First-principles prediction of coexistence of magnetism and ferroelectricity in rhombohedral Bi2FeTiO6

First principles calculations based on the density functional theory within the local spin density approximation plus U(LSDA + U) scheme, show rhombohedral Bi₂FeTiO₆ is a potential multiferroic in which the magnetism and ferroelectricity coexist. A ferromagnetic configuration with magnetic moment of 4μB per formula unit has been reported with respect to the minimum total energy. Spontaneous polarization of 27.3 μC/cm², caused mainly by the ferroelectric distortions of Ti, was evaluated using the berry phase approach in the modern theory of polarization. The Bi-6s stereochemical activity of long-pair and the ‘d⁰-ness’ criterion in off-centring of Ti were coexisting in the predicted new system. In view of the oxidation state of Bi³⁺, Fe²⁺, Ti⁴⁺, and O²⁻ from the orbital-resolved density of states of the Bi-6p, Fe-3d, Ti-3d, and O-2p states, the valence state of Bi₂FeTiO₆ in the rhombohedral phase was found to be Bi³⁺₂Fe²⁺Ti⁴⁺O₆.     

Improvement of the electrical properties of TiO2-doped Bi5Nb3O15 thin films by the addition of MnO2

The leakage current density of a 1.0 mol% TiO₂-doped Bi₅Nb₃O₁₅ (TB₅N₃) film was high, and the breakdown electric field was low. This could be attributed to the presence of intrinsic oxygen vacancies and free electrons. The electrical properties of the TB₅N₃ film improved upon the addition of MnO₂ because of the formation of extrinsic oxygen vacancies, which caused the number of intrinsic oxygen vacancies to decrease in order to maintain the equilibrium concentration of oxygen vacancies in the film. However, the electric properties degraded when the MnO₂ content exceeded 15.0 mol% because of the formation of interstitial oxygen ions and holes. The dielectric constant (?_r) of the TB₅N₃ film slightly decreased upon the addition of a small amount of MnO₂. The TB₅N₃ film with 15.0 mol% MnO₂, which exhibited a small leakage current density of 2.5 × 10^?11 A/cm² at 0.15 MV/cm and a high breakdown electric field of 0.47 MV/cm, still maintained a large ?_r of 118 with a small loss tangent of 2.0% at 100.0 kHz.     

Studying local structural, valence, and magnetic states of iron ions in Bi0.9Ca0.1FeO3 perovskite

Mössbauer method was used to study a perovskite compound Bi_0.9Ca_0.1FeO₃ at T = 295 K and at temperature above T _N . It has been established that Bi_0.9Ca_0.1FeO₃ has a rhombohedral crystal structure similar to that of BiFeO₃. The substitution of Ca²⁺ for Bi³⁺ ions leads to the formation of three states of Fe³⁺ ions with an octahedral surroundings and one state with a tetrahedral oxygen surroundings with substantially different hyperfine magnetic fields. All Fe ions are in a trivalent state; the compensation of the charge deficit occurs via the formation of oxygen vacancies. Above T _N , two structurally nonequivalent states of Fe³⁺ ions exist in the Bi_0.9Ca_0.1FeO₃ sample, which correspond to the Fe³⁺ ions with an octahedral and tetrahedral oxygen coordination.     

Effect of oxygen partial pressure and VO<Subscript>2</Subscript> content on hexagonal WO<Subscript>3</Subscript> thin films synthesized by pulsed laser deposition technique

We report on the effect of oxygen partial pressure and vacuum annealing on structural and optical properties of pulsed laser-deposited nanocrystalline WO₃ thin films. XRD results show the hexagonal phase of deposited WO₃ thin films. The crystallite size was observed to increase with increase in oxygen partial pressure. Vacuum annealing changed the transparent as-deposited WO₃ thin film to deep shade of blue color which increases the optical absorption of the film. The origin of this blue color could be due to the presence of oxygen vacancies associated with tungsten ions in lower oxidation states. In addition, the effects of VO₂ content on structural, electrochemical, and optical properties of (WO₃)_1−x (VO₂) _x nanocomposite thin films have also been systematically investigated. Cyclic voltammogram exhibits a modification with the appearance of an extra cathodic peak for VO₂–WO₃ thin film electrode with higher VO₂ content (x ≥ 0.2). Increase of VO₂ content in (WO₃)_1−x (VO₂) _x films leads to red shift in optical band gap.     

Determination of surface oxygen vacancy position in SnO2 nanocrystals by Raman spectroscopy

Raman spectra acquired from SnO₂ nanocrystals with different sizes show a size-independent Raman mode at ∼574 cm⁻¹. The intensity increases as the nanocrystal size decreases and this tendency is contrary to that of the normal bulk Raman modes. By considering the existence of oxygen vacancies at the nanocrystal surface, we adopt the density functional theory to calculate the Raman spectra with different oxygen vacancy positions and concentrations. The results clearly demonstrate that the in-plane oxygen vacancy is responsible for the 574 cm⁻¹ mode and the intensity enhancement is a result of the higher in-plane oxygen vacancy concentration.     

