Enhanced dielectric properties of lead barium zirconate thin films by manganese doping

(Pb_0.5Ba_0.5)ZrO₃ (PBZ) and 1 mol% Mn-doped (Pb_0.5Ba_0.5)ZrO₃ (Mn-PBZ) sol were successfully fabricated, and corresponding thin films were deposited on Pt(1 1 1)/TiO₂/SiO₂/Si(1 0 0) substrates by spin-coating method. Effects of Mn doping on the microstructure and electrical properties of PBZ thin films were investigated systemically. X-ray diffraction patterns showed that both films had a polycrystalline perovskite structure, and that the degree of (1 1 1) orientation were increased by Mn doping. Dielectric measurements illustrated that Mn-doped PBZ thin films not only had a larger dielectric constant, but also possessed a smaller dielectric loss. Accordingly, the tunability and the figure of merit of PBZ films were improved by Mn doping.     

Room-temperature ferromagnetism in Sn1−xMnxO2 nanocrystalline thin films prepared by ultrasonic spray pyrolysis

Sn_1−xMn_xO₂ (x=0.01-0.05) thin films were synthesized on quartz substrate using an inexpensive ultrasonic spray pyrolysis technique. The influence of doping concentration and substrate temperature on structural and magnetic properties of Sn_1−xMn_xO₂ thin films was systematically investigated. X-ray diffraction (XRD) studies of these films reflect that the Mn³⁺ ions have substituted Sn⁴⁺ ions without changing the tetragonal rutile structure of pure SnO₂. A linear increase in c-axis lattice constant has been observed with corresponding increase in Mn concentration. No impurity phase was detected in XRD patterns even after doping 5 at% of Mn. A systematic change in magnetic behavior from ferromagnetic to paramagnetic was observed with increase in substrate temperature from 500 to 700 °C for Sn_1−xMn_xO₂ (x=0.01) films. Magnetic studies reveal room-temperature ferromagnetism (RTFM) with 3.61×10⁻⁴ emu saturation magnetization and 92 Oe coercivity in case of Sn_1−xMn_xO₂ (x=0.01) films deposited at 500 °C. However, paramagnetic behavior was observed for the films deposited at a higher substrate temperature of 700 °C. The presence of room-temperature ferromagnetism in these films was observed to have an intrinsic origin and could be obtained by controlling the substrate temperature and Mn doping concentration.     

Ferromagnetism in amorphous Ge1−xMnx grown by low temperature vapor deposition

Magnetic properties of amorphous Ge_1−xMn_x thin films were investigated. The thin films were grown at 373 K on (100) Si wafers by using a thermal evaporator. Growth rate was ∼35 nm/min and average film thickness was around 500 nm. The electrical resistivities of Ge_1−xMn_x thin films are 5.0×10⁻⁴∼100 Ω cm at room temperature and decrease with increasing Mn concentration. Low temperature magnetization characteristics and magnetic hysteresis loops measured at various temperatures show that the amorphous Ge_1−xMn_x thin films are ferromagnetic but the ferromagnetic magnetizations are changing gradually into paramagnetic as increasing temperature. Curie temperature and saturation magnetization vary with Mn concentration. Curie temperature of the deposited films is 80-160 K, and saturation magnetization is 35-100 emu/cc at 5 K. Hall effect measurement at room temperature shows the amorphous Ge_1−xMn_x thin films have p-type carrier and hole densities are in the range from 7×10¹⁷ to 2×10²² cm⁻³.     

Effects of vanadium doping on structure and electrical properties of SrBi4Ti4O15 thin films

The effects of vanadium(V) doping into SrBi₄Ti₄O₁₅ (SBTi) thin films on the structure, ferroelectric, leakage current, dielectric, and fatigue properties have been studied. X-ray diffraction result showed that the crystal structure of the SBTi thin films with and without vanadium is the same. Enhanced ferroelectricity was observed in the V-doped SrBi₄Ti₄O₁₅ (SrBi_4−x/3Ti_4−xV_xO₁₅, SBTiV-x (x = 0.03, 0.06, and 0.09)) thin films compared to the pure SrBi₄Ti₄O₁₅ thin film. The values of remnant polarization (2P_r) and coercive field (2E_c) of the SBTiV-0.09 thin film capacitor were 40.9 μC/cm² and 105.6 kV/cm at an applied electric field of 187.5 kV/cm, respectively. The 2P_r value is over five times larger than that of the pure SBTi thin film capacitor. At 100 kHz, the values of dielectric constant and dielectric loss were 449 and 0.04, and 214 and 0.06 for the SBTiV-0.09 and the pure SBTi thin film capacitors, respectively. The leakage current density of the SBTiV-0.09 thin film capacitor measured at 100 kV/cm was 6.8 × 10⁻⁹ A/cm², which is more than two and a half orders of magnitude lower than that of the pure SBTi thin film capacitor. Furthermore, the SBTiV-0.09 thin film exhibited good fatigue endurance up to 10¹⁰ switching cycles. The improved electrical properties may be related to the reduction of internal defects such as bismuth and oxygen vacancies with changes in the grain size by doping of vanadium into SBTi.     

