroscopy technique at ambient and high pressures. Although hemin is known as a model substance of hemoproteins, the pressure effect on the electronic structure has not yet been explored owing to the large ZFS. In this study, high-field and high-frequency EPR measurements were carried out in the frequency range up to 700 GHz and at hydrostatic pressures up to 2 GPa. At ambient pressure, multiple EPR branches were clearly observed, and the axial and rhombic components of ZFS were determined as $$D = 6.90\pm 0.01\hbox { cm}^{-1}$$ and $$E = 0.055 \pm 0.005\hbox { cm}^{-1}$$ , respectively. Upon pressure application, we observed a systematic shift of the resonance field, indicating a monotonous increase of the axial component from D = 6.9 to 7.9 $$\hbox {cm}^{-1}$$ at 2 GPa. The origin of this unusually large shift was discussed from a microscopic viewpoint of the electronic structure of iron under pressure.

THz electron spin resonance (ESR) measurement has been a powerful means to study novel magnetic systems because of the advantages of high spectral resolution, ESR measurement beyond the zero-field splitting or the magnetic phase transition. Therefore, we have been developing this THz ESR system since 1988, and we are now extending to the multi-extreme THz ESR. Here the multi-extreme corresponds to the high magnetic field, the high pressure, the low temperature and the micro-mechanically detected ESR. Recent new developments, especially focusing on the high pressure THz ESR, will be shown.

Due to the advantages of high spectral resolution, ESR measurement beyond the zero field splitting or the magnetic phase transition, THz electron spin resonance (ESR) measurement has been a powerful means to study novel magnetic systems. We have been developing this THz ESR system since 1988, and we are now extending to the multi-extreme THz ESR. Here the multi-extreme corresponds to the high magnetic field, the high pressure, the low temperature and the micro-mechanically detected ESR. Recent new developments, and the application of the high pressure THz ESR will be shown.

We have developed a high-pressure electron spin resonance probe and successfully installed into the world’s highest-field cryogen-free superconducting magnet having a maximum central field of 24.6 T. The high pressure of 2.5 GPa is achieved by the specially designed piston-cylinder pressure cell using THz-wave-transparent components. In the first application of this high-pressure high-field ESR system, we observed that the orthogonal dimer spin system SrCu2(BO3)2 undergoes a quantum phase transition from the dimer singlet ground to the plaquette singlet ground states.

High-field electron spin resonance measurements of perovskite compound YCrO3 powder have been performed to obtain the magnetic anisotropy. Isotropic absorption lines of electron paramagnetic resonance, which can be described as single Lorentzian shape, are observed. The g value of paramagnetic state is estimated to be 1.983 at 265 K. Magnitude of D vector of Dzyaloshinskii–Moriya interaction is estimated to be 0.36 K from Moriya’s formula using the obtained g value. Powder patterns of antiferromagnetic resonance (AFMR) with large antiferromagnetic gaps are observed below T N = 140 K. Two antiferromagnetic gaps at zero field have been estimated to be 181 GHz (6.5 T) and 338 GHz (12.1 T), and a spin flop transition field have been estimated to be 3.5 T from widely observed frequency–field diagram at 1.9 K. Although obtained AFMR modes seem to be typical AFMR modes of two sublattice antiferromagnet with triaxial magnetic anisotropy, the obtained zero-field gap is twice as large as the obtained spin flop transition field which suggests the unconventional antiferromagnetic order.

We have developed a high-pressure and multi-frequency electron spin resonance (ESR) system in the submillimeter wave region. The pressure is generated by the piston–cylinder pressure cell whose inner parts are all made of ceramics. The requirements for the inner parts of the pressure cell are toughness and transmission in the submillimeter wave region and they enable us to observe the transmitted light through a sample subjected to high pressure. It was found that both properties can be achieved by the combination of the inner parts made of the ZrO2-based ceramic and the Al2O3 ceramic. For the Shastry-Sutherland compound SrCu2(BO3)2, we observed the direct ESR transition from the singlet ground state to the first excited triplet sates at 1.5 GPa successfully in the frequency region from 300 to 700 GHz.

The S = 1/2 kagome-lattice antiferromagnet is investigated by the numerical diagonalization of 18-spin finite-size cluster. The matrix elements proportional to the intensity of the singlet--triplet electron spin resonance (ESR) transition are calculated in the presence of the Dzyaloshinsky--Moriya interaction. Some angle-dependent selection rules are also proposed. The present result would be useful to examine whether the kagome-lattice antiferromagnet has a spin gap or not, with the ESR experiment.