Electronic structure,ferroelectricity and optical properties of CaBi<Subscript>2</Subscript>Ta<Subscript>2</Subscript>O<Subscript>9</Subscript>

Using first-principles calculations based on density-functional theory in its local-density approximation, we investigated the Electronic structure, ferroelectricity and optical properties of CaBi₂Ta₂O₉ (CBT) for the first time. It is found that CBT compound has an indirect band gap of 3.114 eV and the O 2s and 2p states are strongly hybridized with the 6s states of Bi which belong to the (Bi₂O₂)²⁺ planes. The quite strong Ta–O and Bi–O hybridization is the primary source for ferroelectricity. Our results imply that the interaction between Bi and O is highly covalent. The anisotropy occurs mainly above 4 eV in the optical properties. The different optical properties have been discussed.     

Room-temperature and solution-processed vanadium oxide buffer layer for efficient charge injection in bottom-contact organic field-effect transistors

We introduce a room temperature and solution-processible vanadium oxide (VO_x) buffer layer beneath Au source/drain electrodes for bottom-contact (BC) organic field-effect transistors (OFETs). The OFETs with the VO_x buffer layer exhibited higher mobility and lower threshold voltages than the devices without a buffer layer. The hole mobility with VO_x was over 0.11 cm²/V with the BC geometry with a short channel length (10 μm), even without a surface treatment on SiO₂. The channel width normalized contact resistance was decreased from 98 kΩ cm to 23 kΩ cm with VO_x. The improved mobility and the reduced contact resistance were attributed to the enhanced continuity of pentacene grains, and the increased work function and adhesion of the Au electrodes using the VO_x buffer layer.     

Ferroelectric and structural instability in double perovskites Me1+Bi3+Me3+Nb5+O6 (Me1+ = Na, K, Rb; Me3+ = Sc, Ga, In, Lu)

Within the Gordon-Kim generalized model with regard to the polarizabilities of ions, the lattice constants, the high-frequency permittivity, the Born dynamic charges, and the vibration constants of the crystal lattice are calculated for cation-ordered double perovskites Me¹⁺Bi³⁺Me³⁺Nb⁵⁺O₆. The vibration spectra of all the compounds exhibit two types of instabilities: instability associated with the rotation of the oxygen octahedron and ferroelectric instability. Various combinations of distortions with respect to the rotation mode yield five energetically most favorable distorted phases. The symmetry and the energy characteristics of these phases are discussed. In four of the five phases, the distortions associated with the oxygen octahedron rotation lead to polar phases, thus allowing one to speak of improper ferroelectricity in these compounds. One phase turns out to be nonpolar; however, it contains unstable polar modes such that a displacement along the eigenvectors of these modes gives rise to polarization in the crystal.     

C-V studies on metal-ferroelectric bismuth vanadate (Bi2VO5.5)-semiconductor structure

Ferroelectric bismuth vanadate Bi₂VO_5.5 (BVO) thin films have been successfully grown on p-type Si(100) substrate by using chemical solution decomposition (CSD) technique followed by rapid thermal annealing (RTA). The crystalline nature of the films has been studied by X-ray diffraction (XRD). Atomic force microscopy (AFM) was used to study the microstructure of the films. The dielectric properties of the films were studied. The capacitance-voltage characteristics have been studied in metal-ferroelectric-insulator-semiconductor (MFIS) configuration. The dielectric constant of BVO thin films formed on Si(100) is about 146 measured at a frequency of 100 kHz at room temperature. The capacitance-voltage plot of a Bi₂VO_5.5 MFIS capacitor subjected to a dc polarizing voltages shows a memory window of 1.42 V during a sweep of ±5 V gate bias. The flatband voltage (V_f) shifts towards the positive direction rather than negative direction. This leads to the asymmetric behavior of the C-V curve and decrease in memory window. The oxide trap density at a ramp rate of 0.2 V/s was estimated to be as high as 1.45×10¹² cm⁻².     

Bismuth ferrite composite thin films

0.60Bi_0.90La_0.10FeO₃–0.40Pb(Zr_0.52Ti_0.48)O₃ composite thin films were deposited on Pt/TiO₂/SiO₂/Si(100) substrates by radio-frequency sputtering and their ferroelectric and fatigue properties were mainly investigated. The composite thin films have a low dielectric loss, a high dielectric constant, and enhanced ferroelectric properties of 2P _r～122.6 μC/cm² and 2E _c～479.3 kV/cm, together with a fatigue-free behavior at 200 kHz. Their fatigue behavior is strongly dependent on measurement frequencies, and the concentration of oxygen vacancies plays an important role in their fatigue behavior.     