Synthesis, structural and magnetic study of polycrystalline LaNi1−xMnxO3 films

Polycrystalline double perovskite LaNi_1−xMn_xO₃ (x=0.3, 0.4, 0.5 and 0.7, which is defined as Mn03, Mn04, Mn05 and Mn07, respectively) thin films are successfully deposited on Si (1 0 0) substrates via chemical solution deposition method. Their structural and magnetic properties are measured. All the thin films are of single phase. Raman spectra indicate that relative intensity of Mn05 is stronger than that of others that can be attributed to the higher degree of B-site ordering. The low temperature magnetic moment of Mn05 is about 500 emu/cm³, which is obviously larger than that of Mn03 and Mn07 because of the long-range ordering of Mn and Ni ions in Mn05.     

Magnetoelectric properties of Mn-substituted BiFeO3 thin films with a TiO2 barrier

Multiferroic thin films with the general formula TiO₂/BiFe_1−xMn_xO₃ (x=0.00, 0.05, 0.10 and 0.15) (TiO₂/BFMO) were synthesized on Au/Ti/SiO₂/Si substrates using a chemical solution deposition (CSD) method assisted with magnetron sputtering. X-ray diffraction analysis shows the thin films contained perovskite structures with random orientations. Compared with BFMO films, the leakage current density of the TiO₂/BFMO thin films was found to be lower by nearly two orders of magnitude, and the remnant polarizations were increased by nearly ten times. The enhanced ferroelectric properties may be attributed to the lower leakage current caused by the introduction of the TiO₂ layer. The J-E characteristics indicated that the main conduction mechanism for the TiO₂/BFMO thin film was trap-free Ohmic conduction over a wide range of electric fields (0-500 kV/cm). In addition, ferromagnetism was observed in the Mn doped BFO thin films at room temperature. The origin of ferromagnetism is related to the competition between distortion of structure and decrease of grain size and decreasing net magnetic moment in films due to Mn doping.     

Effect of Sr concentration on microstructure and magnetic properties of (Ba1−xSrx)(Ti0.3Fe0.7)O3 ceramics

Fe-doped (Ba_1−xSr_x)TiO₃ ceramics were prepared by solid-state reaction, and ferromagnetism was realized at room temperature. The microstructure and magnetism were modified by the Sr concentration control (0≤x≤75 at%) at a fixed Fe concentration, and the relevant magnetic exchange mechanism was discussed. All the samples are shown to have a single perovskite structure. When increasing the Sr concentration, the phase structure is transformed from a hexagonal perovskite into a cubic perovskite, with a monotonic decrease in lattice parameters induced by ionic size effect. The room-temperature ferromagnetism is expected to originate from the super-exchange interactions between Fe³⁺ on pentahedral and octahedral Ti sites mediated by the O²⁻ ions. The increase in Sr addition modifies two main influencing factors in magnetic properties: the ratio of pentahedral to octahedral Fe³⁺ and the concentration of oxygen vacancies, leading to a gradually enhanced saturation magnetization. The highest value, obtained for Fe-doped (Ba_0.25Sr_0.75)TiO₃, is an order of magnitude higher than that of the Fe-doped BaTiO₃ system with similar Fe concentration and preparation conditions, which may indicate (Ba_1−xSr_x)TiO₃ as a more suitable matrix material for multiferroic research.     

