Niobate Phase Research Articles

Mesoscopic Architectures Made of Electrically Charged Binary Colloidal Nanosheets in Aqueous System.

Inorganic layered materials can be converted to colloidal liquid crystals through exfoliation into inorganic nanosheets, and binary nanosheet colloids exhibit rich phase behavior characterized by multiphase coexistence. In particular, niobate-clay binary nanosheet colloids are characterized by phase separation at a mesoscopic (∼several tens of micrometers) scale whereas they are apparently homogeneous at a macroscopic scale. Although the mesoscopic structure of the niobate-clay binary colloid is advantageous to realize unusual photochemical functions, the structure itself has not been clearly demonstrated in real space. The present study investigated the structure of niobate-clay binary nanosheet colloids in detail. Four clay nanosheets (hectorite, saponite, fluorohectorite, and tetrasilisic mica) with different lateral sizes were compared. Small-angle X-ray scattering (SAXS) indicated lamellar ordering of niobate nanosheets in the binary colloid. The basal spacing of the lamellar phase was reduced by increasing the concentration of clay nanosheets, indicating the compression of the liquid crystalline niobate phase by the isotropic clay phase. Scattering and fluorescence microscope observations using confocal laser scanning microscopy (CLSM) demonstrated the phase separation of niobate and clay nanosheets in real space. Niobate nanosheets assembled into domains of several tens of micrometers whereas clay nanosheets were located in voids between the niobate domains. The results clearly confirmed the spatial separation of two nanosheets and the phase separation at a mesoscopic scale. Distribution of clay nanosheets is dependent on the employed clay nanosheets; the nanosheets with large lateral length are more localized or assembled. This is in harmony with larger basal spacings of niobate lamellar phase for large clay particles. Although three-dimensional compression of the niobate phase by the coexisting clay phase was observed at low clay concentrations, the basal spacing of niobate phase was almost constant irrespective of niobate concentrations at high clay concentrations, which was ascribed to competition of compression by clay phase and restoring of the niobate phase.

Research and Compensation of Frequency Response of LiNbO3 Phase Modulator for High-Performance Fiber-Optic Gyroscope

A lithium niobate (LN) phase modulator is widely spread because ofhigh electro-optic coefficients. Particularly, it is a highly required component for a closed-loop fiber-optic gyroscope (FOG) of navigation and tactical grade. However, low-frequency distortions of LN phase modulator frequency response can degrade the FOG performance. This paper deals with the research and compensation of frequency response of an LN phase modulator. It is a complex task to measure the response of the LN phase modulator in a FOG because of its Sagnac interferometer. Therefore, the special and novel modulation/demodulation algorithm is proposed. To the best of our knowledge and belief, the proposed method is the first published method that provides the measurement of the pulse response of a phase modulator as a part of a closed-loop FOG. The pulse response obtained in the proposed way allows getting appropriate high order transfer function of a phase modulator. For the first time to the best of our knowledge, the humidity dependence of the LN phase modulator frequency response is found. Influence of the phase modulator frequency response on FOG angular random walk, bias drift, and scale factor nonlinearity and instability is theoretically analyzed and mathematically simulated. The algorithmic method of the phase modulator response compensation is proposed and experimentally confirmed. The experimental results show that the proposed measurement technique of the phase modulator transfer function allows creating the compensating inverse filter that provides phase modulator response being close to flat. The application of the proposed method in the FOG operating mode allows reducing unwanted spikes to the noise level.

All-fiber self-compensating polarization encoder for quantum key distribution.

Quantum key distribution (QKD) allows distant parties to exchange cryptographic keys with unconditional security by encoding information on the degrees of freedom of photons. Polarization encoding has been extensively used for QKD along free-space, optical fiber, and satellite links. However, the polarization encoders used in such implementations are unstable, expensive, and complex and can even exhibit side channels that undermine the security of the protocol. Here we propose a self-compensating polarization encoder based on a lithium niobate phase modulator inside a Sagnac interferometer and implement it using only commercial off-the-shelf (COTS) components. Our polarization encoder combines a simple design and high stability reaching an intrinsic quantum bit error rate as low as 0.2%. Since realization is possible from the 800 to the 1550nm band using COTS devices, our polarization modulator is a promising solution for free-space, fiber, and satellite-based QKD.

