Louis-Claude Brunel

Nonresonant detection of terahertz radiation in field effect transistors

We present an experimental and theoretical study of nonresonant detection of subterahertz radiation in GaAs/AlGaAs and GaN/AlGaN heterostructure field effect transistors. The experiments were performed in a wide range of temperatures (8–300 K) and for frequencies ranging from 100 to 600 GHz. The photoresponse measured as a function of the gate voltage exhibited a maximum near the threshold voltage. The results were interpreted using a theoretical model that shows that the maximum in photoresponse can be explained by the combined effect of exponential decrease of the electron density and the gate leakage current.

Resonant detection of subterahertz radiation by plasma waves in a submicron field-effect transistor

The resonant detection of subterahertz radiation by two-dimensional electron plasma confined in a submicron gate GaAs/AlGaAs field-effect transistor is demonstrated. The results show that the critical parameter that governs the sensitivity of the resonant detection is ωτ, where ω is the radiation frequency and τ is the momentum scattering time. By lowering the temperature and hence increasing τ and increasing the detection frequency ω, we reached ωτ∼1 and observed resonant detection of 600 GHz radiation in a 0.15 μm gate length GaAs field-effect transistor. The evolution of the observed photoresponse signal with temperature and frequency is reproduced well within the framework of a theoretical model.

A multifrequency high-field pulsed electron paramagnetic resonance/electron-nuclear double resonance spectrometer.

We describe a pulsed electron paramagnetic resonance spectrometer operating at several frequencies in the range of 110-336 GHz. The microwave source at all frequencies consists of a multiplier chain starting from a solid state synthesizer in the 12-15 GHz range. A fast p-i-n-switch at the base frequency creates the pulses. At all frequencies a Fabry-Perot resonator is employed and the pi/2 pulse length ranges from approximately 100 ns at 110 GHz to approximately 600 ns at 334 GHz. Measurements of a single crystal containing dilute Mn(2+) impurities at 12 T illustrate the effects of large electron spin polarizations. The capabilities also allow for pulsed electron-nuclear double resonance (ENDOR) experiments as demonstrated by Mims ENDOR of (39)K nuclei in Cr:K(3)NbO(8).We describe a pulsed multi-frequency electron paramagnetic resonance spectrometer operating at several frequencies in the range of 110-336 GHz. The microwave source at all frequencies consists of a multiplier chain starting from a solid state synthesizer in the 12-15 GHz range. A fast PIN-switch at the base frequency creates the pulses. At all frequencies a Fabry-Perot resonator is employed and the pi/2 pulse length ranges from ~100 ns at 110 GHz to ~600 ns at 334 GHz. Measurements of a single crystal containing dilute Mn2+ impurities at 12 T illustrate the effects of large electron spin polarizations. The capabilities also allow for pulsed electron nuclear double resonance experiments as demonstrated by Mims ENDOR of 39K nuclei in Cr:K3NbO8.

Coherent Manipulation and Decoherence of S = 10 Single-Molecule Magnets

We report coherent manipulation of S=10 Fe8 single-molecule magnets. The temperature dependence of the spin decoherence time T2 measured by high-frequency pulsed electron paramagnetic resonance indicates that strong spin decoherence is dominated by Fe8 spin bath fluctuations. By polarizing the spin bath in Fe8 single-molecule magnets at magnetic field B=4.6 T and temperature T=1.3 K, spin decoherence is significantly suppressed and extends the spin decoherence time T2 to as long as 712 ns. A second decoherence source is likely due to fluctuations of the nuclear spin bath. This hints that the spin decoherence time can be further extended via isotopic substitution to smaller nuclear magnetic moments.

High-frequency electron paramagnetic resonance investigation of the Fe3+ impurity center in polycrystalline PbTiO3 in its ferroelectric phase

The intrinsic iron(III) impurity center in polycrystalline lead titanate was investigated by means of high-frequency electron paramagnetic resonance spectroscopy in order to determine the local-environment sensitive fine-structure parameter D. At a spectrometer frequency of 190GHz, a spectral analysis of a powder sample was unambiguously possible. The observed mean value D=+35.28GHz can be rationalized if Fe3+ ions substitute for Ti4+ at the B site of the perovskite ABO3 lattice forming a directly coordinated FeTi′–VO∙∙ defect associate. A consistent fit of the multifrequency data necessitated the use of a distribution of the D values with a variance of about 1GHz. This statistical distribution of values is probably related to more distant defects and vacancies.

Single‐Ion versus Dipolar Origin of the Magnetic Anisotropy in Iron(III)‐Oxo Clusters: A Case Study

