Effects of co-substitution on the electrical properties of BiFeO3 thin films prepared by chemical solution deposition

Ferroelectric BiFeO₃ thin films with Nd-Cr (or Sm-Cr) co-substitution (denoted by BNdFCr and BSmFCr, respectively) were deposited on the Pt(2 0 0)/TiO₂/SiO₂/Si(1 0 0) substrates by a chemical solution deposition method. X-ray diffraction patterns revealed the formation of BNdFCr and BSmFCr thin films without any secondary phases. The co-substituted BNdFCr (or BSmFCr) thin films, which were annealed at 550 °C for 30 min in N₂ atmosphere, exhibited enhanced electrical properties compared to BFO thin films with the remanent polarization (2P_r) and coercive electric field (2E_c) of 196, 188 μC/cm² and 600, 570 kV/cm with the electric field of 800 kV/cm, respectively. The leakage current densities of BNdFCr and BSmFCr thin films measured at room temperature were approximately three orders of magnitude lower than that of BFO thin film, and the leakage current at room temperature of the thin films exhibited three distinctive conduction behaviors. Furthermore, the values of pulse polarizations [i.e., +(P*-P^{^}) or −(P*-P^{^})] of BNdFCr and BSmFCr thin films were reasonably unchanged up to 1.4 × 10¹⁰ switching cycles.     

Surface chemical states of barium zirconate titanate thin films prepared by chemical solution deposition

Ba(Zr_0.05Ti_0.95)O₃ (BZT) thin films grown on Pt/Ti/SiO₂/Si(1 0 0) substrates were prepared by chemical solution deposition. The structural and surface morphology of BZT thin films has been studied by X-ray diffraction (XRD) and scanning electron microscope (SEM). The results showed that the random oriented BZT thin film grown on Pt/Ti/SiO₂/Si(1 0 0) substrate with a perovskite phase. The SEM surface image showed that the BZT thin film was crack-free. And the average grain size and thickness of the BZT film are 35 and 400 nm, respectively. Furthermore, the chemical states and chemical composition of the films were determined by X-ray photoelectron spectroscopy (XPS) near the surface. The XPS results show that Ba, Ti, and Zr exist mainly in the forms of BZT perovskite structure.     

Pb(Zr0.53Ti0.47)O3 thin films with different thicknesses obtained at low temperature by microwave irradiation

Pb(Zr_0.53Ti_0.47)O₃ (PZT) thin films with different thicknesses (99-420 nm) were prepared on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by sol-gel method and films were annealed at 450 °C for 30 min using a single-mode cavity of 2.45 GHz microwaves. X-ray diffraction analysis indicated that the pyrochlore phase was transformed to the perovskite phase at above 166 nm films. The grain sizes were increased, surface roughnesses were decreased, and electrical properties were improved with film thickness. The leakage current density was 9 × 10⁻⁸ A/cm² at an applied electrical field of 100 kV/cm. The ohmic and field-enhanced Schottky emission mechanisms were used to explain leakage current behavior of the PZT thin films. These results suggest that microwave annealing is effective for obtaining low temperature crystallization of thin films with better properties.     

Photoluminescence in amorphous (PbLa)TiO3 thin films deposited on different substrates

Pb_1−XLa_XTiO₃ thin films, (X=0.0; 13 and 0.27 mol%) were prepared by the polymeric precursor method. Thin films were deposited on Pt/Ti/SiO₂/Si (1 1 1), Si (1 0 0) and glass substrates by spin coating, and annealed in the 200-300°C range in an O₂ atmosphere. X-ray diffraction, scanning electron microscopy and atomic force microscopy were used for the microstructural characterization of the thin films. Photoluminescence (PL) at room temperature has been observed in thin films of (PbLa)TiO₃. The films deposited on Pt/Ti/SiO₂/Si substrates present PL intensity greater than those deposited on glass and silicon substrates. The intensity of PL in these thin films was found to be dependent on the thermal treatment and lanthanum molar concentration.     

Improvement of fatigue resistance on La modified BiFeO3 thin films

The effect of lanthanum (La) addition in BiFeO₃ (BFO) thin films deposited on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates prepared by soft chemical method was explained. Increasing La concentration promotes changes on structure, microstructure and dielectric/ferroelectric response of films. X-ray diffraction reveals that the films are free of preferred orientations and structural distortion. La addition promotes an increase in dielectric permittivity. The polarization switching and the fatigue behavior of the BFO films were significantly enhanced by the La concentration.     