Sol-Gel and Electrospinning Synthesis of Lithium Niobate-Silica Nanofibers

Lithium niobate-silica fibers were produced by the combination of the sol-gel method and the electrospinning technique. Two sol-gel solutions starting from niobium-lithium ethoxide and tetraethyl orthosilicate were prepared and then mixed with polyvinylpyrrolidone; the solutions were electrospun in a coaxial setup. The obtained lithium niobate-silica polymeric fibers were approximately 760 nm in diameter. Raman spectroscopy confirmed the composite composition by showing signals corresponding to lithium niobate and silica. Scanning electron microscopy showed coaxial fibers with a diameter of around 330 nm arranged as a fibrillar membrane at 800 °C. At 1000 °C the continuous shape of fibers was preserved; the structure is composed of silica and lithium niobate nanoparticles within the fibers. The formation of crystalline lithium niobate and amorphous SiO2 phase was also confirmed by XRD peaks.

Stable Low-Repetition-Rate Time-Lens Picosecond Seed Source

The design and performance of a sub-10-picosecond source based on temporal focusing implemented with a lithium niobate phase modulator and a grating compressor are presented. The source is optimized taking into account spectral gain narrowing in subsequent amplifiers. It advantageously delivers low-repetition-rate pulses with tunable pulse duration, and its short-term jitter and long-term drift over extended periods of time are of the order of a few picoseconds.

20 GHz actively mode-locked thulium fiber laser.

A high repetition-rate actively mode-locked thulium fiber laser is demonstrated where an electro-optic lithium niobate phase modulator is used to synchronize the longitudinal modes in the cavity. The repetition rate of the actively mode-locked laser is tunable from 14.6 MHz to 19 GHz, where the 19 GHz pulses exhibit a super-mode suppression ratio of 46 dB. Furthermore, the output pulse width could be manipulated through finely controlling the detuning frequency or repetition rate. We have also experimentally observed rational harmonic mode-locking in the laser and obtained 14 GHz and 21 GHz repetition rate pulses using a 7 GHz modulating signal. To the best of our knowledge, we have improved the repetition-rate of actively mode-locked thulium fiber laser by more than one order of magnitude. Such a high repetition source can be readily synchronized to a master clock, which makes it very suitable for high speed optical data processing, communication and remote sensing.

Control of residual amplitude modulation in Lithium Niobate phase modulators

This work provides a simple model for Residual Amplitude Modulation observed in Lithium Niobate phase modulators. It operates under two key assumptions: the optical field incident on the modulator is not perfectly aligned to the preferred axis, and the two linear polarizations become spatially separated while travelling down the waveguide. These assumptions allow for a straight forward transfer matrix based approach. The effects of chromatic dispersion present in the optical fiber following the modulator are included, as they become important for modulation frequencies over 20 GHz. The result is a closed form expression for the intensity modulated signal seen by the photodetector in a phase modulated system. The model describes a near-instantaneous control mechanism, which is useful in minimizing the residual amplitude modulation in fielded systems by offering over 40 dB of suppression. The model is compared to direct measurements, validating the polarization effects and control mechanism proposed. Furthermore, etalon effects are ruled out by doing a course temperature dependence measurement.

Spark plasma sintering and decomposition of the Y3NbO7:Eu phase

The spark plasma sintering (SPS) of Eu3+-doped Y3NbO7 niobate phase was investigated to obtain dense ceramics. Although SPS allowed obtaining high-density ceramics, decomposition of the niobate phase occurred at high temperature and was promoted by the SPS process, which limited its use as an optical material. The niobate phase has been prepared by two synthesis methods: a solid-state route and a sol–gel method. The purity, density and microstructure of the dense ceramics were analyzed after spark plasma sintering. Translucent ceramics were only obtained from sol–gel powders after SPS at 1600 °C during 20 min with a heating rate of 5 °C/min. The sintering study of the pure niobate phase showed that during SPS process and especially in the presence of the high electrical field the Y3NbO7 phase is metastable at 1600 °C. A decomposition of the niobate compound is clearly demonstrated by luminescence measurements when high heating rates were used.

First-principles examination of low tolerance factor perovskites

Perovskites are generally formed in the non-polar Pnma phase. The materials found in the polar subgroup of Pnma are not common. This article reports how perovskites having a low tolerance factor display ferroelectric instabilities in artificially constrained Pnma phase. The bond length distribution and the bond valence sum were analyzed to examine the origin of the ferroelectric behavior of low tolerance factor materials. However, the ground state structure of low tolerance perovskite is not Pnma phase, but either ilmenite (R 3¯) or lithium niobate (R3c) phase. Here, epitaxial strain was used as a tuning parameter to stabilize the polar subgroup of Pnma. The rationalized principles from these studies will be valuable for designing new ferroelectric materials in the future.