The influence of lanthanum doping on the physical and electrical properties of BTV ferroelectric thin films

In this study, the ferroelectricity of as-deposited Bi_3.9La_0.1Ti_2.9V_0.1O₁₂ (BLTV), Bi_3.9Ti_2.9V_0.1O₁₂ (BTV), and Bi₄Ti₃O₁₂ (BIT) thin films was prepared and compared by rf magnetron sputtering technology. For the BLTV, BTV, and BIT thin films deposited on Pt/Ti/SiO₂/Si and SiO₂/Si substrate, the physical and electrical characteristics of lanthanum doped BTV (BLTV) were better than those of BIT and BTV thin films. Regarding the physical properties, the micro-structure of as-deposited BTV and BLTV thin films were obtained and compared by XRD patterns and SEM images. The BLTV and BTV thin films were also exhibited clear the ferroelectricity. The remanent polarization (P _r ) of as-deposited BLTV thin films was 11 μC/cm² as the measured frequency of 100 kHz. It was higher than those of BTV thin films. Finally, the polarization of BLTV thin film capacitor decreased by 9%, while that of the BTV decreased by 15% after the fatigue test with 10⁹ switching cycles.     

First-principle study of the electronic structures and ferroelectric properties in BaZnF<Subscript>4</Subscript>

The electronic structures and ferroelectric properties of barium fluoride BaZnF₄were investigated by employing ab initio calculations based on the density-functional theory within generalized gradient approximation. We discussed the possible origin of ferroelectricity of BaZnF₄ by the analysis of Born effective charges, orbital-resolved density of states, and distribution of charge density. The results show that the barium and fluorine atoms are very important polarization unity. The calculated spontaneous polarization of 14.2 μC/cm² by using Berry-phase approach is reasonable agreement with previous experimental data. Barium fluorides are promising candidates for use in nonvolatile memories devices.     

Impact of annealing atmosphere on the multiferroic and dielectric properties of BiFeO3/Bi3.25La0.75Ti3O12 thin films

Multiferroic BiFeO₃/Bi_3.25La_0.75Ti₃O₁₂ films annealed in different atmospheres (N₂ or O₂) were prepared on Pt/Ti/SiO₂/Si substrates via a metal organic decomposition method. Based on our experimental results, it is considered that, in the films annealed in N₂, fewer Fe²⁺ ions while more oxygen vacancies are involved. As a result, at room temperature, predominated by the reduced Fe²⁺ fraction, lower leakage current and dielectric loss, better ferroelectric property while reduced magnetization are observed. However, the oxygen vacancies might be thermally activated at elevated temperature; thus, more strongly temperature-dependent leakage current and a higher dielectric relaxation peak are observed for the films annealed in N₂.     

The coexistence of ferroelectricity and ferromagnetism in Mn-doped BaTiO3 thin films

Due to the fault of the first author, this article entitled “The coexistence of ferroelectricity and ferromagnetism in Mn-doped BaTiO3 thin films”, published in “Chinese Physics B”, 2011,Vol.20, Issue 12, Article No. 127701, has been found to copy from the article entitled“Decisive role of oxygen vacancy in ferroelectric versus ferromagnetic Mn-doped BaTiO3 thin films”, published in “Journal of Applied Physics”, 2011,Vol.109, Issue 8, article No. 084105. So the above article in “Chinese Physics B” has been withdrawn from the publication.<     

Evolution of microstructure and dielectric properties of (LiCe)-doped Na0.5Bi2.5Nb2O9 Aurivillius type ceramics

Aurivillius type (NaBi)_0.5?x(LiCe)_xBi₂Nb₂O₉ ceramics were prepared by the standard ceramics route. The single crystal structural ceramics were achieved for all compositions and lattice distortion was decreased by (LiCe) dopants. The temperature dependent dielectric properties revealed that all compositions possess a high Curie-temperature (>780 °C). A modified Curie–Weiss relationship is used to study the diffuseness behavior of a ferroelectric phase transition indicating the degree of diffuseness of NBN-based ceramics increased with (LiCe) modifications. The degradation of resistance implied a plausible model that Ce⁴⁺ ions entered into the B-site of the pseudo-perovskite structure and acted as acceptor doping. Further investigation demonstrated that both electrical conduction and dielectric relaxation processes were associated with the oxygen vacancies produced by the substitution of Nb⁵⁺ ions by the Ce⁴⁺ ions.     