We have developed the high-pressure electron spin resonance (ESR) system using a micro-coil in the frequency region up to around 2 GHz and potentially 10 GHz. The hybrid-type piston-cylinder pressure cell whose maximum pressure reaches 4 GPa was used. In this study, we obtained ESR spectra at 2.3 GPa successfully, which can never be obtained by the single-layer piston-cylinder pressure cell. The minimum detectable spin number was estimated to be the order of 1012 spins/G. Moreover, it is shown that the sensitivity can be improved by two orders of magnitude using the field modulation technique. This high-pressure ESR technique is a promising one to achieve the sensitivity and the high pressure simultaneously.

YSrCrO4 is first synthesized and found to be a hettotype of the K2NiF4 structure, although the combination of Y and Sr ions in K2NiF4-type oxides is very rare. The space group of the compound is determined to be orthorhombic Pccn by the electron diffraction and the powder X-ray diffraction. Magnetic and dielectric properties of the compound, together with LaSrCrO4, YCaCrO4 and A2MnO4 (A = Sr and Ca), are investigated. YSrCrO4 shows two-dimensional (2D) spin correlations and a canted antiferromagnetic (AF) ordering. With increasing distortion of the crystal structure, 2D spin correlations and the AF transition temperature decrease, while spontaneous magnetization increases. From the multi-frequency electron spin resonance (ESR) measurements, the g-values of the paramagnetic state are estimated to be 1.976, 1.978 and 1.976 for YSrCrO4, LaSrCrO4 and YCaCrO4, respectively. Evidence of AF ordering of the Cr oxides is obtained microscopically from ESR. The dielectric measurements suggest the existence of in-gap states, while no magneto-dielectric coupling was observed in the above compounds.

Due to the advantages of high spectral resolution, ESR measurement beyond the zero field splitting or the magnetic phase transition, THz electron spin resonance (ESR) measurement has been a powerful means to study novel magnetic systems. We have been developing this THz ESR system since 1988, and we are now extending to the multi-extreme THz ESR. Here the multi-extreme corresponds to the high magnetic field, the high pressure, the low temperature and the micro-cantilever ESR. Recent new developments and the application to the study of multiferroic system will be shown.

To develop a new spin-crossover functional material, a magnetic hybrid compound [Fe(qsal)(2)][Ni(mnt)(2)] was designed and synthesized (Hqsal = N-(8-quinolyl)salicylaldimine, mnt = maleonitriledithiolate). The temperature dependence of magnetic susceptibility suggested the coexistence of the high-spin (HS) Fe(III) cation and pi-radical anion at room temperature and a magnetic transition below 100 K. The thermal variation of crystal structures revealed that strong pi-stacking interaction between the pi-ligand in the [Fe(qsal)(2)] cation and [Ni(mnt)(2)] anion induced the distortion of an Fe(III) coordination structure and the suppression of a dimerization of the [Ni(mnt)(2)] anion. Transfer integral calculations indicated that the magnetic transition below 100 K originated from a spin-singlet formation transformation in the [Ni(mnt)(2)] dimer. The magnetic relaxation of Mossbauer spectra and large thermal variation of a g-value in electron paramagnetic resonance spectra below the magnetic transition temperature implied the existence of a magnetic correlation between d-spin and pi-spin.

Various light sources for plant production have been developed to establish a completely controlled factory. We propose a pulse light source using Xe discharge. For the rapid growth of the plant, an intense light covering the absorption spectral region of chlorophyll is demanded, and periodic irradiation is also required because the photosynthetic reaction has a certain period. In this study, Sr3MgSi2O8:Eu,Mn phosphor powders with various Eu and Mn content, which show two emission peaks in the absorption region of photosynthetic pigment and phytochrome, were synthesized, and were analyzed using X-ray diffraction, photoluminescence and electron spin resonance spectroscopy. It was found that the exchange-coupled Mn-Mn and Eu-Mn pairs lead the rapid decay of Mn emission and efficient energy transfer from Eu and Mn ions, respectively. A plasma tube array panel using the phosphor was also fabricated and the similar emission spectrum of Sr3MgSi2O8:Eu,Mn is obtained under vacuum-UV excitation in comparison to the UV excitation.