Fabrication and characterization of Pt intermediate transparent and conducting ITO/Pt/ITO multilayer films

Platinum intermediate transparent and conducting ITO/metal/ITO (IMI) multilayered films were deposited by RF and DC magnetron sputtering on polycarbonate substrates without intentional substrate heating. Changes in the microstructure and optoelectrical properties of the films were investigated with respect to the thickness of the intermediate Pt layer in the IMI films. The thickness of Pt film was varied from 5 to 20 nm.In XRD measurements, neither ITO single-layer films nor IMI multilayer films showed any characteristic diffraction peaks for In₂O₃ or SnO₂. Only a weak diffraction peak for Pt (1 1 1) was obtained in the XRD spectra. Thus, it can be concluded that the Pt-intermediated films in the IMI films did not affect the crystallinity of the ITO films. However, equivalent resistivity was dependent on the presence and thickness of the Pt-intermediated layer. It decreased as low as 3.3×10⁻⁴ Ω cm for ITO 50 nm/Pt 20 nm/ITO 30 nm films. Optical transmittance was also strongly influenced by the Pt-intermediated layer. As Pt thickness in the IMI films increased, optical transmittance decreased to as low as 30% for ITO 50 nm/Pt 20 nm/ITO 30 nm films.     

Thickness dependent magnetic and ferroelectric properties of LaNiO3 buffered BiFeO3 thin films

BiFeO₃ (BFO) thin films with thickness increasing from 40 to 480 nm were successfully grown on LaNiO₃ (LNO) buffered Pt/Ti/SiO₂/Si(100) substrate and the effects of thickness evolution on magnetic and ferroelectric properties are investigated. The LNO buffer layer promotes the growth and crystallization of BFO thin films. Highly (100) orientation is induced for all BFO films regardless of the film thickness together with the dense microstructure. All BFO films exhibited weak ferromagnetic response at room temperature and saturation magnetization is found to decrease with increase in film thickness. Well saturated ferroelectric hysteresis loops were obtained for thicker films; however, the leakage current dominated the ferroelectric properties in thinner films. The leakage current density decreased by three orders of magnitude for 335 nm film compared to 40 nm film, giving rise to enhanced ferroelectric properties for thicker films. The mechanisms for the evolution of ferromagnetic and ferroelectric characteristics are discussed.     

Annealing effects on the structural and electrical transport properties of n-type Bi2Te2.7Se0.3 thin films deposited by flash evaporation

N-type Bi₂Te_2.7Se_0.3 thermoelectric thin films with thickness 800 nm have been deposited on glass substrates by flash evaporation method at 473 K. Annealing effects on the thermoelectric properties of Bi₂Te_2.7Se_0.3 thin films were examined in the temperature range 373-573 K. The structures, morphology and chemical composition of the thin films were characterized by X-ray diffraction, field emission scanning electron microscope and energy dispersive X-ray spectroscopy, respectively. Thermoelectric properties of the thin films have been evaluated by measurements of the electrical resistivity and Seebeck coefficient at 300 K. The Hall coefficients were measured at room temperature by the Van der Pauw method. The carrier concentration and mobility were calculated from the Hall coefficient. The films thickness of the annealed samples was measured by ellipsometer. When annealed at 473 K, the electrical resistivity and Seebeck coefficient are 2.7 mΩ cm and −180 μV/K, respectively. The maximum of thermoelectric power factor is enhanced to 12 μW/cm K².     