Structural and vibrational properties of PVT grown Bi2Te3 microcrystals

High-quality Bi₂Te₃ microcrystals have been grown by physical vapor transport (PVT) method without using a foreign transport agent. The microcrystals grown under optimal temperature gradient are well facetted and they have dimensions up to ～100 μm. The phase composition of grown crystals has been identified by X-ray single crystal structure analysis in space group R3?m, a=4.3896(2) Å, b=30.5019(10) Å, Z=3 (R=0.0271). Raman microspectrometry has been used to describe the vibration parameters of Bi₂Te₃ microcrystals. The FWHM parameters obtained for representative Raman lines at 61 cm^?1 and 101 cm^?1 are as low as 3.5 cm^?1 and 4.5 cm^?1, respectively.     

Structural,ferroelectric, optical properties of A-site-modified Bi0.5(Na0.78K0.22)0.5Ti0.97Zr0.03O3 lead-free piezoceramics

We reported the role of A-site modification on the structural, ferroelectric, optical and electrical field-induced strain properties of Bi_0.5(Na_0.78K_0.22)_0.5Ti_0.97Zr_0.03O₃ lead-free piezoceramics. The Li⁺ ions with concentration from 0 to 5 mol% were used to substitute at A-site. There was no phase transition when Li⁺ ions was added up to 5 mol%. The electric field-induced strain (S_max/E_max) values increased from 600 to 643 pm/V for 2 mol% Li⁺-added which results from distortion both rhombohedral and tetragonal phase structures. The band gap reduced from 2.88 to 2.68 eV and the saturation polarization decreased from 46.2 to 26.1 μC/cm² when Li⁺ ions concentration increased from 0 to 5 mol% respectively. We expect that this work could be helpful for further understanding the role of A-site dopants in comparison with B-site modification in lead-free Bi_0.5(Na,K)_0.5TiO₃-based ceramics.     

MWA and scanning-probe study of argon-ion irradiation effects on superconducting properties of Bi2Sr2CaCu2O8 thin films

Bi₂Sr₂CaCu₂O₈ films with thickness of 200 and 800 nm were irradiated with monovalent argon ions with an energy of 40 keV and a dose ranging between 10¹⁴ and 10¹⁷ ion/cm². The dose dependences of (i) the superconducting transition temperature, (ii) the critical current density value and (iii) the irreversibility line position on the magnetic field-temperature phase diagram were determined for two series of samples of different thickness. Atomic force microscopy images of the irradiated samples showed an appearance of defects in the form of surface holes. The obtained data were used to establish conditions for improving properties of thin-film superconducting materials. Firstly, the irradiation dose should be at least 10¹⁶ ion/cm² to form embedded gas bubbles and surface holes serving as artificial pinning centers. Secondly, the film thickness and the average depth of the defect formation should be of a comparable value and sufficiently exceed the thickness of the surface layer sputtered as a result of irradiation.     

Effect of Li2CO3 addition on the structural,optical, ferroelectric,and electric-field-induced strain of lead-free BNKT-based ceramics

In this work, we reported the effect of Li₂CO₃ addition on the structural, optical, ferroelectric properties and electric-field-induced strain of Bi_0.5(Na,K)_0.5TiO₃ (BNKT) solid solution with CaZrO₃ ceramics. Both rhombohedral and tetragonal structures were distorted after adding Lithium (Li). The band gap values decreased from 2.91 to 2.69 eV for 5 mol% Li-addition. The maximum polarization and remanent polarization decreased from 49.66 μC/cm² to 27.11 μC/cm² and from 22.93 μC/cm² to 5.35 μC/cm² for un-doped and 5 mol% Li- addition BNKT ceramics, respectively. The maximum S_max/E_max value was 567 pm/V at 2 mol% Li₂CO₃ access. We expected this work will help to understand the role of A-site dopant in lead-free ferroelectric BNKT materials.     

Anionic conductors Ln2/3[Bi12O14](MoO4)5 with Ln = La,Nd, Gd,Ho, Yb. Synthesis–spark plasma sintering–structure–electric properties

A new series of columnar phases Ln_2/3□_1/3[Bi₁₂O₁₄](MoO₄)₅ (□ vacancy) with Ln = La, Nd, Gd, Ho and Yb have been synthesized and structurally characterized. They feature the same formula as the molybdate phase Bi_2/3□_1/3[Bi₁₂O₁₄](MoO₄)₅ and crystallize in the monoclinic system, space group P2/c. These phases are isostructural with the prototype structure Bi[Bi₁₂O₁₄](MoO₄)₄(VO₄). Pellets of this rare-earth series obtained by spark plasma sintering and measured by impedance spectroscopy show a good anionic conductivity with a parabolic evolution whose maximum is raised by the Gd species at a determined value σ = 6.6 × 10^− 3 S cm^− 1 at 980 K.