X- and Q-band EPR with cryogenic amplifiers independent of sample temperature

Inspired by the success of NMR cryoprobes, we recently reported a leap in X-band EPR sensitivity by equipping an ordinary EPR probehead with a cryogenic low-noise microwave amplifier placed closed to the sample in the same cryostat [Šimėnas et al. J. Magn. Reson. 322, 106876 (2021)]. Here, we explore, theoretically and experimentally, a more general approach, where the amplifier temperature is independent of the sample temperature. This approach brings a number of important advantages, enabling sensitivity improvement irrespective of sample temperature, as well as making it more practical to combine with ENDOR and Q-band resonators, where space in the sample cryostat is often limited. Our experimental realisation places the cryogenic preamplifier within an external closed-cycle cryostat, and we show CW and pulsed EPR and ENDOR sensitivity improvements at both X- and Q-bands with negligible dependence on sample temperature. The cryoprobe delivers signal-to-noise ratio enhancements that reduce the equivalent pulsed EPR measurement time by 16× at X-band and close to 5× at Q-band. Using the theoretical framework we discuss further improvements of this approach which could be used to achieve even greater sensitivity

Q-band EPR cryoprobe

Following the success of cryogenic EPR signal preamplification at X-band, we present a Q-band EPR cryoprobe compatible with a standard EPR resonator. The probehead is equipped with a cryogenic ultra low-noise microwave amplifier and its protection circuit that are placed close to the sample in the same cryostat. Our cryoprobe maintains the same sample access and tuning which is typical in Q-band EPR, as well as supports high-power pulsed experiments on typical samples. The performance of our setup is benchmarked against that of existing commercial and home-built Q-band spectrometers, using CW EPR and pulsed EPR/ENDOR experiments to reveal a significant sensitivity improvement which reduces the measurement time by a factor of about 40× at 6 K temperature at reduced power levels

Electron paramagnetic resonance study of ferroelectric phase transition and dynamic effects in a Mn²⁺ doped [NH₄][Zn(HCOO)₃] hybrid formate framework

We present an X- and Q-band continuous wave (CW) and pulse electron paramagnetic resonance (EPR) study of a manganese doped [NH4][Zn(HCOO)3] hybrid framework, which exhibits a ferroelectric structural phase transition at 190 K. The CW EPR spectra obtained at different temperatures exhibit clear changes at the phase transition temperature. This suggests a successful substitution of the Zn2+ ions by the paramagnetic Mn2+ centers, which is further confirmed by the pulse EPR and 1H ENDOR experiments. Spectral simulations of the CW EPR spectra are used to obtain the temperature dependence of the Mn2+ zero-field splitting, which indicates a gradual deformation of the MnO6 octahedra indicating a continuous character of the transition. The determined data allow us to extract the critical exponent of the order parameter (β = 0.12), which suggests a quasi two-dimensional ordering in [NH4][Zn(HCOO)3]. The experimental EPR results are supported by the density functional theory calculations of the zero-field splitting parameters. Relaxation time measurements of the Mn2+ centers indicate that the longitudinal relaxation is mainly driven by the optical phonons, which correspond to the vibrations of the metal–oxygen octahedra. The temperature behavior of the transverse relaxation indicates a dynamic process in the ordered ferroelectric phase

Suppression of phase transitions and glass phase signatures in mixed cation halide perovskites

Cation engineering provides a route to control the structure and properties of hybrid halide perovskites, which has resulted in the highest performance solar cells based on mixtures of Cs, methylammonium, and formamidinium. Here, we present a multi-technique experimental and theoretical study of structural phase transitions, structural phases and dipolar dynamics in the mixed methylammonium/dimethylammonium MA1-xDMAxPbBr3 hybrid perovskites (0 ≤ x ≤ 1). Our results demonstrate a significant suppression of the structural phase transitions, enhanced disorder and stabilization of the cubic phase even for a small amount of dimethylammonium cations. As the dimethylammonium concentration approaches the solubility limit in MAPbBr3, we observe the disappearance of the structural phase transitions and indications of a glassy dipolar phase. We also reveal a significant tunability of the dielectric permittivity upon mixing of the molecular cations that arises from frustrated electric dipoles

Effect of Trap Levels and Defect Inhomogeneities on Carrier Transport in SiC Crystals and Radiation Detectors