We have developed a high-field and high-frequency ESR system using a commercially available magnetometer equipped with the superconducting quantum interference device (SQUID). This is magnetization detection type ESR and ESR is observed as a change of the magnetization at the resonance condition under irradiation of the electromagnetic wave. The frequency range is from 70 to 315 GHz and the maximum magnetic field is 5 T. The sensitivity is estimated to be 10 13 spins/G. The advantage of this system is that the high-field ESR measurements can be made very easily and quantitatively. Moreover, this high-field ESR can be applied to the measurements under pressure by using a widely used piston-cylinder pressure cell.

A hybrid-type piston-cylinder pressure cell for the electron spin resonance (ESR) measurement has been developed. The cylinder of this pressure cell consists of a NiCrAl inner cylinder and a CuBe outer sleeve, and all inner parts are made of zirconium oxide which has good transmittance to the millimeter and submillimeter waves. We confirmed that the pressure reaches 2.1 GPa. We have also developed a transmission-type high-field ESR system having two different modulation methods for this pressure cell. A test measurement without pressure cell for the two-dimensional orthogonal-dimer spin system of SrCu2(BO3)2 has been done successfully in the wide frequency region. The combination of this electromagnetic wave transmission-type pressure cell and this high-field ESR system is a promising tool for the study of the pressure-induced phase transition of SrCu2(BO3)2.

Recent developments of “multi-extreme” high magnetic field electron spin resonance (ESR) in Kobe will be reviewed. Our high magnetic field ESR covers the frequency region between 0.03 and 7 THz and the temperature region between 1.8 and 300 K. With this high magnetic field ESR system we can apply the magnetic field up to 55 T using a Cu-Ag pulsed magnet and a 300 kJ (10 kV) capacitor bank. Under this high magnetic field we can also apply the high pressure up to 1.4 GPa. As we can make the measurement under low temperature, high magnetic field and high pressure simultaneously, we name it as “multi-extreme” ESR. Moreover, in order to gain the sensitivity of our high magnetic field ESR, we have developed a micro-cantilever ESR system using a torque method, which enables the ESR measurement of micrometer size single crystal at low temperature. At the moment we are in the process of extending the magnetic field region of micro-cantilever ESR. Recently we have succeeded in making the measurement up to 369 GHz and the achieved sensitivity is about 1010 spins/G, which is much higher than that using the conventional transmission method. Finally our development of magnetization detected ESR using SQUID magnetometer (SQUID ESR) will be also presented.

High-frequency electron spin resonance (ESR) measurements of S = 1/2 one-dimensional Heisenberg antiferromagnetic zig-zag chain substance (VO)(SO4)(2,2-bpy) were performed in the temperature region from 1.8 to 265 K. ESR measurements at 265 K show typical powder pattern spectra of the V4+ ion and g || = 1.925 ± 0.001 and g ⊥ = 1.976 ± 0.001 were obtained. Although the magnetic susceptibility shows a maximum at 3.1 K suggesting the existence of a short-range order, no g-shift and line width broadening were observed down to 1.8 K. We suggest that these temperature-independent features of ESR can be attributed to the result of frustration in (VO)(SO4)(2,2-bpy).

High-pressure and high-field electron spin resonance (ESR) measurements have been performed on a single crystal of the orthogonal-dimer spin system SrCu$_{2}$(BO$_{3}$)$_{2}$. With frequencies below 1 THz, ESR signals associated with transitions from the singlet ground state to the one-triplet excited states and the two-triplet bound state were observed at pressures up to 2.1 GPa. We obtained directly the pressure dependence of the gap energies, finding a clear first-order phase transition at $P_{c}=1.85\pm0.05$ GPa. By comparing this pressure dependence with the calculated excitation energies obtained from an exact diagonalization, we determined the precise pressure dependence for inter- ($J'$) and intra-dimer ($J$) exchange interactions considering the Dzyaloshinski-Moriya interaction. Thus this system undergoes a first-order quantum phase transition from the dimer singlet phase to a plaquette singlet phase above the ratio $(J'/J)_{c}=0.660\pm0.003$.

Development of multi-extreme electron spin resonance (ESR) measurement system is in progress in Kobe. We have installed the pulsed magnetic field up to 55 T and our high field ESR system can cover the frequency region from 30 GHz to 7 THz. Our aim is to extend our high field ESR system to the multi-extreme ESR measurement system by combining low temperature, high pressure and nano techniques, and the combination with the high pressure is focused in the paper. High pressure can be achieved up to 1.4 GPa by using the transmission type piston cylinder pressure cell. We have succeeded in combining the high field and the high pressure. As an example, the pressure dependence of the spin gap in SrCu2(BO3)2, S=1/2 Shustally-Sutherland dimer system, observed by our multi-extreme ESR measurement is presented. This measurement is the direct and precise measurement of the spin gap, and the spin gap decreased from 723 GHz (34.7 K) to 581 GHz (27.9 K) at 1.2 GPa.