Structural, magnetic and electronic transport properties of MnxGe1−x/Ge(0 0 1) films grown by MBE at 350 °C

We report on the structural, magnetic and electronic transport properties of thin Mn_xGe_1−x films grown at 350 °C. Isolated Mn₅Ge₃ nanoclusters, about 100 nm in size, were formed at the top surface of the film, dominating the magnetic properties of the whole film. Electronic transport properties show Mn doping effect indicating the presence of substitutional Mn ions dispersed in the Ge host, contributing to the formation of a Mn_xGe_1−x diluted phase. Electrical behaviour indicates a saturation effect with the raise of the nominal Mn concentration in the film, above x ≅ 0.03.     

Third-order optical nonlinearity of (Ba0.7Sr0.3)TiO3 ferroelectric thin films fabricated by soft solution processing

(Ba_0.7Sr_0.3)TiO₃ (BST) ferroelectric thin films with perovskite crystal structure were fabricated by soft solution processing on a quartz substrate. The third-order nonlinear optical properties were investigated by using Z-scan technique. Positive nonlinear refractive index and nonlinear absorption coefficient were determined to be 4×10⁻⁷ esu and 1.2×10⁻⁶ m/w, respectively. The real part and imaginary part of third-order optical nonlinear susceptibility were calculated and the values were 6.43×10⁻⁸ and 5.14×10⁻⁸ esu, respectively. All of these results show ferroelectric BST thin film is promising for applications in nonlinear optical devices.     

Manganese doping effects on interband electronic transitions,lattice vibrations,and dielectric functions of perovskite-type Ba<Subscript>0.4</Subscript>Sr<Subscript>0.6</Subscript>TiO<Subscript>3</Subscript> ferroelectric ceramics

The Ba_0.4Sr_0.6−x Mn _x TiO₃ (BSMT) ceramics with different Mn composition (from 1% to 10%) have been prepared via the conventional solid-state reaction sintering. The X-ray diffraction analysis shows that the ceramics are polycrystalline with the single perovskite phase. The lattice vibrations and optical properties have been investigated using Raman scattering, spectroscopic ellipsometry (SE), and infrared reflectance spectra. It was found that the optical bandgap for the BSMT ceramics is varied between 3.40 and 3.65 eV. The three first-order Raman-active phonon modes can be observed, and the frequency of the A ₁(LO₃)/E(LO) mode shows a blue shift of 8 cm⁻¹ with the Mn composition, which can be attributed to the distortion of the TiO₆ octahedron. With increasing Mn composition, the frequency of the infrared-active TO₄ mode decreases from 532 to 520 cm⁻¹, owing to the local variation of the lattice constant induced by the Mn incorporation. Moreover, the optical functions of the ceramics from the far-infrared to ultraviolet region are obtained based on the SE and reflectance spectra, which is useful for the potential applications in ferroelectric-based optoelectronic devices.     

Neutron-powder-diffraction study of structural and magnetic structure of La0.7Sr0.3Mn1−xTixO3 (x=0, 0.10, 0.20, and 0.30)

Neutron-diffraction and magnetic measurements have been used in order to study the structure and magnetic changes of La_0.7Sr_0.3Mn_1−xTi_xO₃ (x=0, 0.10, 0.20, and 0.30) perovskites. Magnetic measurements show that our samples exhibit a ferromagnetic–paramagnetic transition with decreasing temperature. Effects of Ti doping on the magnetic and nuclear structures are studied here by neutron-powder-diffraction for La_0.7Sr_0.3Mn_1−xTi_xO₃ (x=0.10, 0.20, and 0.30). Our analysis indicates that the three representative samples, with x=0.10, 0.20, and 0.30, have a hexagonal system of R3¯c space group, and that the magnetic moments order ferromagnetically into the (1 0 1) crystallographic planes, i.e. the magnetic moments of the Mn ion are in the ac plane, with no component along the b-axis. There is no crystalline structure changes when the Ti doping level increases.     

Enhanced spontaneous polarization in Sr and Ca co-doped BaTiO3 ceramics

The dielectric and ferroelectric properties of (Ba_xSr_1−x)_0.77Ca_0.23TiO₃ ceramics with x=1 to 0.7 were studied and compared with those of Ba_xSr_1−xTiO₃ and Ba_0.77Ca_0.23TiO₃ ceramics. It has been found that Sr doping of the Ba_0.77Ca_0.23TiO₃ ceramics causes a drastic decrease of the Curie temperature, just like Sr doping of pure BaTiO₃ ceramics, demonstrating a cell volume effect. However, the (Ba_xSr_1−x)_0.77Ca_0.23TiO₃ ceramics with x=0.9 and 0.8 have larger spontaneous polarization than those of the corresponding Ba_xSr_1−xTiO₃ and Ba_0.77Ca_0.23TiO₃ ceramics, along with sufficient insulating properties. The enhancement of their polarization was explained by the increase of the lattice parameter c/a ratio due to the lattice distortion and strain developed in the ceramics.     

