Dielectric-breakdown-like forming process in the unipolar resistance switching of Ta2O5−x thin films

We report unipolar resistance switching (URS) in Ta₂O_5−x thin films. The current increased suddenly when we applied voltages up to 5-7 V to the pristine state of Pt/Ta₂O_5−x/Pt, Ni/Ta₂O_5−x/Pt, and Ti/Ta₂O_5−x/Pt cells. Just after this forming process, we observed a repetitive URS occurring independently of the electrodes. We found that the required voltages for the forming process did not depend on the top electrode type, but on the film thickness. These results suggest that the forming process is driven by a dielectric-breakdown-like phenomenon, and that URS occurs due to the formation and rupture of conducting channels inside the Ta₂O_5−x thin film.     

Electrical properties of pulsed laser-deposited SrxBiyTa2O9 thin films on Bi/Sr ratios

The dependence of the electrical properties of Sr_xBi_yTa₂O₉ thin films on the (Bi/Sr ratio 1.6, 2.3, 2.8, 3.4) has been investigated. The Sr_xBi_yTa₂O₉ ferroelectric thin films were synthesized on Pt/Ti/SiO₂/Si substrates using the pulsed laser deposition method. Saturation polarization (P_st) and coercive field (2E_c) depend on the Bi/Sr ratio. P_st increases while E_c decreases with an increase in Bi/Sr ratio. Atomic Force Microscopy images show that the grain size grows with increasing Bi/Sr ratio. It is observed that the impedance behavior in Sr_xBi_yTa₂O₉ thin film, conforms to the Constant Phase Element (CPE) model. It is believed that the diffuse charges at the grain boundary build up a surface polarization because the impedance behavior close to pure capacitor with grain size increased.     

Anomalous Hall effect in Cu and Fe codoped In2O3 and ITO thin films

We present a systematic study of the structure, magnetization, resistivity, and Hall effect properties of pulsed laser deposited Fe- and Cu-codoped In₂O₃ and indium-tin-oxide (ITO) thin films. Both the films show a clear ferromagnetism and anomalous Hall effect at 300 K. The saturated magnetic moments are almost the same for the two samples, but their remanent moments M_r and coercive fields H_C are quite different. M_r and H_C values of ITO film are much smaller than that of In₂O₃. The ITO sample shows a typical semiconducting behavior in whole studied temperature range, while the In₂O₃ thin film is metallic in the temperature range between 147 and 285 K. Analysis of different conduction mechanisms suggest that charge carriers are not localized in the present films. The profile of the anomalous Hall effect vs. magnetic field was found to be identical to the magnetic hysteresis loops, indicating the possible intrinsic nature of ferromagnetism in the present samples.     

Electrical behavior of BaZr0.1Ti0.9O3 and BaZr0.2Ti0.8O3 thin films

BaZr_0.1Ti_0.9O₃ and BaZr_0.2Ti_0.8O₃ (BZT) thin films were deposited on Pt/Ti/LaAlO₃ (1 0 0) substrates by radio-frequency magnetron sputtering, respectively. The films were further annealed at 800 °C for 30 min in oxygen. X-ray diffraction θ-2θ and Φ-scans showed that BaZr_0.1Ti_0.9O₃ films displayed a highly (h 0 0) preferred orientation and a good cube-on-cube epitaxial growth on the LaAlO₃ (1 0 0) substrate, while there are no obvious preferential orientation in BaZr_0.2Ti_0.8O₃ thin films. The BaZr_0.1Ti_0.9O₃ films possess larger grain size, higher dielectric constant, larger tunability, larger remanent polarization and coercive electric field than that of BaZr_0.2Ti_0.8O₃ films. Whereas, BaZr_0.1Ti_0.9O₃ films have larger dielectric losses and leakage current density. The results suggest that Zr⁴⁺ ion can decrease dielectric constant and restrain non-linearity. Moreover, the enhancement in dielectric properties of BaZr_0.1Ti_0.9O₃ films may be attributed to (1 0 0) preferred orientation.     