Magnetic interactions in a site-disordered multicomponent vanadate Mn3Fe4(VO4)6 are studied using DC magnetization and multifrequency Electron Paramagnetic Resonance (EPR). The static magnetic susceptibility χ shows antiferromagnetic interactions between Fe3+ and Mn2+ spins with a Curie–Weiss temperature Θ = −165(5) K. EPR measurements indicate a strong dependence of χ on the frequency and temperature. The EPR spectra due to iron and manganese ions are observed in the X-band. It is mostly manganese ions that are observed at 80 GHz while two kinds of magnetic centers are identified at frequencies above 160 GHz. The observed shifts of the resonance lines for Fe3+ ions at low frequencies differ from those at high frequencies. The observed features may be due to different magnetic sublattices which modify the magnetic ground state, while competing magnetic interactions may lead to magnetic frustration. It appears that the very high magnetic fields employed in our high-frequency EPR measurements may affect the spin-flop transitions anticipated below Neel temperature TN.

A multiextreme (high-field, low-temperature, high-pressure and nanoscale) electron spin resonance (ESR) measurement system is under development in Kobe. In this connection, our recent development is introduced and two applications of our high-frequency high-field ESR are described. High-frequency high-field ESR measurements of dioptase (Cu6Si6O18·6H2O), which has an interesting antiferromagnetic Cu2+ network, have been performed using a pulsed magnetic field of up to 55 T. Antiferromagnetic resonances (AFMR) are clearly observed at 4.2 K with the light sources of up to 1017 GHz. However, a deviation from the conventional two-sublattice AFMR theory is observed in the high field. Temperature dependence of the X-band and high-frequency ESR has been also observed in the triangular lattice antiferromagnet EtMe3P[Pd(dmit)2]2 which shows the spin-Peierls-like transition below Tc = 25 K. The preliminary field dependence of the spin gap estimated from the analyses of our ESR results has been shown in connection with the previous magnetic susceptibility results.

We report the anomalous effect of the polarization dependence of electron paramagnetic resonance absorption in CuGeO3 doped with 2% of Co. While the resonance line of Cu2+ chains is independent of the microwave polarization in the Faraday geometry, the resonant mode of Co impurity exhibits a strong polarization dependence for all directions of the external magnetic field. Possible reasons of such behavior are discussed.

A single crystal S=3/2 perfect kagome lattice antiferromagnet $\mathrm{KCr_3(OH)_6(SO_4)_2}$ (Cr-jarosite) has been studied by X-band and high-frequency electron spin resonance (ESR). The g-values perpendicular to the kagome plane (c-axis) and in the plane are determined to be $g_c=1.9704 \pm 0.0002$ and $g_\xi=1.9720 \pm 0.0003$, respectively, by high-frequency ESR observed at 265 K. Antiferromagnetic resonances (AFMR) with the antiferromagnetic gap of 120 GHz are observed at 1.9 K, which is below $T_N$=4.5 K. The analysis of AFMR modes by the conventional molecular field theory shows $d_p=0.27$ K and $d_z=0.07$ K, where $d_p$ and $d_z$ are in-plane and out-of-plane components of DM d vector, respectively. From these results and the estimated exchange interaction J=6.15 K by Okuta et al., the ground state of Cr-jarosite is discussed in connection with the Monte Carlo simulations result with classical Heisenberg spins on the kagome lattice by Elhajal et al. Finally, the angular dependence of linewidth and the lineshape observed at 296 K by X-band ESR show typical behavior of a two-dimensional Heisenberg antiferromagnet, suggesting a good two-dimensionality of Cr-jarosite.

Doping of CuGeO3 by 2% Co was found to cause a new magnetic resonance, which has anomalous polarization characteristics. In the Faraday geometry, where a microwave field B ω is directed along certain crystallographic directions, this mode is suppressed, which indicates that the character of magnetic oscillations in this mode differs strongly from standard spin precession. This resonance coexists with the EPR on Cu2+ chains and is likely to be caused by an unknown collective mode of magnetic oscillations of an antiferromagnetic quantum S = 1/2 spin chain.

