Low-frequency magnetic sensing by magnetoelectric metglas/bidomain LiNbO3 long bars

We present an investigation into the magnetic sensing performance of magnetoelectric bilayered metglas / bidomain LiNbO3 long thin bars operating in a cantilever or free vibrating regime and under quasi-static and low-frequency resonant conditions. Bidomain single crystals of Y+128o-cut LiNbO3 were engineered by an improved diffusion annealing technique with a polarization macrodomain structure of the “head-to-head” and “tail-to-tail” type. Long composite bars with lengths of 30, 40 and 45 mm, as well as with and without attached small tip proof masses, were studied. ME coefficients as large as 550 V/cm∙Oe, corresponding to a conversion ratio of 27.5 V/Oe, were obtained under resonance conditions at frequencies of the order of 100 Hz in magnetic bias fields as low as 2 Oe. Equivalent magnetic noise spectral densities down to 120 pT/Hz1/2 at 10 Hz and to 68 pT/Hz1/2 at a resonance frequency as low as 81 Hz were obtained for the 45 mm long cantilever bar with a tip proof mass of 1.2 g. In the same composite without any added mass the magnetic noise was shown to be as low as 37 pT/Hz1/2 at a resonance frequency of 244 Hz and 1.2 pT/Hz1/2 at 1335 Hz in a fixed cantilever and free vibrating regimes, respectively. A simple unidimensional dynamic model predicted the possibility to drop the low-frequency magnetic noise by more than one order of magnitude in case all the extrinsic noise sources are suppressed, especially those related to external vibrations, and the thickness ratio of the magnetic-to-piezoelectric phases is optimized. Thus, we have shown that such systems might find use in simple and sensitive room-temperature low-frequency magnetic sensors, e.g., for biomedical applications.publishe

Magnetoelectric metglas/bidomain y + 140°-cut lithium niobate composite for sensing fT magnetic fields

We investigated the magnetoelectric properties of a new laminate composite material based on y+140°-cut congruent lithium niobate piezoelectric plates with an antiparallel polarized “head-to-head” bidomain structure and metglas used as a magnetostrictive layer. A series of bidomain lithium niobate crystals were prepared by annealing under conditions of Li2O outdiffusion from LiNbO3 with a resultant growth of an inversion domain. The measured quasi-static magnetoelectric coupling coefficient achieved |αE31| = 1.9 V·(cm·Oe)–1. At a bending resonance frequency of 6862 Hz, we found a giant |αE31| value up to 1704 V·(cm·Oe)–1. Furthermore, the equivalent magnetic noise spectral density of the investigated composite material was only 92 fT/Hz1/2, a record value for such a low operation frequency. The magnetic-field detection limit of the laminated composite was found to be as low as 200 fT in direct measurements without any additional shielding from external noises.publishe

Effect of contact phenomena on the electrical conductivity of reduced lithium niobate

Lithium niobate is a ferroelectric material finding a wide range of applications in optical and acoustic engineering. Annealing of lithium niobate crystals in an oxygen-free environment leads to appearance of black coloration and concomitant increasing electrical conductivity due to chemical reduction. There are plenty of literary data on the electrophysical properties of reduced lithium niobate crystals though contact phenomena occurring during electrical conductivity measurement as well as issues of interaction between the electrode material and the test specimens are almost disregarded. The effect of chromium and indium tin oxide electrodes on the results of measurements of electrophysical parameters at room temperature for lithium niobate specimens reduced at 1100 °C has been investigated. It was found that significant nonlinearities in the VACs of the specimens at below 5 V distort the specific resistivity readings for lithium niobate. This requires measurements at higher voltages. Impedance spectroscopy studies have shown that the measurement results are largely affected by capacities including those probably induced near the contacts. It has been shown that the experimental results are described adequately well by a model implying the presence of near-contact capacities that are parallel to the specimen’s own capacity. Possible mechanism of the induction of these capacities has been described and a hypothesis has been proposed of the high density of electron states at the electrode/specimen interface that can trap carriers, the concentration of trapped carriers growing with an increase in annealing duration

Enhancement of piezoelectric properties of lithium niobate thin films by different annealing parameters

Piezoelectric materials with useful properties find a wide range of applications including opto- and acousto- electronics. Lithium niobate in the form of a thin film is one of those promising materials and has a potential to improve ferroelectric random access memories devices, optical waveguides or acoustic delay lines by virtue of its physical characteristics, e.g. electro-optic coefficient, acoustic velocity, refractive indices etc. The key challenge to overcome is lithium nonstoichiometry as it leads to the appearance of parasite phases and thus aggravates physical and structural properties of a film. According to literature data, in order to obtain microcrystalline piezoelectric phase in previously amorphous films a set of methods is used. In our case we tried to synthesize LN films using congruent target and non-heated silicon substrate and then attain the piezoelectric phase by different annealing parameters. Afterwards LN films were compared to the ones synthesized on the silicon substrate with an additional buffer layer of platinum. Samples were studied by scanning probe microscope. Self-polarization vectors were defined. Based on domain structure images, the histograms of distribution of piezoresponse signals were built

