Lattice distortion and room-temperature ferroelectric properties of (Sm, Cr) co-doped BiFeO3 thin films

Pure BiFeO₃ (BFO) and Bi_0.85Sm_0.15Fe_0.97Cr_0.03O₃ (BSFCO) thin films were prepared on FTO/glass (SnO₂: F) substrates by using a chemical solution deposition method. The effects of (Sm, Cr) co-doping on the microstructure and ferroelectric properties of the BSFCO thin films were studied. The X-ray diffraction and Raman scattering spectra proved that the co-doped BSFCO thin film has a lattice distortion compared with the pure BFO thin film. The remnant polarization (2P _r) of the BSFCO thin film was 153.67 μC/cm² at 1 kHz in the applied electric field of 1,270 kV/cm. At an applied electric field of 100 kV/cm, the leakage current density of the co-doped BSFCO thin film (2.12 × 10^?6 A/cm²) was 3 orders lower than that of the pure BFO thin film (3.8 × 10^?3 A/cm²). The improved properties of the co-doped thin film could be attributed to lattices distortion, more grain boundaries, higher binding energy of Sm–O and the mixed-valence states of Cr³⁺ and Cr ⁶⁺.     

Structure,conduction mechanisms and multiferroic properties of (Sm,Cr) co-doped Bi0.89Sm0.11Fe0.97Cr0.03O3–NiFe2O4 composition thin films

(Sm, Cr) co-doped Bi_0.89Sm_0.11Fe_0.97 Cr_0.03O₃ (BSFC)–NiFe₂O₄ (NFO) composition thin films were successfully prepared on FTO/glass (SnO₂:F) substrates via a sol–gel method. The structure, surface morphology, leakage current, ferroelectricity and ferromagnetism of BSFC–NFO composition thin film have been investigated. X-ray diffraction analysis indicates that the thin film is polycrystalline and consisted of a rhombohedral perovskite (R3m space group) BiFeO₃ phase and a cubic (Fd-3m space group) inverse spinel NiFe₂O₄ phase. The BSFC–NFO composition thin film is promising in practical application because of its well saturated ferromagnetic (Ms = 19.45 emu/cm³) and ferroelectric (Pr = 39 µC/cm²) hysteresis loops with low order of leakage current density (J = 6.73 × 10^?6 A/cm², at an applied electric field of 100 kV/cm). Which suggest the ferroelectric and ferromagnetic properties can be improved by this composition thin film structure. Moreover, the various conduction mechanisms of BSFC–NFO composition thin film have also been studied.     

Enhanced multiferroic and dielectric properties of Sr2+-doped BiFe0.94(Mn0.04Cr0.02)O3 thin films

Sr²⁺-doped B_1?xSr_xFe_0.94(Mn_0.04Cr_0.02)O₃ (B_1?xSr_xFMC, x = 0.00, 0.05 and 0.09) thin films were prepared on FTO/glass (SnO₂: F) substrates by using a sol–gel spin-coating method. X-ray diffraction (XRD), Rietveld refined XRD data and Raman scattering spectra illustrate a structural evolution from trigonal (R3c: H) to tetragonal (P4) occurs in B_1?xSr_xFMC thin films with the increase of Sr²⁺ concent. Superiorly multiferroic and dielectric properties were obtained in the B_1?xSr_xFMC thin films, e.g., large remanent polarization value, a high dielectric constant (P _r = 139.21 μC/cm² and ε_r = 396.7 for x = 0.09) and large saturation magnetization (M _s = 2.08 emu/cm³ for x = 0.05). The leakage current density of B_1?xSr_xFMC thin films is increased with increasing Sr²⁺ concentration, wherein the leakage current density of all the B_1?xSr_xFMC films is of the order of magnitude of 10^?5 A/cm², which are still lower than that in the pure BFO film (10^?3 A/cm²).     