A new piston-cylinder pressure cell for electron spin resonance (ESR) has been developed. The pressure cell consists of a double-layer hybrid-type cylinder with internal components made of the ZrO2-based ceramics. It can generate a pressure of 2 GPa repeatedly and reaches a maximum pressure of around 2.5 GPa. A high-pressure ESR system using a cryogen-free superconducting magnet up 10T has also been developed for this hybrid-type pressure cell. The frequency region is from 50 GHz to 400 GHz. This is the first time a pressure above 2 GPa has been achieved in multi-frequency ESR system using a piston-cylinder pressure cell. We demonstrate its potential by showing the results of the high-pressure ESR of the S=1 system with the single ion anisotropy NiSnCl6·6H2O and the S=1/2 quantum spin system CsCuCl3. We performed ESR measurements of these systems above 2 GPa successfully.

Anomalous polarization characteristics of magnetic resonance in CuGeO3 doped with 2% Co impurity are reported. For the Faraday geometry, this mode is damped for the microwave field B ω aligned along a certain crystallographic direction, showing that the character of magnetic oscillation differs from the standard spin precession. The observed resonance coexists with the ESR on Cu2+ chains; it is argued not to be caused by “impurity” EPR, as previously claimed, but to correspond to a previously unknown collective mode of magnetic oscillations in an S = 1/2 AF quantum spin chain.

For the CuGeO3 single crystals doped with 1% of Fe the quantum critical behavior in a wide temperature range 1–40 K is reported. The critical exponents for susceptibility along different crystallographic axes are determined: α = 0.3 4 (B||a and B||c) and α = 0.3 1 (B||b). The description of the temperature dependences of the linewidth and g-factor could be obtained in the Oshikawa–Affleck theory assuming that staggered component of the magnetic moment is located predominantly along b-axis. Possible arguments favoring the competition between effects of the staggered field and antiferromagnetic ordering are provided.

Submillimeter and millimeter wave ESR measurements of spin gap systems SrCu 2 (PO 4 ) 2 and PbCu 2 (PO 4 ) 2 , which have four kinds of dimers, have been performed to investigate the magnetic properties of spin gap systems using the pulsed magnetic field up to 35T. The observed ESR spectra of powder sample SrCu 2 (PO 4 ) 2 show sharp and single peak in the temperature range from 4.2 to 80 K. The anisotropy of the g -values turned out to be very small compared to the usual anisotropic powder spectra of copper compounds. The dynamical properties will be discussed from the temperature dependence measurements.

The EPR spectra along different crystallographic axes for single crystals of CuGeO3 containing 1% of Fe impurity have been studied in the frequency range 60-360 GHz at temperatures 0.5-30 K. The analysis based on the Oshikawa-Affleck (OA) theory suggests that the temperature dependences of the line width and g-factor are formed as a result of the competition between interchain antiferromagnetic interactions and staggered Zeeman energy. It is found that staggered magnetic moments in CuGeO3:Fe are located predominantly along b axis., Comment: 9 pages, 4 figures; submitted to QSS04 symposium

Resonance magnetoabsorption spectra of CuGeO3 single crystals containing 2% Co impurity have been studied in the frequency range 60–360 GHz in magnetic fields of up to 16 T and in the temperature interval 2–60 K with the magnetic field B aligned parallel to the a crystallographic axis. In addition to the Cu2+ chain resonance, a new absorption line (unobserved previously in doped CuGeO3 and deriving apparently from the Co2+ ions) was detected in EPR spectra. Quantitative analysis of the spectra suggests that the spin-Peierls transition occurs in about 10% Cu2+ chains, while the spin-Peierls state in the remaining 90% chains is completely destroyed by cobalt doping. The results obtained reveal considerable deviations from the universally accepted scenario of CuGeO3 doping and are discussed within alternative theoretical models, namely, the quantum critical behavior (based on the EPR theory for quasi-one-dimensional systems) and a three-dimensional antiferromagnet with the Neel temperature lowered by disorder.

Intensive high-field ESR studies have been performed to investigate the peculiar ground state of a quasi-one dimensional cupric oxide Ca 1- x CuO 2 ( x =0.164), to which a two-sublattice model (chain-dimer model) composed of a Heisenberg antiferromagnetic chain and dimer state with low spin density is proposed from the results of magnetic susceptibility and specific heat measurements. Using the powder sample and high frequency sources from 60 to 490 GHz, we observed antiferromagnetic resonance mode with a typical frequency–field relation of the easy-axis type at 1.8 K. Moreover, weak ESR signals are also observed in the ordered state. From the analysis of the integrated intensity for those weak signals, it is found that the dimer model reproduces the temperature dependent behaviors quite well. These results support the chain-dimer model from the microscopic point of view.