Mg diffusion in K(Ta0.65Nb0.35)O3 thin films grown on MgO evidenced by Auger electron spectroscopy investigation

The diffusion of Mg in pulsed laser deposited K(Ta_0.65Nb_0.35)O₃ thin films epitaxially grown on (1 0 0) MgO single crystal substrate were investigated by Auger electron spectroscopy (AES). A diffusion of Mg from the substrate into the whole thickness (400 nm) of the as-deposited K(Ta_0.65Nb_0.35)O₃ films was observed with an accumulation of Mg at the surface. Ex situ post-annealing (750 °C/2 h) has led to a homogeneous distribution of Mg in all the ferroelectric coating. This strong reaction between film and substrate promotes a doping effect, responsible for the reduction of K(Ta_0.65Nb_0.35)O₃ dielectric losses in comparison with films grown on other substrates.     

Writing of two-dimensional crystal curved lines at the surface of Sm2O3-Bi2O3-B2O3 glass by samarium atom heat processing

Two-dimensional crystal curved lines consisting of the nonlinear optical Sm_xBi_1−xBO₃ phase are fabricated at the surface of 8Sm₂O₃·37Bi₂O₃·55B₂O₃ glass by continuous wave Nd:YAG laser (wavelength: 1064 nm) irradiation (samarium atom heat processing) with a power of ∼0.9 W and a laser scanning speed of 5 μm/s. The curved lines with bending angles of 0-90° or with sine-shapes are written by just changing the laser scanning direction. The polarized micro-Raman scattering spectra for the line after bending are the same as those for the line before bending, indicating that the crystal plane of Sm_xBi_1−xBO₃ crystals to the crystal growth direction might be maintained even after the change in the laser scanning direction. It is found from laser scanning microscope observations that the crystal lines at the surface are swelled out smoothly, giving a height of about 10 μm.     

Ion beam etching of high resolution structures in Ta2O5 for grating-assisted directional coupler applications

An investigation on thin Ta₂O₅ films patterning using argon ion beam etching (IBE) is presented. The etch rates are characterised by varying the angle of incidence of the beam onto the substrate. Ta₂O₅ gratings with a period of 2.2 μm (1.1 μm linewidth) and 0.25 μm thickness are fabricated using an angle of incidence of 0°. The resulting Ta₂O₅ grating cross sectional profiles are analysed using AFM and SEM imaging. A fabrication method is thus demonstrated which could be used to implement wavelength selective gratings in applications such as grating-assisted directional couplers (GADCs).     

The effect of potential of impedance in the pulsed-laser-deposited SrBi2Ta2O9 thin film

Ferroelectrics SrBi₂Ta₂O₉ (SBTO) thin films were grown on a highly oriented Pt/Ti/SiO₂/Si substrates using the pulsed laser ablation. The ac impedance of SBTO thin films have been measured at room temperature both in the frequency range from 10⁻¹ to 10⁶ Hz and bias voltage range from −6 to 6 V. The ac impedance dispersion was observed at low frequency with increasing bias voltage, which was interpreted based on a blocked charge. We can explain that the blocking interface gives rise to constant phase element (CPE) response, and we give an impedance model function that can fit data along the low frequency range when such a CPE is found. The low frequency dispersion phenomena of SBTO thin film are related to a charge diffusion process at the surface of thin film.     

Dielectric properties of continuous composition spreaded MgO-Ta2O5 thin films

The dielectric properties of MgO-Ta₂O₅ continuous composition spread (CCS) thin films were investigated. The MgO-Ta₂O₅ CCS thin films were deposited on Pt/Ti/SiO₂/Si substrates by off-Axis RF magnetron sputtering system, and then the films were annealed at 350 °C with rapid thermal annealing system in vacuum. The dielectric constant and loss of MgO-Ta₂O₅ CCS thin films were plotted via 1500 micron-step measuring. The specific point of Ta₂O₅-MgO CCS thin film (post annealed at 350 °C) showing superior dielectric properties of high dielectric constant (k ∼ 28) and low dielectric loss (tan δ < 0⋅004) at 1 MHz were found in the area of 3-5 mm apart from Ta₂O₅ side on the substrate. The cation's composition of thin film was Mg:Ta = 0.4:2 at%.     