A multitechnique approach has allowed the first experimental determination of single-ion anisotropies in a large iron(III)-oxo cluster, namely [NaFe6(OCH3)12(pmdbm)6ClO4 (1) in which Hpmdbm = 1,3-bis(4-methoxyphenyl)-1,3-propanedione. High-frequency EPR (HF-EPR). bulk susceptibility measurements, and high-field cantilever torque magnetometry (HF-CTM) have been applied to iron-doped samples of an isomorphous hexagallium(III) cluster [NaGa6(OCH3)12-(pmdbm)6]ClO4, whose synthesis and X-ray structure are also presented. HF-EPR at 240 GHz and susceptibility data have shown that the iron(III) ions have a hard-axis type anisotropy with DFe = 0.43(1) cm(-1) and EFe = 0.066(3) cm(-1) in the zero-field splitting (ZFS) Hamiltonian H = DFe[S2(z) - S(S + 1)/3] + Fe[S2(x) - S2(y)]. HF-CTM at 0.4 K has then been used to establish the orientation of the ZFS tensors with respect to the unique molecular axis of the cluster, Z. The hard magnetic axes of the iron(III) ions are found to be almost perpendicular to Z, so that the anisotropic components projected onto Z are negative, DFe(ZZ)= -0.164(4) cm(-1). Due to the dominant antiferromagnetic coupling, a negative DFe(ZZ) value determines a hard-axis molecular anisotropy in 1, as experimentally observed. By adding point-dipolar interactions between iron(III) spins, the calculated ZFS parameter of the triplet state, D1 = 4.70(9) cm(-1), is in excellent agreement with that determined by inelastic neutron scattering experiments at 2 K, D1 = 4.57(2) cm(-1). Iron-doped samples of a structurally related compound, the dimer [Ga2(OCH3)2(dbm)4] (Hdbm = dibenzoylmethane), have also been investigated by HF-EPR at 525 GHz. The single-ion anisotropy is of the hard-axis type as well, but the DFe parameter is significantly larger [DFe = 0.770(3) cm(-1). EFe = 0.090(3) cm(-1)]. We conclude that, although the ZFS tensors depend very unpredictably on the coordination environment of the metal ions, single-ion terms can contribute significantly to the magnetic anisotropy of iron(III)-oxo clusters, which are currently investigated as single-molecule magnets.

Fabry-Pérot resonator for high-field multi-frequency ESR at millimetre and submillimetre wavelengths

The design and performance of a Fabry-Perot (FP) resonator for high-field multi-frequency electron spin resonance (ESR) at microwave frequencies from 110 GHz to 330 GHz and corresponding Zeeman fields between 3.9 T and 12 T (at g = 2) is described. The tunable semiconfocal FP arrangement includes an inductive copper mesh that can be mechanically adjusted to obtain best performance in the entire temperature range from room temperature to 4 K. Sensitivity improvements (as compared to transmission mode experiments without a resonator) of about two orders of magnitude are obtained at 330 GHz. The potential of the configuration for investigating spin systems of low concentration with millimetre and submillimetre ESR is demonstrated on three examples.

High-frequency and -field electron paramagnetic resonance of high-spin manganese(III) in tetrapyrrole complexes

High-field and -frequency electron paramagnetic resonance (HFEPR) spectroscopy has been used to study three complexes of high spin Manganese(III), 3d4, S = 2. The complexes studied were tetraphenylporphyrinatomanganese(III) chloride (MnTPPCI), phthalocyanatomanganese(III) chloride (MnPcCl), and (8,12-diethyl-2,3,7,13,17,18-hexamethylcorrolato)manganese(III) (MnCor). We demonstrate the ability to obtain both field-oriented (single-crystal like) spectra and true powder pattern HFEPR spectra of solid samples. The latter are obtained by immobilizing the powder, either in an n-eicosane mull or KBr pellet. We can also obtain frozen solution HFEPR spectra with good signal-to-noise, and yielding the expected true powder pattern. Frozen solution spectra are described for MnTPPCl in 2:3 (v/v) toluene/CH2Cl2 solution and for MnCor in neat pyridine (py) solution. All of the HFEPR spectra have been fully analyzed using spectral simulation software and a complete set of spin Hamiltonian parameters has been determined for each complex in each medium. Both porphyrinic complexes (MnTPPCl and MnPcCl) are rigorously axial systems, with similar axial zero-field splitting (zfs): D approximately -2.3 cm(-1), and g values quite close to 2.00. In contrast, the corrole complex, MnCor, exhibits slightly larger magnitude, rhombic zfs: D approximtely -2.6 cm(-1), absolute value(E) approximately 0.015 cm(-1), also with g values quite close to 2.00. These results are discussed in terms of the molecular structures of these complexes and their electronic structure. We propose that there is a significant mixing of the triplet (S = 1) excited state with the quintet (S= 2) ground state in Mn(III) complexes with porphyrinic ligands, which is even more pronounced for corroles.

Recent developments in high frequency/high magnetic field CW EPR. Applications in chemistry and biology

A recent review of developments in high magnetic field/high frequency continuous wave electron paramagnetic resonance (EPR) spectroscopy is presented. The main motivations to develop instrumentation beyond “conventional” spectrometers are the desire to increase the spectral resolution and the need for high frequencies in the case of large zero field splitting systems. The potential of high frequency EPR is illustrated with the study of a Mn based spin cluster, which also confirms the need for multifrequency measurements. Examples of high field/high frequency EPR applications to chemistry and biology demonstrate that additional structural information can be obtained with the resolution achieved at 245 GHz.

Submegahertz linewidth at 240GHz from an injection-locked free-electron laser

Radiation from an ultrastable 240GHz solid state source has been injected, through an isolator, into the cavity of the University of California, Santa Barbara millimeter-wave free-electron laser (FEL). High-power FEL emission, normally distributed among many of the cavity’s longitudinal modes, is concentrated into the single mode to which the solid state source has been tuned. The linewidth of the FEL emission is 0.5MHz, consistent with the Fourier transform limit for the 2μs pulses. This demonstration of frequency-stable, ultranarrow-band FEL emission is a critical milestone on the road to FEL-based pulsed electron paramagnetic resonance spectroscopy.