Recent developments of the high-field facility in Kobe University are presented. A far infrared radiation (FIR) laser system, which can generate electromagnetic waves from 500 GHz to 3 THz has been installed. Now the frequency region for high-field ESR is extended from 30 GHz to 3 THz using Gunn oscillators, BWOs and a FIR laser. Recent high-field ESR results of quantum spin systems CsFeBr3 and Cu3(CO3)2(OH)2 using these light sources are presented. CsFeBr3 is known as a field-induced antiferromagnetic ordering substance, and we found new ESR modes in the high-field phase of CsFeBr3 for B//c at 2.0 K . Cu3(CO3)2(OH)2 is the model substance for the S= 1 2 quantum diamond chain, and we observed the direct transition in the ESR measurement at 1.9 K for B//c.

High field ESR measurements of novel spin chain substance Bi4Cu3V2O14 have been performed in the frequency region from 105 to 540 GHz using the pulsed magnetic field up to 35 T . Broad absorption lines appear below 6 K , and the observed resonances at 1.9 K are attributed to antiferromangetic resonances (AFMR). The g-values are estimated to be 1.40 and 1.43 from the AFMR results, and the origin of these anomalous g-values will be discussed.

High-field ESR technique has been applied to the novel frustrated spin chain system KCu5V3O13, to reveal the peculiar ground state proposed by the previous results of the magnetic susceptibility and the magnetization measurements. We successfully observed the antiferromagnetic resonance with the easy axis type anisotropy below 7 K . In addition, small shifts of the resonance field probably due to the re-arrangements of spin configuration in the ordered phase were also observed at about 4 K in the detailed temperature dependence measurements. This result confirmed the observation of double peaks at 3.9 and 7 K in the specific heat measurements performed in advance to the high-field ESR measurements. We will discuss about the ground state of KCu5V3O13 based on these results together with those obtained in the KMgCu4V3O13, where no antiferromagnetic resonance was observed.

Recent advances in the high-field ESR studies of low-dimensional quantum spin systems in Kobe are presented. Among many systems studied, the results of S= 1 2 quasi-one-dimensional (1D) antiferromagnet BaCu 2 (Si 1− x Ge x ) 2 O 7 with the staggered field and S= 1 2 diamond chain system Cu 3 OH 2 (CO 3 ) 2 are discussed. As the interchain interaction is almost canceled in the BaCu 2 (Si 1− x Ge x ) 2 O 7 ( x =0.65) system, we have found that the field and temperature dependences of the linewidth and the resonance field obey the Oshikawa–Affleck (OA) ESR theory of 1D antiferromagnet. The effect of the interchain interaction from the x dependence measurement and the existence of the breather mode at low temperature are also discussed. On the other hand, the high-field ESR measurements at 1.8 K revealed the direct transition in Cu 3 OH 2 (CO 3 ) 2 . The direct transition turned out to be anisotropic and it will be discussed in connection with the 1 3 magnetization plateau which is also anisotropic.

High-field ESR measurements of S= 1 2 triangular antiferromagnet CsCuCl3 have been performed at 6 K under pressure using the pulsed magnetic field up to 16 T in the frequency region from 120 to 360 GHz . We found that both the phase transition field and the antiferromagnetic gap increased under pressure. The origin of the increase of the antiferromagnetic gap was concluded to be due to the increase of the easy-plane type anisotropy as well as the increase of the interchain interaction of this system. The increase of the easy-plane type anisotropy was consistent with the increase of the phase transition field under pressure as suggested by Nikuni and Shiba's theory.

We have developed a low-temperature ESR system under pressure, which has the frequency region above 70 GHz, the pulsed magnetic field up to 16 T and the pressure region up to about 3.5 kbar. A suitable pressure-calibration method using the change of the ESR of ruby under pressure has been also developed. We can determine the pressure and observe ESR signals of a sample at the same time. The high-field ESR measurements with the pulsed magnetic field up to 16 T have been performed on triangular antiferromagnet CsCuCl 3 for H||c around 6 K at 1 bar and at 3.1 ± 0.6 kbar in the frequency region from 120 GHz to 370 GHz. We observed the increase of the phase transition field from the umbrella-type configuration to the coplanar configuration due to the quantum fluctuation and the increase of the antiferromagnetic gap under pressure. The possible origin of this increase of the phase transition field was discussed in connection with the recent magnetization measurements under pressure.