Photoluminescence in europium ion–substituted bismuth niobate particles

ABSTRACTIn order to understand the influence of the substitution of europium ion for bismuth ion in the structural and photoluminescence properties of bismuth niobate, bismuth niobate ceramic powders, with different amount of europium ion, were prepared using sol–gel citrate route. The structural and morphological studies were made with X-ray diffraction, Raman, and scanning electron microscopy measurements. Rietveld’s analysis of X-ray diffraction proves the formation and increment of europium niobate phase in europium ion–substituted bismuth niobate samples with increase of europium ion concentration. Photoluminescence results also concur to that of X-ray diffraction and Raman with gradual swapping of europium ion emission from one phase to the other phase at higher concentration.

Chloride flux growth of crystalline strontium niobates and nitridation to perovskite SrNbO2N

Highly crystalline (110) layered perovskite Sr2Nb2O7, (111) layered perovskite Sr5Nb4O15 and complex perovskite Sr4Nb2O9 were prepared by NaCl-KCl flux growth method from SrCO3 and Nb2O5. This flux synthesis achieves single strontium niobate phase in contrast to mixed niobates from the solid state reaction with the same heating parameters. A little excess of Sr source was found to be required for the synthesis of Sr5Nb4O15 and Sr4Nb2O9 at elevated temperature due to slight evaporation. The three strontium niobates were converted to perovskite SrNbO2N via thermal ammonolysis under NH3 flow at 900°C. Post-wash treatment was performed to remove the byproduct SrO. This makes additional nanopores in SrNbO2N in the cases of Sr5Nb4O15 and Sr4Nb2O9, and results in increasing surface areas of SrNbO2N with Sr:Nb ratios in the precursors (from 9.9 to 19.8 and 35.5m2/g). On the other hand, the UV–Vis diffusion reflectance spectra reveal decreasing light absorption by defects in SrNbO2N in this order. This suggests fewer low-valent Nb defects in SrNbO2N prepared from precursor with higher Sr:Nb ratio. SrNbO2N prepared from Sr4Nb2O9 would be advantageous for applications that require high surface area and low defect density of the material.

Spectral evolution of Eu3+ doped Y3NbO7 niobate induced by temperature

A Eu3+ doped Y3NbO7 niobate powder was synthetized using a polymerizable complex route. It gave rise to nanometric particles that crystallized in the fluorine structure, corresponding to the Y3NbO7 phase. The thermal evolution of this powder was followed up to 1600°C, using X-ray diffraction and optical characterizations. The fluorine structure was maintained in the whole temperature range. However, spectral evolution of the samples calcined above 900°C showed a more complex situation. Emission spectra of powders heat treated at different temperatures showed an evolution of the emission lines that can be attributed first to a better crystallization of the niobate phase and second to its partial decomposition in favor of the formation of YNbO4 and Y2O3. Although the Y3NbO7 phase appeared stable up to 1650°C, from X-ray diffraction analysis, spectral analysis showed that the local environment of the doping element is modified from 1100°C.

Growth, defect structure, and THz application of stoichiometric lithium niobate

Owing to the extraordinary richness of its physical properties, congruent lithium niobate has attracted multidecade-long interest both for fundamental science and applications. The combination of ferro-, pyro-, and piezoelectric properties with large electro-optic, acousto-optic, and photoelastic coefficients as well as the strong photorefractive and photovoltaic effects offers a great potential for applications in modern optics. To provide powerful optical components in high energy laser applications, tailoring of key material parameters, especially stoichiometry, is required. This paper reviews the state of the art of growing large stoichiometric LiNbO3 (sLN) crystals, in particular, the defect engineering of pure and doped sLN with emphasis on optical damage resistant (ODR) dopants (e.g., Mg, Zn, In, Sc, Hf, Zr, Sn). The discussion is focused on crystals grown by the high temperature top seeded solution growth (HTTSSG) technique using alkali oxide fluxing agents. Based on high-temperature phase equilibria studies of the Li2O–Nb2O5–X2O ternary systems (X = Na, K, Rb, Cs), the impact of alkali homologue additives on the stoichiometry of the lithium niobate phase will be analyzed, together with a summary of the ultraviolet, infrared, and far-infrared absorption spectroscopic methods developed to characterize the composition of the crystals. It will be shown that using HTTSSG from K2O containing flux, crystals closest to the stoichiometric composition can be grown characterized by a UV-edge position of at about 302 nm and a single narrow hydroxyl band in the IR with a linewidth of less than 3 cm−1 at 300 K. The threshold concentrations for ODR dopants depend on crystal stoichiometry and the valence of the dopants; Raman spectra, hydroxyl vibration spectra, and Z-scan measurements prove to be useful to distinguish crystals below and above the photorefractive threshold. Crystals just above the threshold are preferred for most nonlinear optical applications apart holography and have the additional advantage to minimize the absorption even in the far-infrared (THz) range. The review also provides a discussion on the progress made in the characterization of non-stoichiometry related intrinsic and extrinsic defect structures in doped LN crystals, with emphasis on ODR-ion-doped and/or closely stoichiometric systems, based on both spectroscopic measurements and theoretical modelling, including the results of first principles quantum mechanical calculations on hydroxyl defects. It will also be shown that new perspective applications, e.g., the generation of high energy THz pulses with energies on the tens-of-mJ scale, are feasible with ODR-doped sLN crystals if optimal conditions, including the contact grating technique, are applied.