Ce-doped bismuth ferrite thin films with improved electrical and functional properties

Bi_1?xCe_xFeO₃ (BCFO) thin film capacitors (x = 0 to 0.2) are fabricated on indium tin oxide coated corning glass substrate by chemical solution deposition method. X-ray diffraction results show a partial phase transition from rhombohedral to tetragonal structure induced in BCFO thin film having preferred (110) orientation with increase in Ce dopant concentration. Current density–field (J–E) characteristics indicate that the leakage current density reduces by several orders of magnitude in Ce-doped BFO thin films resulting from smaller grain sizes and smoother surfaces. Space-charge-limited current and Fowler–Nordheim tunneling are identified as dominating leakage behavior in BCFO thin film capacitors at moderate and high field regions, respectively. Enhanced ferroelectric response with well-saturated (P–E) hysteresis loop is observed for Bi_0.88Ce_0.12FeO₃ thin film having high remnant polarization (P _r—127 µC/cm²) at an applied field of 1080 kV/cm. Bi_0.88Ce_0.12FeO₃ thin film exhibiting well-defined capacitance–field (C–E) butterfly loop with dielectric loss (tan δ—0.03) measured at 10 kHz suggested good ferroelectric properties with high tunability of about 88 %.     

Structural,optical and magnetic properties of Cr doped In<Subscript>2</Subscript>O<Subscript>3</Subscript> powders and thin films

The (In_1?xCr_x)₂O₃ powders as well as thin films of x = 0.03, 0.05 and 0.07 were synthesized using a solid state reaction and an electron beam evaporation technique (on glass substrate), respectively. The influence of Cr doping concentration on structural, optical and magnetic properties of the In₂O₃ samples was systematically studied. The X-ray diffraction results confirmed that all the Cr doped In₂O₃ samples exist cubic structure of In₂O₃ without any secondary phases presence. The chemical composition analyses showed that all the Cr doped In₂O₃ compounds were nearly stoichiometric. The X-ray photoelectron spectroscopy analysis of the Cr doped In₂O₃ thin films showed an increase of oxygen vacancies with Cr concentration and the existence of Cr as Cr³⁺ state in the host In₂O₃ lattice. A small blue shift in the optical band gap was observed in the powder compounds, when the dopant concentration increased from x = 0.03 to x = 0.07. In thin films, the band gap found to increase from 3.63 to 3.74 eV, with an increase of Cr concentration. The magnetic measurements show that the undoped In₂O₃ bulk powder sample has the diamagnetic property at room temperature. And a trace of paramagnetism was observed in Cr doped In₂O₃ powders. However (In_1?xCr_x)₂O₃ thin films (x = 0.00, 0.03, 0.05 and 0.07) samples shows soft ferromagnetism. The observed ferromagnetism in thin films are attributed to oxygen vacancies created during film prepared in vacuum conditions. The ferromagnetic exchange interactions are established between metal cations via free electrons trapped in oxygen vacancies (F-centers).     

Structure transition and enhanced ferroelectric properties of (Mn, Cr) co-doped BiFeO3 thin films

Pure BiFeO₃ (BFO) and (Mn, Cr) co-doped BiFe_0.96?yMn_0.04Cr_yO₃ thin films were prepared on FTO/glass (SnO₂:F) substrates by using a sol–gel method. The effects of (Mn, Cr) co-doped on the microstructure and electric properties of the BiFeO₃ thin films were studied. The result indicates that the co-doped BiFe_0.94Mn_0.04Cr_0.02O₃ (BFMCO) thin film has a structure transition and better ferroelectric properties compared with the pure BFO thin film. The Rietveld refined XRD patterns of BFO and BFMCO thin films conform the trigonal (R3c:H) and the biphasic (R3c:H + R3m:R) structure, respectively. The co-existence of two phases and the mixed valences of Cr^3+/6+ and Mn^2+/3+, which apparently improves the electric properties of the (Mn, Cr) co-doped BFMCO thin films. The remnant polarization (P _r) of the BFMCO thin film was 93.58 μC/cm² at 1 kHz in the applied electric field of 636 kV/cm. At an applied electric field of 100 kV/cm, the leakage current density of (Mn, Cr) co-doped BFMCO thin film is 6.2 × 10^?6 A/cm². It is about three orders much lower than that of the BFO thin film (1.43 × 10^?3 A/cm²).     