Effect of Sc substitution on the structure,electrical, and magnetic properties of multiferroic BiFeO3 thin films grown by a sol–gel process

Multiferroic BiFeO₃ (BFO), Bi_1−xSc_xFeO₃ (BSF), and BiFe_1−xSc_xO₃ (BFS) (x=0.3 mol%) thin films are prepared on Pt/Ti/SiO₂/Si substrates using a sol–gel technique. The effect of Sc substitution along with the annealing ambient (N₂ and O₂) on the structure, electrical, and magnetic properties of the films are reported. X-ray diffraction (XRD) analysis reveals that the films can be prepared with the single-phase perovskite structure by annealing at 700 °C for 10 min either in O₂ or N₂ ambient. The unit cell volume increases on the substitution of Sc, which are 61.39, 62.50, and 62.57 (Å)³ for BFO, BSF, and BFS, respectively. X-ray photoelectron spectroscopy (XPS) study reveals that the chemical environments of Bi and Fe are different in BFO, BSF, BFS films. Similarly, XPS spectra for Sc2p lines in BSF and BFS also have different peak positions; this indicates Sc doping has certain chemical impact on BSF and BFS films. Systematic studies of Sc substitution along with the effect of annealing ambient on the dielectric constant (ε) and dielectric loss (tan δ), leakage current, remnant polarization (P_r), coercive field (E_c), and magnetic properties of the films are carried out. The room temperature values of ε and tan δ at 1 kHz for BFO and BFS films annealed in N₂ ambient are (∼208; 0.035) and (∼235; 0.023), respectively. The comparative value of leakage current for the BFO and BFS films at an applied field strength of 50 kV/cm are 2.997×10⁻⁴ and 1.87×10⁻⁵ A/cm², respectively. Room temperature value of coercive magnetization for BFS films has one order small compared to that of the BFO films; this indicates BFS films are magnetically soft and more suitable for potential device applications. Finally, among the studied compositions, the BFS films annealed in N₂ ambient show the best property.     

Multilayer Bi1.5Zn1.0Nb1.5O7/Ba0.6Sr0.4TiO3/Bi1.5Zn1.0Nb1.5O7 thin films for tunable microwave applications

Bi_1.5Zn_1.0Nb_1.5O₇/Ba_0.6Sr_0.4TiO₃/Bi_1.5Zn_1.0Nb_1.5O₇ tunable multilayer thin film has been fabricated by pulsed laser ablation and characterized. Phase composition and microstructure of multilayer films were characterized by X-ray diffraction, scanning electron microscopy (SEM) and atomic force microscopy (AFM). The film has very smooth surface with RMS roughness of 1.5-2 nm and grain size of 100-150 nm. Total film thickness has been measure to be 375 nm. The BZN thin films at 300 K, on Pt(1 1 1)/SiO₂/Si substrate showed zero-field dielectric constant of 105 and dielectric loss tangent of 0.002 at frequency of 0.1 MHz. Thin films annealed at 700 °C shows the dielectric tunability of 18% with biasing field 500 kV/cm at 0.1 MHz. The multilayer thin film shows nonferroelectric behavior at room temperature. The good physical and electrical properties of multilayer thin films make them promising candidate for tunable microwave device applications.     

Correlation between local hysteresis and crystallite orientation in PZT thin films deposited on Si and MgO substrates

(0 0 1)-Oriented tetragonal ferroelectric PbZr_0.53Ti_0.47O₃ (PZT) thin films (90 nm of thickness) have been grown on TiO_x/Pt/TiO₂/SiO₂/Si and TiO_x/Pt/MgO substrates. The existence of (1 0 0)-oriented crystallites in the c-axis matrix of the (0 0 1)-oriented films has been evidenced by using four circles X-ray diffraction. Depending on the substrate, the ratio of the lattice parameters c/a was found to be 1.02 (Si) and 1.07 (MgO) and this was correlated with the coercive field values. Local piezoelectric hysteresis loops produced by atomic force microscopy have been taken with profit to characterize the switching properties of the ferroelectric domains at the scale of individual crystallites. In each case, (1 0 0)-oriented crystallites require much higher voltage than (0 0 1)-oriented crystallites for switching. These results are explained by taking into account the strain imposed by the substrate in the film. We conclude that piezoelectric hysteresis loops produced by atomic force microscopy provide very rich information for addressing the local switching property of individual crystallites in PZT thin films.     