Ferroelectric properties of Pr and Nb co-substituted Sr0.8Bi2.2Ta2O9 thin films

Thin film of both A- and B-site co-substituted Sr_0.8Bi_2.2Ta₂O₉ (SBT) by Pr³⁺ and Nb⁵⁺, i.e. Sr_0.8Pr_0.1Bi_2.1Ta_1.5Nb_0.5O₉ (SPBTN) was fabricated on Pt/Ti/SiO₂/Si substrates by metalorganic decomposition method. The Nb⁵⁺ substitution at B-site and Pr³⁺ substitution at A-site enhanced the remanent polarization and reduced the coercive field of the films, respectively. The remanent polarization (2P_r) value of the SPBTN film was 22 μC/cm². The coercive field (2E_c) value of the SPBTN film was 102 kV/cm, which was much lower than that of SBTN (165 kV/cm). The effects of substitution on structural and ferroelectric properties of SBT were discussed in detail. As a result, the A- and B-sites co-substitution may be one of the promising ways to improve ferroelectric properties of SBT.     

Synthesis and characterization of room-temperature ferromagnetism in Fe- and Ni-co-doped In2O3

Observation of room-temperature ferromagnetism in Fe- and Ni-co-doped In₂O₃ samples (In_0.9Fe_0.1−xNi_x)₂O₃ (0?x?0.1) prepared by citric acid sol-gel auto-igniting method is reported. All of the samples with intermediate x values are ferromagnetic at room-temperature. The highest saturation magnetization (0.453 μ_B/Fe+Ni ions) moment is reached in the sample with x=0.04. The highest solubility of Fe and Ni ions in the In₂O₃ lattice is around 10 and 4 at%, respectively. The 10 at% Fe-doped sample is found to be weakly ferromagnetic, while the 10 at% Ni-doped sample is paramagnetic. Extensive structure including Extended X-ray absorption fine structure (EXAFS), magnetic and magneto-transport including Hall effects studies on the samples indicate the observed ferromagnetism is intrinsic rather than from the secondary impurity phases.     

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.     

Modulation of the photoluminescence of Si quantum dots by means of CO2 laser pre-annealing

Si quantum dots (QDs) embedded in SiO₂ can be normally prepared by thermal annealing of SiO_x (x < 2) thin film at 1100 °C in an inert gas atmosphere. In this work, the SiO_x thin film was firstly subjected to a rapid irradiation of CO₂ laser in a dot by dot scanning mode, a process termed as pre-annealing, and then thermally annealed at 1100 °C for 1 h as usual. The photoluminescence (PL) intensity of Si QD was found to be enhanced after such pre-annealing treatment. This PL enhancement is not due to the additional thermal budget offered by laser for phase separation, but attributed to the production of extra nucleation sites for Si dots within SiO_x by laser irradiation, which facilitates the formation of extra Si QDs during the subsequent thermal annealing.     

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.     

Power-law scaling of proton conductivity in amorphous silicate thin films

Amorphous hafnium silicate, a-Hf_0.1Si_0.9O_x, thin film with thickness of 32, 41, 55, 80, 110, 120, 180 and 320 nm was prepared by multiple spin-cast process and the proton conductivity across the films was measured at intermediate temperatures (100-400 °C) in dry atmosphere. The morphologically- and compositionally-uniform films were prepared on a substrate as confirmed by SEM, RBS and XPS measurements. a-Hf_0.1Si_0.9O_x thin film clearly revealed the H/D isotope effect on ionic conductivity, indicating that protonic conduction is dominant in the measured temperature range. The films did not reveal thickness-dependent proton conductivity in dry air and the σ at given temperatures is almost constant at any thickness. No increment of σ in a-Hf_0.1Si_0.9O_x thin films by reduction of thickness might be related to the absence of the highly-conductive acid network with mesoscopically-sized length because of the relatively low concentration of Brønsted acid sites inside films.     

Effects of protons and acceptor substitution on the electrical conductivity of La6WO12

Transport properties and non-stoichiometry of La_1−xCa_xW_1/6O₂ and La_1−yW_1/6O₂ (x=0, 0.005, 0.05; y=0.05, 0.1) have been characterized by means of impedance spectroscopy, the EMF-technique, H⁺/D⁺ isotope exchange, and thermogravimetry in the temperature range 300-1200 °C as a function of oxygen partial pressure and water vapor partial pressure. The materials exhibit mixed ionic and electronic conductivities; n- and p-type electronic conduction predominate at high temperatures under reducing and oxidizing conditions, respectively. Protons are the major ionic charge carrier under wet conditions and predominates the conductivity below ∼750 °C. The maximum in proton conductivity is observed for LaW_1/6O₂ with values reaching 3×10⁻³ S/cm at approximately 800 °C. The high proton conductivity for the undoped material is explained by assuming interaction between water vapor and intrinsic (anti-Frenkel) oxygen vacancies.     