Fabrication and characterization of compositionally graded Bi1−x Gd x FeO3 thin films

An undoped BiFeO₃ thin film, Gd doped Bi_0.95Gd_0.05FeO₃ thin film with a constant composition, Gd up-graded doped Bi_1?x Gd _x FeO₃ and Gd down-graded doped Bi_1?x Gd _x FeO₃ thin films were successfully grown on Pt (111)/Ti/SiO₂/Si (100) substrates using a sol-gel and spin coating technique. The crystal structure, ferroelectric and dielectric characteristics as well as the leakage currents of these samples were thoroughly investigated. The XRD (X-Ray Diffraction) patterns indicate that all these thin films consist of solely perovskite phase with polycrystalline structure. No other secondary phases have been detected. Clear polarization-electric field (P-E) hysteresis loops of all these thin films demonstrate that the incorporation of Gd³⁺ into the Bi site of BFO thin film have enhanced the ferroelectric performance of pure BiFeO₃ thin film, and the Gd down-graded doped Bi_1?x Gd _x FeO₃ thin film has the best ferroelectric properties. Compared to other thin films, the optimal ferroelectric behavior of the Gd down-graded doped Bi_1?x Gd _x FeO₃ thin film results from its large dielectric constant, low dissipation factor and low leakage current.     

Study on Mn-induced Jahn–Teller distortion in BiFeO3 thin films

Present work reports Raman spectroscopy study of single-phase Mn-doped BiFeO₃ [BiFe_1?x Mn _x O₃ (0 ≤ x ≤ 0.20)] polycrystalline thin films carried out in backscattering geometry. De-convolution of Raman spectra showed a gradual transition in the crystal symmetry from rhombohedral (?R) to multiphase [rhombohedral (?R) + tetragonal (?T)] structure with increasing Mn doping concentration in BiFe_1?x Mn _x O₃ (BFMO) thin films. X-ray diffraction (XRD) along with Le-Bail extraction refinement confirms that the structural symmetry lowering in BFMO thin films occurs at about 10 % Mn doping concentration. A blue shift is observed in the direct energy band gap of BFMO thin films from 2.53 to 2.87 eV (at T = 295 K) and is attributed to the local symmetry lowering and local induced strain in Fe³⁺ environment resulted from Jahn–Teller distortion in (MnFe)³⁺O₆ octahedral unit. Second-derivative analysis of FTIR spectra in the spectral regions (420–470) cm^?1 and (480–680) cm^?1 further indicates the favourable structure distortion leading to the simultaneous exhibition of enhanced ferromagnetic and ferroelectric properties owing to Mn substitution in host BiFeO₃ lattice.     

Enhanced dielectric and tunable properties of barium strontium titanate thin films through introducing Nd(Zn1/2Ti1/2)O3 and adjusting Ba/Sr

Ba_0.6Sr_0.4TiO₃ (BST) and 0.06Nd(Zn_1/2Ti_1/2)O₃–0.94Ba _x Sr_1?x TiO₃ (NZT–BST) thin films with x = 0.6, 0.7, 0.75, and 0.8 were fabricated on Pt/Ti/SiO₂/Si substrates by sol–gel method. The structures, surface morphology, dielectric, and ferroelectric properties, and thermal stability of BST and NZT–BST thin films were investigated as a function of NZT and Ba content. It was found that introducing NZT into BST decreased significantly dielectric loss, however, along with the tunability. On this basis, increasing Ba/Sr in NZT–BST thin films led to the simultaneous increase of dielectric constant and tunability of thin films. As a result, optimized dielectric and tunable properties were obtained for 0.06Nd(Zn_1/2Ti_1/2)O₃–0.94Ba_0.7Sr_0.3TiO₃ thin film with the highest FOM value of 43.22. It awakens us that, for reducing dielectric loss, introducing a certain amount of low permittivity oxides or non-ferroelectrics like NZT into weak ferroelectric perovskite tunable materials, not into paraelectric perovskite tunable materials, may obtain more excellent dielectric and tunable performances.     