We give an overview of our studies on the electron spin resonance (ESR) in the hexagonal triangular antiferromagnets of ABX 3 type using millimeter and submillimeter waves and static and pulsed high magnetic fields. Novel ESR modes, which cannot be understood by the conventional theory of the antiferromagnetic resonance, were observed. Examples of this include that there exists the gapless excitation even for the easy-axis anisotropy. The ESR modes can be classified by the signs of the exchange interaction J 0 along the c-axis and the anisotropy. The ESR modes were calculated within the framework of the mean-field approximation using three-sublattice and six-sublattice models for the ferromagnetic and antiferromagnetic J 0 interaction, respectively. The experimental results were well described by the present calculations.

Submillimeter wave ESR measurements using the pulsed magnetic field is a powerful spectroscopic technique covering the wide frequency and magnetic field range with many advantages compared to the conventional X-band ESR measurements. Recent submillimeter wave ESR results showed that it is especially powerful to study the low dimensional antiferromagnets, that is, quantum spin systems. In accordance, the submillimeter wave ESR facilities in Japan are also presented. As an example of the study of quantum spin system, the investigation of the S=1/2 one dimensional antiferromagnets BaCu 2 (Si 1-x Ge x ) 2 O 7 (x=0, x=0.65), which have the staggered field effect in the system, is also presented in connection with the recent ESR theory by Oshikawa and Affleck (OA). Although both x=0 and x=0.65 systems show one dimensional behavior from the magnetic susceptibility, the temperature and frequency dependences of the mixed crystal x=0.65 system are well interpreted by the OA theory while they are not for the pure x=0 system. The antiferromagnetic resonance measurements of x=0 system (T N =8.9 K) have been performed up to 30 T at 1.8 K, and the magnetic phase transitions at 7 T and 16 T for H//α and H//c, respectively, are suggested for the first time.

The microscopic magnetic properties of high-quality GdN thin films have been investigated by electron spin resonance (ESR) and ferromagnetic resonance (FMR) measurements. Detailed temperature dependence ESR measurements have shown the existence of two ferromagnetic components at lower temperatures, which was not clear from the previous magnetization measurements. The temperature, where the resonance shift occurs for the major ferromagnetic component, seems to be consistent with the Curie temperature obtained from the previous magnetization measurement. On the other hand, the divergence of line width is observed around 57 K for the minor ferromagnetic component. The magnetic anisotropies of GdN thin films have been obtained by the analysis of FMR angular dependence observed at 4.2 K. Combining the X-ray diffraction results, the correlation between the magnetic anisotropies and the lattice constants is discussed.

High field ESR measurements of S =1/2 one-dimensional quantum antiferromagnetic (AF) system BaCu 2 (Si 1− x Ge x ) 2 O 7 have been performed using powder samples and pulsed magnetic field. High field electron paramagnetic resonance at 352 GHz and 86 K enabled us to determine the x dependence of g -values even when we used the powder samples. The x dependence will be discussed in connection with the crystal field. Moreover, antiferromagnetic resonances of x =0 and x =1 samples below T N were observed and their frequency–field relations suggest the existence of Dzyaloshinsky–Moriya interaction.

Recent advance of a field theoretical approach of a low-temperature electron spin resonance (ESR) in S=½ antiferromagnetic chain, which has Dzyaloshinskii-Moriya (DM) interactions and staggered g-tensor sites, by Oshikawa and Affleck (OA) suggests peculiar magnetic field dependence of ESR. Although BaCu 2 (Si 1 - x Ge x ) 2 O 7 is an antiferromagnetic chain system with mixed antiferromagnetic and ferromagnetic interchain interactions, we found that x=0.65 substance shows the peculiar field dependence of ESR predicted by OA theory. The temperature dependence of the line width showed the power-law dependence and strong field dependence in the gapless spinon regime which can be well interpreted by OA theory. The temperature dependence of the resonance shift turned out to be also consistent with OA theory. These results are also discussed in connection with Cu-Benzoate which is considered as a model substance of OA theory.