We present investigation of carrier transport and trapping in 4H-SiC single crystals and high-energy radiation detectors. SiC detectors were produced from bulk vanadium-compensated semi-insulating single crystal 4H-SiC and provided with nickel ohmic and titanium Schottky contacts. The prevailing defect levels were revealed by means of thermally stimulated current and thermally stimulated depolarization methods and their advanced modification - multiple heating technique. From I-V measurements a Schottky barrier height of≈1.9 eV was found. In 4H-SiC:Va the following thermal activation values were deduced: 0.18-0.19 eV, 0.20-0.22 eV, 0.3-0.32 eV, 0.33 -0.41 eV, and 0.63 eV. The maximum with activation energy of 0.33-0.41 eV appears below 125 K and most probably is caused by thermal carrier generation from defect levels. In contrast, the first three maxima with lowest activation energies, which appear at higher temperatures, are likely associated with material inhomogeneities causing potential fluctuations of the band gap. The existence of different polarization sources in different temperature ranges is also demonstrated by thermally stimulated depolarization

Effect of Trap Levels and Defect Inhomogeneities on Carrier Transport in SiC Crystals and Radiation Detectors

We present investigation of carrier transport and trapping in 4H-SiC single crystals and high-energy radiation detectors. SiC detectors were produced from bulk vanadium-compensated semi-insulating single crystal 4H-SiC and provided with nickel ohmic and titanium Schottky contacts. The prevailing defect levels were revealed by means of thermally stimulated current and thermally stimulated depolarization methods and their advanced modification - multiple heating technique. From I-V measurements a Schottky barrier height of≈1.9 eV was found. In 4H-SiC:Va the following thermal activation values were deduced: 0.18-0.19 eV, 0.20-0.22 eV, 0.3-0.32 eV, 0.33 -0.41 eV, and 0.63 eV. The maximum with activation energy of 0.33-0.41 eV appears below 125 K and most probably is caused by thermal carrier generation from defect levels. In contrast, the first three maxima with lowest activation energies, which appear at higher temperatures, are likely associated with material inhomogeneities causing potential fluctuations of the band gap. The existence of different polarization sources in different temperature ranges is also demonstrated by thermally stimulated depolarization

Investigation of Carrier Transport in GaN Single Crystals and Radiation Detectors by Thermally Stimulated Methods

We investigated single crystals of GaN and thin film GaN radiation detectors by thermally stimulated currents and thermally stimulated depolarization methods in order to characterize carrier transport properties as influenced by material defect structure. In thick GaN no expressed structure of the thermally stimulated current spectra was observed in the temperature range from 100 K up to 350 K, which could be characteristic of the thermal carrier generation from trap levels. The experimental facts imply that the thermally stimulated current spectra might be caused not by carrier generation, but it could be due to thermal mobility changes. Therefore we had applied the numerical analysis by taking into account carrier scattering by ionized impurities and phonons. It was found that mobility limited by ionized impurities varies as T$\text{}^{2.8}$ and lattice scattering causes the dependence T$\text{}^{-3.5}$. The highest mobility values were up to 1550 cm$\text{}^{2}$/(V s) at 148-153 K. Such high values indicate relatively good quality of the single GaN thick crystals. In high resistivity GaN detectors irradiated by high doses of high-energy neutrons and X-rays current instabilities were observed which could be caused by the change of carrier drift paths in a highly disordered matter. A model of carrier percolation transport is presented

Influence of Irradiation by High-Energy Protons on GaN Detectors

We had investigated effects of the irradiation by 24 GeV protons with doses ranging from $1×10^{14}$ up to $1×10^{16} p//cm^2$ on the properties of GaN ionising radiation detectors. In theγ-spectra of the samples radiation of $\text{}^7Be,$ $\text{}^{22}Na,$ and other long-lived radionuclides with A <70 was identified. Their activities were proportional to the irradiation dozes. Device contact properties were analysed by current-voltage I-V dependences. Created defects were revealed by the thermally stimulated defect spectroscopy. In the less irradiated samples the following values of the effective thermal activation energies were found: 0.12-0.16 eV, 0.18-0.22 eV, 0.35-0.42 eV, and 0.84-0.94 eV. Meanwhile, in the detectors irradiated with the highest doses only current growth with the activation energy of about 0.8-1.0 eV could be identified. Effects of percolation transport in disordered media were proved in the irradiated material

Suppression of phase transitions and glass phase signatures in mixed cation halide perovskites

Cation engineering provides a route to control the structure and properties of hybrid halide perovskites, which has resulted in the highest performance solar cells based on mixtures of Cs, methylammonium, and formamidinium. Here, we present a multi-technique experimental and theoretical study of structural phase transitions, structural phases and dipolar dynamics in the mixed methylammonium/dimethylammonium MA1-xDMAxPbBr3 hybrid perovskites (0 ≤ x ≤ 1). Our results demonstrate a significant suppression of the structural phase transitions, enhanced disorder and stabilization of the cubic phase even for a small amount of dimethylammonium cations. As the dimethylammonium concentration approaches the solubility limit in MAPbBr3, we observe the disappearance of the structural phase transitions and indications of a glassy dipolar phase. We also reveal a significant tunability of the dielectric permittivity upon mixing of the molecular cations that arises from frustrated electric dipoles