Dielectric enhancement of the trilayered Bi3.15Eu0.85Ti3O12/Bi3.15Nd0.85Ti3O12/Bi3.15Eu0.85Ti3O12 thin film deposited on Pt/Ti/SiO2/Si substrate

The trilayered Bi_3.15Eu_0.85Ti₃O₁₂/Bi_3.15Nd_0.85Ti₃O₁₂/Bi_3.15Eu_0.85Ti₃O₁₂ (BET/BNT/BET) thin film was deposited on Pt/Ti/SiO₂/Si(100) substrates by metal organic decomposition at annealing temperature of 650 °C, and the microstructure, chemical composition, leakage current, dielectric and ferroelectric properties were investigated by field emission scanning electron microscopy, X-ray diffraction, energy dispersive X-ray spectroscopy, semiconductor characterization system, impedance analyzer and ferroelectric tester. The trilayered thin film is of crack-free and dense surface with some discrete cluster distribution, and typical Bi-layered perovskite polycrystalline phase. The dielectric constant ε _r and dissipation factor tanδ are 1,233 and 0.0215 at 100 kHz for the trilayered thin film. Comparing with the pure BET and BNT thin films, the dielectric constant of trilayered thin film is enhanced, which is due to the space charge and the intermediate superlattice. The trilayered thin film shows excellent dielectric properties and can be promisingly used for the high dielectric layer of silicon-based embedded capacitors in package substrate.     

Effects of niobium content on electrical and mechanical properties of (Na0.85K0.15)0.5Bi0.5Ti(1-x)Nb x O3 thin films

(Na_0.85K_0.15)_0.5Bi_0.5Ti_(1-x)Nb _x O₃ (NKBT-N100x) thin films were deposited on Pt/Ti/SiO₂/Si(100) substrates by metal–organic decomposition method and annealed in oxygen atmosphere at 750 °C. The effects of niobium concentration on the microstructures, ferroelectric, piezoelectric, leakage current and mechanical properties of the NKBT-N100x (x = 0, 0.01, 0.03, 0.05) thin films have been investigated in detail. The NKBT-3N thin film has the largest remnant polarization (7 μC/cm²) and statistically averaged d _33eff (140 pm/V), the smallest leakage current, elasticity modulus (102.0 Gpa), hardness (5.1 Gpa) and residual stress (297.0 Mpa). The evaluation of residual stresses of these thin films will offer useful guidelines of safe working condition for their potential application in microelectromechanical system.     

Preparation and properties of ferroelectric Pb1 − xCaxTiO3 thin films produced by the polymeric precursor method

Pb_{1 – x} Ca _x TiO₃ thin films with x = 0.24 composition were prepared by the polymeric precursor method on Pt/Ti/SiO₂/Si substrates. The surface morphology and crystal structure, and the ferroelectric and dielectric properties of the films were investigated. X-ray diffraction patterns of the films revealed their polycrystalline nature. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) analyses showed the surface of these thin films to be smooth, dense and crack-free with low surface roughness. The multilayer Pb_{1 – x} Ca _x TO₃ thin films were granular in structure with a grain size of approximately 60–70 nm. The dielectric constant and dissipation factor were, respectively, 174 and 0.04 at a 1 kHz frequency. The 600-nm thick film showed a current density leakage in the order of 10^–7 A/cm² in an electric field of about 51 kV/cm. The C-V characteristics of perovskite thin films showed normal ferroelectric behavior. The remanent polarization and coercive field for the deposited films were 15 C/cm² and 150 kV/cm, respectively.     