Effect of substrate temperature and annealing temperature on the structural, electrical and microstructural properties of thin Pt films by rf magnetron sputtering

Influence of both substrate temperature, T_s, and annealing temperature, T_a, on the structural, electrical and microstructural properties of sputtered deposited Pt thin films have been investigated. X-ray diffraction results show that as deposited Pt films (T_s = 300, 400 °C) are preferentially oriented along (1 1 1) direction. A little growth both along (2 0 0) and (3 1 1) directions are also noticed in the as deposited Pt films. After annealing in air (T_a = 500-700 °C), films become strongly oriented along (1 1 1) plane. With annealing temperature, average crystallite size, D, of the Pt films increases and micro-strain, e, and lattice constant, a₀, decreases. Residual strain observed in the as deposited Pt films is found to be compressive in nature while that in the annealed films is tensile. This change in the strain from compressive to tensile upon annealing is explained in the light of mismatch between the thermal expansion coefficients of the film material and substrate. Room temperature resistivity of Pt films is dependant on both the T_s and T_a of the films. Observed decrease in the film resistivity with T_a is discussed in terms of annihilation of film defects and grain-boundary. Scanning electron microscopic study reveals that as the annealing temperature increases film densification improves. But at an annealing temperature of ∼600 °C, pinholes appear on the film surface and the size of pinhole increases with further increase in the annealing temperature. From X-ray photoelectron spectroscopic analysis, existence of a thin layer of chemisorbed atomic oxygen is detected on the surfaces of the as deposited Pt films. Upon annealing, coverage of this surface oxygen increases.     

Infrared optical properties of Ba(Zr0.20Ti0.80)O3 and Ba(Zr0.30Ti0.70)O3 thin films prepared by sol-gel method

Ba(Zr_xTi_1−x)O₃ (BZT) (x = 0.20 and 0.30) thin films are deposited on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrate by sol-gel method. X-ray diffraction patterns show that the thin films have a good crystallinity. Optical properties of the films in the wavelength range of 2.5-12 μm are studied by infrared spectroscopic ellipsometry (IRSE). The optical constants of the BZT thin films are determined by fitting the IRSE data using a classical dispersion formula. As the wavelength increases, the refractive index decreases, while the extinction coefficients increase. The effective static ionic charges are derived, which are smaller than that in a purely ionic material for the BZT thin films.     

Low temperature deposition of transparent conducting ITO/Au/ITO films by reactive magnetron sputtering

Transparent conducting indium tin oxide/Au/indium tin oxide (ITO) multilayered films were deposited on unheated polycarbonate substrates by magnetron sputtering. The thickness of the Au intermediated film varied from 5 to 20 nm. Changes in the microstructure, surface roughness and optoelectrical properties of the ITO/Au/ITO films were investigated with respect to the thickness of the Au intermediated layer. X-ray diffraction measurements of ITO single layer films did not show characteristic diffraction peaks, while ITO/Au/ITO films showed an In₂O₃ (2 2 2) characteristic diffraction peak. The optoelectrical properties of the films were also dependent on the presence and thickness of the Au thin film. The ITO 50 nm/Au 10 nm/ITO 40 nm films had a sheet resistance of 5.6 Ω/□ and an average optical transmittance of 72% in the visible wavelength range of 400-700 nm. Consequently, the crystallinity, which affects the optoelectrical properties of ITO films, can be enhanced with Au intermediated films.     

Epitaxial growth and structural characterization of Pb(Fe1/2Nb1/2)O3 thin films

We have grown lead iron niobate thin films with composition Pb(Fe_1/2Nb_1/2)O₃ (PFN) on (0 0 1) SrTiO₃ substrates by pulsed laser deposition. The influence of the deposition conditions on the phase purity was studied. Due to similar thermodynamic stability spaces, a pyrochlore phase often coexists with the PFN perovskite phase. By optimizing the kinetic parameters, we succeeded in identifying a deposition window which resulted in epitaxial perovskite-phase PFN thin films with no identifiable trace of impurity phases appearing in the X-ray diffractograms. PFN films having thicknesses between 20 and 200 nm were smooth and epitaxially oriented with the substrate and as demonstrated by RHEED streaks which were aligned with the substrate axes. X-ray diffraction showed that the films were completely c-axis oriented and of excellent crystalline quality with low mosaicity (X-ray rocking curve FWHM?0.09°). The surface roughness of thin films was also investigated by atomic force microscopy. The root-mean-square roughness varies between 0.9 nm for 50-nm-thick films to 16 nm for 100-nm-thick films. We also observe a correlation between grain size, surface roughness and film thickness.     