Spectral changes induced by a phase modulator acting as a time lens

We show both numerically and experimentally that a phase modulator, acting as a time lens in the Fourier-lens configuration, can induce spectral broadening, narrowing, or shifts, depending on the phase of the modulator cycle. These spectral effects depend on the maximum phase shift that can be imposed by the modulator. In our numerical simulations, pulse spectrum could be compressed by a factor of 8 for a 30 rad phase shift. Experimentally, spectral shifts over a 1.35 nm range and spectral narrowing and broadening by a factor of 2 were demonstrated using a lithium niobate phase modulator with a maximum phase shift of 16 rad at a 10 GHz modulation frequency. All spectral changes were accomplished without employing optical nonlinear effects such as self- or cross-phase modulation.

High-Speed BPSK Modulation in Silicon

Binary phase-shift keying (BPSK) modulator is the basic component for generating advanced modulation formats such as polarization-division-multiplexed quadrature phase-shift keying. In this letter, we demonstrate BPSK modulation using a silicon traveling-wave modulator at data rate up to 48 Gb/s, with 7.4-V <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">pp</sub> differential RF driving voltage and record 8.75-pJ/b dynamic energy efficiency. The performance of the silicon BPSK modulator is compared with a commercial lithium niobate phase modulator, showing better dispersion tolerance.

Effect of Impregnation on the Structure of Niobium Oxide/Alumina Catalysts Studied by Multinuclear Solid-State NMR, FTIR, and Quantum Chemical Calculations

Multinuclear solid-state 1H, 27Al, and 93Nb NMR experiments and DFT calculations were carried out for structural characterization of alumina-supported niobium oxide catalysts with high niobium content following an every stage in the catalyst preparation. It was found that the first stage of the impregnation procedure plays a key role in determining the catalyst structure and acidity. In order to monitor the presence in catalysts of aluminum niobate phase, AlNbO4, a series of 27Al and 93Nb NMR experiments was performed for several different individual AlNbO4 samples. Aluminum and niobium NMR parameters were determined for AlNbO4, which crystal structure contains two different crystallographic sites for each element. The compound was investigated through a combination of experimental 93Nb and 27Al NMR spectroscopy methods at several magnetic field strengths (9.4, 11.7, 19.4, and 21.1 T) and complemented by ab initio quantum chemical calculations of NMR parameters for these nuclei. The chemical shielding and...

Synthesis of LiNbO&lt;SUB&gt;3&lt;/SUB&gt; Nanoparticles by Citrate Gel Method

We present investigations on the preparation of nearly stoichiometric lithium niobate (LiNbO3) nanoparticles using citrate gel method. Citric acid is used as a chelating agent and ethylene glycol is added for polyestarification between the chelates. In addition to the main lithium niobate phase, the secondary phase of lithium niobate, LiNb3O8, and an unreacted phase of Nb2O5 were also observed in the resultant product. The appearance of unwanted phases is a serious problem in citrate gel method. We have observed that the synthesis parameters such as molar ratio of citric acid to metal ions (R1), pH, molar ratio of ethylene glycol to citric acid (R2) and calcination temperature strongly influence the presence of the unwanted phases and these parameters are optimized to remove these phases. Evolution of the phase was investigated by powder XRD whereas TG/DTA was done to find out the crystallization temperature. It was observed that nearly stoichiometric and pure LiNbO3 nanoparticles can be obtained with the optimized parameters, R1 = 3, pH = 8, R2 ≥ 2 and calcination temperature = 700 degrees C. The stoichiometry of the synthesized LiNbO3 nanoparticles was investigated using Raman spectroscopy.