Laser-induced forward transfer technique for maskless patterning of amorphous V2O5 thin film

A laser-induced forward transfer technique has been applied for the maskless patterning of amorphous V₂O₅ thin films. A sheet beam of a frequency doubled (SHG) Q-switched Nd:YAG laser was irradiated on a transparent glass substrate (donor), the rear surface of which was pre-coated with a vacuum-deposited V₂O₅ 180 nm thick film was either in direct contact with a second glass substrate (receiver) or a 0.14 mm air-gap was maintained between the donor film and the receiving substrate. Clear, regular stripe pattern of the laser-induced transferred film was obtained on the receiver. The pattern was characterized using X-ray diffraction (XRD), optical absorption spectroscopy, scanning electron microscopy (SEM), energy dispersive analysis of X-ray (EDAX), atomic force microscopy (AFM), etc.     

Studies of resistance switching effects in metal/YBa2Cu3O7−x interface junctions

Current-voltage characteristics of planar junctions formed by an epitaxial c-axis oriented YBa₂Cu₃O_7−x thin film micro-bridge and Ag counter-electrode were measured in the temperature range from 4.2 K to 300 K. A hysteretic behavior related to switching of the junction resistance from a high-resistive to a low-resistive state and vice-versa was observed and analyzed in terms of the maximal current bias and temperature dependence. The same effects were observed on a sub-micrometer scale YBa₂Cu₃O_7−x thin film-PtIr point contact junctions using Scanning Tunneling Microscope. These phenomena are discussed within a diffusion model, describing an oxygen vacancy drift in YBa₂Cu₃O_7−x films in the nano-scale vicinity of the junction interface under applied electrical fields.     

Structural and electrical transport properties of ZnxFe3−xO4 thin film deposited on Si (1 1 1) by pulsed-laser deposition

Polycrystalline thin films of Fe_3−xZn_xO₄ (x = 0.0, 0.01 and 0.02) were prepared by pulsed-laser deposition technique on Si (1 1 1) substrate. X-ray diffraction studies of parent as well as Zn doped magnetite show the spinel cubic structure of film with (1 1 1) orientation. The order–disorder transition temperature for Fe₃O₄ thin film with thickness of 150 nm are at 123 K (Si). Zn doping leads to enhancement of resistivity by Zn²⁺ substitution originates from a decrease of the carrier concentration, which do not show the Verwey transition. The Raman spectra for parent Fe₃O₄ on Si (1 1 1) substrate shows all Raman active modes for thin films at energies of T_2g¹, T_2g³, T_2g², and A_1g at 193, 304, 531 and 668 cm⁻¹. It is noticed that the frequency positions of the strongest A_1g mode are at 668.3 cm⁻¹, for all parent Fe₃O₄ thin film shifted at lower wave number as 663.7 for Fe_2.98Zn_0.02O₄ thin film on Si (1 1 1) substrate. The integral intensity at 668 cm⁻¹ increased significantly with decreasing doping concentration and highest for the parent sample, which is due to residual stress stored in the surface.     

Laser-induced voltage characteristics of Bi2Sr2Co2Oy thin films on LaAlO3 substrates

We report the laser-induced voltage (LIV) effects in c-axis oriented Bi₂Sr₂Co₂O_y thin films grown on (0 0 1) LaAlO₃ substrates with the title angle α of 0°, 3°, 5° and 10° by a simple chemical solution deposition method. A large open-circuit voltage with the sensitivity of 300 mV/mJ is observed for the film on 10° tilting LaAlO₃ under a 308 nm irradiation with the pulse duration of 25 ns. When the film surface is irradiated by a 355 nm pulsed laser of 25 ps duration, a fast response with the rise time of 700 ps and the full width at half maximum of 1.5 ns is achieved. In addition, the experimental results reveal that the amplitude of the voltage signal is approximately proportional to sin 2α and the signal polarity is reversed when the film is irradiated from the substrate side rather than the film side, which suggests the LIV effects in Bi₂Sr₂Co₂O_y thin films originate from the anisotropic Seebeck coefficient of this material.