Relaxor behaviour and dielectric properties of BiFeO3 doped Ba(Zr0·1Ti0·9)O3 ceramics

Ba_1???x Bi _x (Ti_0·9Zr_0·1)_1???x Fe _x O₃ ( x = 0–0·075) ceramics are prepared using a conventional solid state reaction method. X-ray diffraction shows the presence of a single phase. Addition of Bi^3?+? and Fe^3?+? strongly influences the crystal structure and dielectric properties of the ceramics. The evolution from a normal ferroelectric to a relaxor ferroelectric is emphasized. Ba_0·99Bi_0·01(Ti_0·9Zr_0·1)_0·99Fe_0·01O₃ ceramic shows a relaxor behaviour at room temperature with Δ T _m =12 K. P– E hysteresis loop of the composition, x = 0·007, shows a remanent polarization ( P _r ) of 0·5 μC/cm² with a coercive field ( E _C ) of 2 kV/cm. Raman spectra of all compounds are performed and correlated well with the X-ray diffraction and dielectric measurement results.     

Bi2MoO6 dielectric thin films fabricated by thermal oxidation of Bi/Mo thin films at ultra-low temperature

Bi/Mo multilayer thin films are deposited on Si/SiO₂/Pt substrates by direct current magnetron sputtering. The effect of annealing temperature on the microstructure, dielectric and electrical properties of the as-sputtered films is characterized systematically. X-ray diffraction data indicate that the films annealed at 450–600 °C are a mixture of diphase with the main phase Bi₂MoO₆ and secondary phase Bi₂Mo₂O₉. Results of scanning electron microscope observation show that the films annealed at 500–550 °C are dense and uniform, in particular the films annealed at 500 °C exhibit optimal dielectric and electrical properties with dielectric constant as high as 37.5, dielectric loss 1.06 %, temperature coefficient of dielectric constant ?10.86 ppm °C^?1 at 1 kHz, and leakage current density of 1.46 × 10^?7 A mm^?2 at an electric field of 18.2 kV mm^?1. With the advantages of ultralow densification temperature (500 °C) and very high sputtering deposition rate (76 nm min^?1), it is anticipated that thermal oxidation method of the sputtered Bi/Mo thin films could be a promising technique for fabrication of Bi₂MoO₆ ceramic thin film embedded-capacitors.     

Ferroelectric and piezoelectric behavior of (111)-oriented Pb(ZrxTi1−x)O3 thin films on cobalt ferrite nano-seed layered Pt(111)/Si substrate

Perfect (111)-oriented Pb(Zr_xTi_1?x)O₃ (PZT) thin films were grown on cobalt ferrite buffered Pt(111)/Ti/SiO₂/Si substrate by pulsed laser deposition method using various targets with different Zr/Ti ratios ranging from 30/70 to 70/30. The results of X-ray diffraction analyses indicated that the composition of morphotropic phase boundary in the present PZT films is same as the bulk PZT (Zr/Ti = 52/48). The effect of Zr/Ti ratio of the PZT films was investigated by the ferroelectric domain structure and the piezoelectric characteristics of the films by piezoresponse force microscopy, as well as polarization measurement. The results revealed that the present tetragonal PZT film has a higher ferroelectric domain switching than rhombohedral one and the film with composition of Zr/Ti = 52/48 showed relatively high value of squareness of P–E loop and E_c as well as high piezoresponse.     

Ferroelectric and dielectric properties of Bi4-xNdxTi3O12 thin films prepared by sol–gel method

Bi_4-xNd_xTi₃O₁₂ (BNT-x, x = 0, 0.25, 0.50, 0.75 and 1.0) thin films were prepared on Pt/Ti/SiO₂/Si substrates by a sol–gel method. The microstructure, ferroelectric and dielectric properties of BNT-x thin films were investigated. The single-phase BNT-x thin films were obtained. With increasing Nd content, the preferred orientation changed from random to (117) and surface morphologies changed from the mixture of rod- and plate-like grains to rod-like grains. The Nd substitution improved the ferroelectric and dielectric properties of BTO films. BNT-x films showed better electrical properties at x = 0.50—1.0. BNT-0.75 film exhibited the best electrical properties with remanent polarization (2P _r) of 26.6 μC/cm², dielectric constant (ε _r) of 366 (at 1 MHz), dielectric loss (tanδ) of 0.034 (at 1 MHz), leakage current density (J) of ±3.0 × 10⁻⁶ A/cm² (at ± 5 V) and fatigue-free characteristics.     