High-field electron spin resonance measurements of an antiferromagnet Ca3ZnMnO6 isostructure, with the Ising-chain multiferroic Ca3CoMnO6, have been carried out. Two distinct resonance modes were observed below TN = 25 K, which is well explained by conventional antiferromagnetic resonance theory with easy-plane anisotropy. The zero-field spin gap is derived to be about 166 GHz, originating from the easy-plane anisotropy and exchange interaction. Our result suggests that the Dzyaloshinsky-Moriya interaction, which may induce spin canting, is absent. Disappearance of Ising anisotropy in Ca3ZnMnO6 suggests that the Co(4+) ion, as well as the Co-Mn superexchange, plays an important role for the Ising nature in Ca3CoMnO6.

Recent development of the high-field facility in Kobe University is presented. We installed a 3 kV, 100 kJ capacitor bank, this is four times larger in energy than the previous one, and we achieved 42 T recently using a Cu–Ag pulsed magnet. Recent high-field ESR studies of quantum spin systems such as high pressure phase (VO)2P2O7 will be presented. The high-pressure phase of (VO)2P2O7 is the S= 1 2 bond alternating antiferromagnet; we found an anomaly in the ESR mode of the high-pressure phase (VO)2P2O7 single crystal at 20 T by observing the frequency dependence at 4.2 K. Finally, we refer to our new development of the high-field ESR system under high pressure. We developed a compact pressure cell with sapphire window which fits into our pulsed magnet. The ESR result using this pressure cell will be presented.

Cyclotron resonances of quasi-two-dimensional (q2D) organic conductor θ-(BEDT-TTF)2I3 have been observed by using strip-line technique at 1.8 K and Millimeter Vector Network Analyzer, V- and W-Band Cavity at 0.5 K. Two resonances are observed, and the mode coupling in the cavity and angular dependence suggest that they are (q2D) cyclotron resonances. The obtained effective masses 0.96me and 2.13me are assigned to the α and β orbits, respectively.

High-field electron spin resonance has been measured on a Ni 2 (μ-N 3 ) 3 (dpt) 2 (ClO 4 ) single crystal, which is an S =1 Heisenberg antiferromagnet with bond alternation, in the frequency region from 50 to 370 GHz using pulsed magnetic fields up to 16 T. The g -values for H perpendicular and parallel to the single-crystal plane were determined to be 2.19 and 2.13, respectively. By analysing our results on frequency dependence at 20 K by the simple dimer model considering the singlet and triplet states, we were able to determine the single-ion anisotropy of the system as | D |=10.6 K and | E |=3.1 K for the first time. The spin gap was estimated to be 93 K from the analysis of the temperature dependence of the integrated intensity. These results will be discussed in connection with other S =1 Heisenberg antiferromagnets with bond alternation.

Due to the existence of strong spin frustration in a system, the spin dynamics of S= 1/2 kagome lattice antiferromagnet at low temperature has attracted much interest. High-field ESR has been measured on its model substances, Cu 3 V 2 O 7 (OH) 2 · 2H 2 O (volborthite) and BaCu 3 V 2 O 3 (OH) 2 (vesignieite), down to 1.8 K using pulsed magnetic fields up to 16 T. The measurements are performed for 160 and 315 GHz using polycrystalline samples. Although both samples showed the g-shift and the change of linewidth at low temperature, volborthite showed a small gap excitation of the order of 40 GHz (1.9 K) while vesignieite showed a paramagnetic behavior down to 1.9 K. Observed difference will be discussed in connection with the crystal structure, and the possible spin liquid state in vesignieite will be discussed.

Quasi-one-dimensional (1-D) cupric oxide Ca1−xCuO2 (x = 0.164) is the system with 25–40% hole-doped edge-sharing CuO2 chains. However, the holes are almost localized in Ca1−xCuO2 and its magnetic susceptibility with a peak at 30 K was explained by the model considering both 1-D antiferromagnetic chains and spin dimers (Z. Hiroi, M. Okumura, Y. Nabeshima, T. Yamada, M. Takano: J. Phys. Soc. Jpn.69, 1824, 2000). To clarify the magnetic nature of Ca1−xCuO2, we performed submillimeter-wave electron spin resonance (ESR) measurements on a powder sample of Ca0.83−6CuO2. The resonance above 12 K showed typical powder ESR of Cu2+ and theg-values were determined to be g∥= 2.33 and g⊥ = 2.06 from the analysis. The resonance below 12 K changed completely from ESR. The frequency-field relation of ESR at 1.8 K clearly showed the easy-axis type antiferromagnetic resonance.