Phase Regeneration of a BPSK Data Signal Using a Lithium Niobate Phase Modulator

We propose a scheme for phase regeneration of an optical binary phase shift keying (BPSK) data signal using a Lithium Niobate (LiNbO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> ) phase modulator. The scheme is based on heterodyne detection of the BPSK data signal with a continuous wave local oscillator (CW-LO). Carrier recovery is then achieved in the electrical domain using a ×2 frequency-multiplier and a narrow-band filtering scheme. Subsequently, a superposition of the recovered carrier and the heterodyne detected data signal is used to modulate the CW-LO in a LiNbO3 phase modulator. The result is a parametric mixing process in the optical domain, leading to a phase-regenerated BPSK data signal by the coherent superposition with a phase-inverted copy. The proposed scheme constitutes a compact and stable setup, where active phase-stabilization of the electrical data- and carrier-paths can potentially be avoided. An analytical derivation of the working principle is provided, using Jacobi-Anger expansions to describe the phase-modulation. A proof-of-principle experiment is carried out, demonstrating regeneration of a 10 Gb/s NRZ-BPSK data signal degraded by a 5-GHz sinusoidal phase-noise tone. In the proof-of-principle demonstration, the decorrelated data- and LO-carriers are derived from the same CW source. A preliminary test with separate CW sources for data and LO, but without the required electrical narrow-band carrier filtering, is also included. Finally, numerical simulations of the regenerator performance in the presence of wideband phase- and amplitude-noise are performed.

High-pressure phase behaviors of ZnTiO3: ilmenite–perovskite transition, decomposition of perovskite into constituent oxides, and perovskite–lithium niobate transition

High-pressure high-temperature phase transitions of ZnTiO3 ilmenite were examined using multianvil apparatus up to 25.5 GPa and 1,500 °C and diamond anvil cell to 26.5 GPa and about 2,000 °C. Combined results of the multianvil quench experiments and in situ diamond anvil cell experiments indicated that at about 10 GPa and 1,200 °C ZnTiO3 ilmenite transforms to orthorhombic perovskite which is converted to lithium niobate phase on release of pressure. The boundary of the ilmenite–provskite transition is expressed by P(GPa) = 15.9 − 0.005T (°C). The high-pressure experiments also indicated that at 20–24 GPa and 1,000–1,400 °C ZnTiO3 orthorhombic perovskite dissociates into rocksalt-type ZnO + baddeleyite-type TiO2 which are recovered, respectively, as wurtzite-type ZnO and α-PbO2-type TiO2 at 1 atm. The boundary of the perovskite dissociation is expressed by P(GPa) = 8.7 + 0.011T (°C). Molar volume changes of ZnTiO3 at ambient conditions were estimated as −4.7 % for the ilmenite–perovskite transition and −3.5 % for the perovskite decomposition into the oxides. The absence of CaIrO3-type postperovskite in ZnTiO3 is consistent with that dissociation of ZnTiO3 perovskite into the oxides has the larger molar volume change than −1 to −2 % of the perovskite–postperovskite transition in various ABO3 compounds and with previous data that ABO3 perovskites with relatively ionic B–O bonds do not transform to the postperovskite. The transition behaviors of ZnTiO3 are similar to those of MnTiO3 and FeTiO3, but ZnTiO3 perovskite dissociates into the constituent oxides.

Synthesis, structural and magnetic characterization of lead-metaniobate/cobalt-ferrite nanocomposite films deposited by pulsed laser ablation

Detailed structural, microstructural and magnetic measurements were performed on (PbNb2O6)1−x –(CoFe2O4) x nanocomposite thin films deposited by laser ablation on Si(001)\Pt substrates, with different cobalt ferrite concentrations. The tuning of the lead concentration, due to the lead volatility, was found to be particularly important in order to obtain the orthorhombic (ferroelectric) lead niobate phase. The lattice parameter of CoFe2O4 was below the bulk value, indicating the presence of compressive strains on this phase. A magnetic anisotropy was observed, which favored the orientation of the magnetization in the direction perpendicular to the plane of the films, for cobalt ferrite concentrations 40–50 %. The shape, stress and magnetocrystalline anisotropy fields on the composites were calculated and compared. It was found that the perpendicular magnetic anisotropy was induced by the presence of strain on the ferrite phase in the films.