Studies of structural evolution and sensing properties of ZnO nanocrystalline films

ZnO nanocrystalline films have been prepared on Si(1 0 0) substrate using direct current (D.C) magnetron sputtering technique at room temperature. The thickness of nanocrystalline films almost linearly increased with deposition duration and the sizes of crystalline grains almost kept unchanged. After deposition, thermal annealing was performed at 800 °C in atmosphere for 2 h in order to improve the qualities of ZnO thin films. Scanning electron microscope (SEM) images showed the surface roughness of the films less than 45 nm. X-ray diffraction (XRD) patterns revealed the slight evolution of the crystal structures. Raman scattering spectra confirmed the data obtained from X-ray diffraction measurements.With these ZnO nanocrystalline films, prototypic gas sensors were fabricated. Both sensitivity and response of the sensors to different gases (H₂ and CH₄) were investigated. A quick response of time, less than 1 second to CH₄ gas sensor has been achieved.     

Homogeneous Si films on CaF2/Si(1 1 1) due to boron enhanced solid phase epitaxy

The structure and morphology of Si/CaF₂/Si(1 1 1) structures have been investigated by X-ray diffraction (XRD, GIXRD) and X-ray photoelectron spectroscopy (XPS). While CaF₂ films were grown via molecular beam epitaxy (MBE), Si films on CaF₂/Si(1 1 1) are fabricated by surfactant enhanced solid phase epitaxy (SE-SPE). Here Boron was used as a surfactant to obtain semiconductor films of homogeneous thickness. The Si films are entirely relaxed while the CaF₂ films have both pseudomorphic and relaxed crystallites. After exposure to ambient conditions, the Si films have a very thin native oxide film. The homogeneous Si film partially prevents the incorporation of impurities at the interface between the Si substrate and CaF₂ via migration along residual defects of the CaF₂ film.     

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.     

Effects of the substrate temperature on the properties of CuIn5S8 thin films

Structural, optical and electrical properties of CuIn₅S₈ thin films grown by thermal evaporation have been studied relating the effects of substrate heating conditions of these properties. The CuIn₅S₈ thin films were carried out at substrate temperatures in the temperature range 100-300 °C. The effects of heated substrate on their physico-chemical properties were investigated using X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), optical transmission and hot probe method. X-ray diffraction revealed that the films are strong preferred orientation along the (3 1 1) plane upon substrate temperature 200 °C and amorphous for the substrate temperatures below 200 °C. No secondary phases are observed for all the films. The composition is greatly affected by heated substrate. From the optical transmission and reflection, an important absorption coefficient exceeds 10⁵ cm⁻¹ at 800 nm was found. As increasing the substrate temperature, the optical energy band gap decreases from 1.70 eV for the unheated films to 1.25 eV for the deposited films at 300 °C. It was found that CuIn₅S₈ thin film is an n-type semiconductor at 250° C.     

Effects of substrates on the structure and dielectric properties of Ba(Sn0.15Ti0.85)O3 thin films

Ba(Sn_0.15Ti_0.85)O₃ (BTS) thin films were grown on Pt(1 1 1)/Ti/SiO₂/Si and LaNiO₃(LNO)/Pt(1 1 1)/Ti/SiO₂/Si substrates by a sol-gel processing technique, respectively. The BTS thin films deposited on annealed Pt(1 1 1)/Ti/SiO₂/Si and annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrates exhibited strong (1 1 1) and perfect (1 0 0) orientations, respectively. The BTS thin films grown on un-annealed Pt(1 1 1)/Ti/SiO₂/Si substrates showed random orientation with intense (1 1 0) peak, while the films deposited on un-annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrate exhibited random orientation with intense (1 0 0) peak, respectively. The dielectric constant of the BTS films deposited on annealed Pt(1 1 1)/Ti/SiO₂/Si, annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si, un-annealed Pt(1 1 1)/Ti/SiO₂/Si and un-annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrates was 512, 565, 386 and 437, respectively, measured at a frequency of 100 kHz. A high tunability of 49.7% was obtained for the films deposited on annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrate, measured at the frequency of 100 kHz with an applied electric field of 200 kV/cm. The high tunability has been attributed to the (1 0 0) texture of the films and larger grain sizes.