BiFeO3/Zn1−xMnxO bilayered thin films

BiFeO₃/Zn_1−xMn_xO (x = 0-0.08) bilayered thin films were deposited on the SrRuO₃/Pt/TiO₂/SiO₂/Si(1 0 0) substrates by radio frequency sputtering. A highly (1 1 0) orientation was induced for BiFeO₃/Zn_1−xMn_xO. BiFeO₃/Zn_1−xMn_xO thin films demonstrate diode-like and resistive hysteresis behavior. A remanent polarization in the range of 2P_r ∼ 121.0-130.6 μC/cm² was measured for BiFeO₃/Zn_1−xMn_xO. BiFeO₃/Zn_1−xMn_xO (x = 0.04) bilayer exhibits a highest M_s value of ∼15.2 emu/cm³, owing to the presence of the magnetic Zn_0.96Mn_0.04O layer with an enhanced M_s value.     

Growth and magnetism in amorphous Si1−xMnx thin films grown by thermal deposition

Si_1−xMn_x   (x?0.22$x?0.22$) thin films were grown by using a thermal evaporator, and their magnetic and electrical properties were investigated. The Si_1−xMn_x semiconductors are amorphous when Mn concentration is 9.0 at% and less. The electrical resistivities of amorphous Si_1−xMn_x   (x?0.09$x?0.09$) semiconductor thin films are in the range of 9.86–6.59×10⁻⁴ Ω cm at room temperature and decrease with increasing Mn concentration. The amorphous Si_1−xMn_x   (x?0.09$x?0.09$) semiconductor thin films are p-type and hole densities are 3.73×10¹⁸–1.33×10²² cm⁻³ at room temperature. Low temperature magnetization characteristics reveal that amorphous Si_1−xMn_x   (x?0.09$x?0.09$) semiconductor thin films are paramagnetic.     

Low dielectric loss Ba0.6Sr0.4TiO3/MgTiO3 composite thin films prepared by a sol–gel process

The dielectric properties of Ba_0.6Sr_0.4TiO₃ (BST)/MgTiO₃ (MT) composite thin films deposited on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by the sol–gel method were investigated. The X-ray pattern analysis indicates that the thin films exhibit good crystalline quality with perovskite phase and that insertion of MT layer does not obviously affect the phase structure of BST thin films. The characterization of dielectric properties demonstrates that configuration of BST/MT/BST thin films is an effective approach to obtain low dielectric loss and dielectric tunability of BST thin films. At room temperature, the tunability of pure BST60 films and BST/MT (15 nm)/BST composite thin films is 47% and 36%, respectively, at the frequency of 1 MHz with an applied electric field of 400 kV/cm. For BST/MT/BST composite thin films, considerable reduction in the dielectric loss values is observed, which renders them attractive for tunable microwave device applications.     

Ferromagnetism of epitaxially grown CaRu1−xMxO3 (M=Ti, Mn) films

Epitaxial thin films of CaRu_1−xM_xO₃ (M=Ti, Mn) were fabricated on a (0 0 1)-SrTiO₃ substrate by spin-coat method using organometallic solutions (metal alkoxides). Results of X-ray diffraction and transmission electron microscopy indicate that the epitaxial films were grown pseudomorphically so as to align the [0 0 l] axis of the CaRu_1−xM_xO₃ films perpendicular to the (0 0 1) plane of the SrTiO₃ substrate. Ferromagnetism and metal-insulator transition are induced by the substitution of transition metal ions. The occurrence of ferromagnetism was explained qualitatively assuming a TiRu₆ cluster model for CaRu_1−xTi_xO₃ film and a mixed valence model for CaRu_1−xMn_xO₃ film. Ferromagnetism was also observed for layered CaRuO₃/CaMnO₃ film and CaRuO₃/CaMnO₃/CaRuO₃/CaMnO₃ multilayer film and the magnetism was explained by an interfacial exchange interaction model with magnetic Mn³⁺, Mn⁴⁺, and Ru⁵⁺ ions.     