Magnetoelectric effect in three-layered gradient LiNbO3/Ni/Metglas composites

The effect of annealing in a permanent magnetic field on the magnitude of magnetoelectric coefficient in three-layered gradient magnetoelectric LiNbO3/Ni/Metglas composites has been studied. A method of electrochemical nickel deposition on bidomain lithium niobate crystals has been demonstrated. We show that the optimum annealing temperature in a permanent magnetic field for the generation of the highest remanence in the Ni layer is 350 °C. The specimens annealed at this temperature exhibit the greatest shift of the magnetoelectric coefficient dependence on external magnetic field magnitude relative to the value Hdc = 0. The quasi-static magnetoelectric coefficient in the absence of an external magnetic field proves to be 1.2 V/(cm ∙ Oe). The highest magnetoelectric coefficient that has been achieved at a bending structure resonance frequency of 278 Hz proves to be 199.3 V/(cm ∙ Oe) without application of an external magnetic field. The experimental magnetoelectric coefficient figures for three-layered gradient LiNbO3/Ni/Metglas composites are not inferior to those for most magnetoelectric composite materials reported earlier

Degradation of the electrical conductivity of charged domain walls in reduced lithium niobate crystals

In this work, the effect of long-term room temperature exposure on the electrical conductivity of the charged domain wall (CDWs) in nonpolar x-cut congruent lithium niobate (LiNbO3, LN) crystals has been studied. Bidomain ferroelectric structures containing head-to-head charged domain boundaries have been produced by diffusion annealing in air near the Curie temperature and by infrared annealing. The crystals have been reduction annealed in a nitrogen atmosphere for the formation of color centers and growth of the electrical conductivity. The current measured during the recording of the I-V curves of the specimens using scanning probe microscope after room temperature exposure for 91 days has been found to decrease. The effect of storage conditions on the electrical conductivity of the CDWs has been studied. Degradation of the electrical conductivity does not originate from the effect of environment on the crystal surface. It has been hypothesized that the degradation is caused by distribution of charge carriers shielding the bound charge of the CDWs

Synthesis of Disubstituted Carboxonium Derivatives of <i>Closo</i>-Decaborate Anion [2,6-B₁₀H₈O₂CC₆H₅]⁻: Theoretical and Experimental Study

A comprehensive study focused on the preparation of disubstituted carboxonium derivatives of closo-decaborate anion [2,6-B10H8O2CC6H5]− was carried out. The proposed synthesis of the target product was based on the interaction between the anion [B10H11]− and benzoic acid C6H5COOH. It was shown that the formation of this product proceeds stepwise through the formation of a mono-substituted product [B10H9OC(OH)C6H5]−. In addition, an alternative one-step approach for obtaining the target derivative is postulated. The structure of tetrabutylammonium salts of carboxonium derivative ((C4H9)4N)[2,6-B10H8O2CC6H5] was established with the help of X-ray structure analysis. The reaction pathway for the formation of [2,6-B10H8O2CC6H5]− was investigated with the help of density functional theory (DFT) calculations. This process has an electrophile induced nucleophilic substitution (EINS) mechanism, and intermediate anionic species play a key role. Such intermediates have a structure in which one boron atom coordinates two hydrogen atoms. The regioselectivity for the process of formation for the 2,6-isomer was also proved by theoretical calculations. Generally, in the experimental part, the simple and available approach for producing disubstituted carboxonium derivative was introduced, and the mechanism of this process was investigated with the help of theoretical calculations. The proposed approach can be applicable for the preparation of a wide range of disubstituted derivatives of closo-borate anions

Low-Frequency Vibration Sensor with a Sub-nm Sensitivity Using a Bidomain Lithium Niobate Crystal

We present a low-frequency sensor for the detection of vibrations, with a sub-nm amplitude, based on a cantilever made of a single-crystalline lithium niobate (LiNbO3) plate, with a bidomain ferroelectric structure. The sensitivity of the sensor-to-sinusoidal vibrational excitations was measured in terms of displacement as well as of acceleration amplitude. We show a linear behavior of the response, with the vibrational displacement amplitude in the entire studied frequency range up to 150 Hz. The sensitivity of the developed sensor varies from minimum values of 20 &#956;V/nm and 7 V/g (where g = 9.81 m/s2 is the gravitational acceleration), at a frequency of 23 Hz, to peak values of 92.5 mV/nm and 2443 V/g, at the mechanical resonance of the cantilever at 97.25 Hz. The smallest detectable vibration depended on the excitation frequency and varied from 100 nm, at 7 Hz, to 0.1 nm, at frequencies above 38 Hz. Sensors using bidomain lithium niobate single crystals, as sensitive elements, are promising for the detection of ultra-weak low-frequency vibrations in a wide temperature range and in harsh environments

New Aspects of the Synthesis of <i>closo</i>-Dodecaborate Nitrilium Derivatives [B₁₂H₁₁NCR]⁻ (R = <i>n</i>-C₃H₇, <i>i</i>-C₃H₇, 4-C₆H₄CH₃, 1-C₁₀H₇): Experimental and Theoretical Studies

The preparation of novel nitrilium derivatives of closo-dodecaborate anion [B12H11NCR]−, R = n-C3H7, i-C3H7, 4-C6H4CH3, 1-C10H7 is described. Target compounds were obtained in good yields (up to 73%). The synthesis of target borylated nitrilium derivatives was characterised by the simplicity of the chemical apparatus and the absence of the necessity for the purification of desired compounds. The crystal structures of previously obtained [B12H11NCCH3]− and novel [B12H11NCC3H7]− were established with the help of X-ray structure analysis. DFT-analysis of several nitrilium derivatives [B12H11NCR]−, R = CH3, C3H7, 4-CH3C6H4 was carried out. The main peculiarities of the C≡N bond of the exo-polyhedral substituent were revealed in terms of bond lengths, bond orders and atomic charges. The LUMO orbitals of the systems considered were examined for understanding of the electrophilic nature of the nitrilium derivatives of the closo-dodecaborate anion