Reduced leakage current and enhanced ferroelectric properties in Mn-doped Bi0.5Na0.5TiO3-based thin films

Bi_0.5(Na_0.76K_0.2Li_0.04)_0.5TiO₃ thin films were deposited on SrRuO₃-coated (001)-SrTiO₃ substrates by pulsed laser deposition. The effects of oxygen pressure and Mn doping on the leakage current and ferroelectric and dielectric properties were investigated. The remnant polarization and dielectric constant (at 10 kHz) of Mn-doped film deposited at 400 mtorr were measured to be 23 μC cm^?2 and 660, respectively. The leakage current density of Mn-doped films was suppressed by more than two orders of magnitude and the polarization was considerably enhanced. The XPS results showed coexistence of Mn²⁺, Mn³⁺, and Mn⁴⁺ in doped films. Oxidation of Mn²⁺ to higher valence states by absorbing holes along with occupation of A-site vacancies was suggested as the possible reason for a reduced leakage current and dielectric loss in Mn-doped films.     

Electrical properties of thin Ba<Subscript>x</Subscript>Sr<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>TiO<Subscript>3</Subscript> films on silicon dioxide substrates

We have studied the electrical properties of thin ferroelectric films of barium strontium titanate (Ba_xSr_1−x TiO₃) obtained on fused quartz (SiO₂) substrates by RF magnetron sputtering. Dependences of the tuning coefficient and dielectric loss tangent on the synthesis temperature and the film thickness are reported. The results are compared to analogous data for films grown on polycrystalline alumina substrates.     

Structural and electrical studies on Bi2VO5.5/Bi4Ti3O12 multilayer thin films

The textured multilayer (ML) thin films of bismuth layered ferroelectric (FE) compounds, Bi₂VO_5.5 (BVO) and Bi₄Ti₃O₁₂ (BTO) with different individual layer thicknesses were fabricated via pulsed laser deposition technique on Pt(111)/TiO₂/SiO₂/Si substrates. X-ray diffraction studies confirmed that BVO and BTO retained their respective crystal structures in these multilayer (ML) thin films. The atomic force microscopy and scanning electron microscopy studies showed smooth and dense microstructures. The polarization hysteresis (P?CE) studies on a representative (BVBT30) ML thin film at 300 K confirmed the remnant polarization (2P _r ) and coercive field (E _c ) to be ~20 ??C/cm² and 250 kV/cm, respectively. The value of P _r obtained was greater than that of the single layer thin film of BVO (P _r  ~ 5.6 ??C/cm²). The room temperature dielectric constant (??_r??) and the loss (D) for BVBT30 ML measured at 100 kHz were 170 and 0.01, respectively. The frequency and temperature dependent dielectric constant, impedance, modulus and ac conductivity of these ML thin films were studied as a function of frequency (100 Hz?C1 MHz) in the 25?C300 °C temperature range. Two distinct electrical responses were observed in these films, which were attributed to the grain effects at low temperatures and grain boundary effects at higher temperatures. The frequency dependent electrical conductivity was fitted well with the double power law which evidenced two different types of contributions to the conductivity; the low frequency conductivity being due to the short range translational hopping and the high frequency conductivity was due to the localized or reorientational hopping.     

Effects of annealing ambient on ferroelectric properties and surface chemistry of sol–gel derived Bi3.25La0.75Ti3O12 thin films

In this work, Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films were prepared by sol–gel coatings followed by rapid thermal annealing in Ar or O₂ ambient. The correlation among annealing ambient, ferroelectric characteristics and surface chemistry of the BLT thin films were investigated. The BLT thin film annealed in Ar showed weaker crystallization, less dense surface and smaller polarization value than that annealed in O₂. After 10⁹ cycles, the remnant polarization of the BLT film annealed in Ar decreased to 83.5 % of the initial value while it remained 89.5 % for the sample annealed in O₂. X-ray photoelectron spectroscopy results indicated the inferior fatigue characteristics of the sample annealed in Ar was the comprehensive result of oxygen vacancies vicinity to Bi and Ti ion in the thin film.