The influence of Co doping on the dielectric, ferroelectric and ferromagnetic properties of Ba0.70Sr0.30TiO3 thin films

Ba_0.70Sr_0.30TiO₃ (BST) thin films doped by Co (BSTC) are fabricated by sol-gel method on a Pt/Ti/SiO₂/Si substrate. A strong correlation is observed among the microstructure, dielectric, ferroelectric, ferromagnetic properties and Co concentration. The dielectric constant of BST thin films can be tailored from 343 to 119 by manipulating the Co concentration. The dielectric loss of BSTC thin films are still kept below 0.020 and the tunability is above 30% at a dc-applied electric field of 500 kV/cm. With increasing Co doping up to 10 mol%, the coexistence of ferromagnetism and ferroelectrics is found. Suitable dielectric constant, low-dielectric loss, and high tunability of this kind of thin films can be useful for potential tunable applications.     

Ferroelectric-relaxor behavior of (Na0.5K0.5)NbO3-based ceramics

We report that ferroelectric-relaxor behavior is induced by doping of SrO and TiO₂, or BaO and TiO₂ into classic ferroelectric (Na_0.5K_0.5)NbO₃. It is found that [(Na_0.5K_0.5)_0.9Sr_0.1](Nb_0.9Ti_0.1)O₃ ceramics exhibit a pronounced ferroelectric-relaxor behavior, comparable to that of [(Na_0.5K_0.5)_0.9Ba_0.1](Nb_0.9Ti_0.1)O₃ ceramics. Our results indicate that the relaxor behavior is closely related to the appearance of micropolar regions in these systems. The relaxor behavior should arise from the dynamic response of micropolar clusters. Raman spectra of [(Na_0.5K_0.5)_1−xSr_x](Nb_1−xTi_x)O₃ ceramics measured in the wavenumber range from 100 to 1200 cm⁻¹ confirm that the first order scattering is dominant in phonon bands should result from both short-range ordered region (micropolar regions) and disordered matrix. The frequency dependence of dielectric permittivity measurements show that the relaxor behavior of SrO and TiO₂, or BaO and TiO₂ doped (Na_0.5K_0.5)NbO₃ ceramics is not a Debye type in the radio frequency range.     

The important role of Mn in the room-temperature ferromagnetism of Mn-doped GaN films

Mn-doped GaN films (Ga_1−xMn_xN) were grown on sapphire (0 0 0 1) using Laser assisted Molecular Beam Epitaxy (LMBE). High-quality nanocrystalline Ga_1−xMn_xN films with different Mn concentration were then obtained by thermal annealing treatment for 30 min in the ammonia atmosphere. Mn ions were incorporated into the wurtzite structure of the host lattice by substituting the Ga sites with Mn³⁺ due to the thermal treatment. Mn³⁺, which is confirmed by XPS analysis, is believed to be the decisive factor in the origin of room-temperature ferromagnetism. The better room-temperature ferromagnetism is given with the higher Mn³⁺ concentration. The bound magnetic polarons (BMP) theory can be used to prove our room-temperature ferromagnetic properties. The film with the maximum concentration of Mn³⁺ presents strongest ferromagnetic signal at annealing temperature 950 °C. Higher annealing temperature (such as 1150 °C) is not proper because of the second phase Mn_xGa_y formation.     

Structural and magnetic properties in the self-doped perovskite manganites with nominal composition La0.7Sr0.3−xMnO3−δ

Perovskite manganites with nominal composition La_0.7Sr_0.3−xMnO_3−δ (0.00≤x≤0.20) have been prepared by the sol-gel method with the highest heat treatment temperature being 1073 K. The XRD patterns indicate that when the doping level is x≤0.10 the samples have only a single phase, with the R3?c perovskite structure, while for x>0.10, the samples have two phases with the R3?c perovskite being the dominant phase and Mn₃O₄ being the second phase. A quantitative analysis and Rietveld fitting of the X-ray powder diffraction data indicate that on the basis of the thermal equilibrium theory of crystal defects there are Mn²⁺ ions at the A sites and Mn³⁺ plus Mn⁴⁺ ions at the B sites in the ABO₃ perovskite phase. The curves of magnetization versus applied magnetic field at 10 K showed that the magnetic moments of the Mn²⁺ ions at the A sites are antiparallel to those of the Mn³⁺ and Mn⁴⁺ ions at the B sites.