Effect of substrate bias voltage on the structure, electric and dielectric properties of TiO(2) thin films by DC magnetron sputtering

Titanium dioxide (TiO(2)) films have been deposited on glass and p-silicon (1 0 0) substrates by DC magnetron sputtering technique to investigate their structural, electrical and optical properties. The surface composition of the TiO(2) films has been analyzed by X-ray photoelectron spectroscopy. The TiO(2) films formed on unbiased substrates were amorphous. Application of negative bias voltage to the substrate transformed the amorphous TiO(2) into polycrystalline as confirmed by Raman spectroscopic studies. Thin film capacitors with configuration of Al/TiO(2)/p-Si have been fabricated. The leakage current density of unbiased films was 1 x10(-6) A/cm(2) at a gate bias voltage of 1.5 V and it was decreased to 1.41 x 10(-7) A/cm(2) with the increase of substrate bias voltage to -150 V owing to the increase in thickness of interfacial layer of SiO(2). Dielectric properties and AC electrical conductivity of the films were studied at various frequencies for unbiased and biased at -150 V. The capacitance at 1 MHz for unbiased films was 2.42 x 10(-10) F and it increased to 5.8 x 10(-10) F in the films formed at substrate bias voltage of -150 V. Dielectric constant of TiO(2) films were calculated from capacitance-voltage measurements at 1 MHz frequency. The dielectric constant of unbiased films was 6.2 while those formed at -150 V it increased to 19. The optical band gap of the films decreased from 3.50 to 3.42 eV with the increase of substrate bias voltage from 0 to -150 V. (C) 2011 Elsevier B. V. All rights reserved.

Alternating current conduction behavior of excimer laser ablated SrBi2Nb2O9 thin films

Bi-layered Aurivillius compounds prove to be efficient candidates of nonvolatile memories. SrBi2Nb2O9 thin films were deposited by excimer laser ablation at low substrate temperature (400 °C) followed by an ex situ annealing at 750 °C. The polarization hysteresis behavior was confirmed by variation of polarization with the external applied electric field and also verified with capacitance versus voltage characteristics. The measured values of spontaneous and remnant polarizations were, respectively, 9 and 6 μC/cm2 with a coercive field of 90 kV/cm. The measured dielectric constant and dissipation factors at 100 kHz were 220 and 0.02, respectively. The frequency analysis of dielectric and ac conduction properties showed a distribution of relaxation times due to the presence of multiple grain boundaries in the films. The values of activation energies from the dissipation factor and grain interior resistance were found to be 0.9 and 1.3 eV, respectively. The deviation in these values was attributed to the energetic conditions of the grain boundaries and bulk grains. The macroscopic relaxation phenomenon is controlled by the higher resistive component in a film, such as grain boundaries at lower temperatures, which was highlighted in the present article in close relation to interior grain relaxation and conduction properties.

Growth and characterization of excimer laser-ablated BaBi2Nb2O9 thin films

The pulsed-laser ablation technique has been employed to deposit polycrystalline thin films of layered-structure ferroelectric BaBi2Nb2O9 (BBN). Low-substrate-temperature growth (Ts = 400 °C) followed by ex situ annealing at 800 °C for 30 min was performed to obtain a preferred orientation. Ferroelectricity in the films was verified by examining the polarization with the applied electric field and was also confirmed from the capacitance–voltage characteristics. The films exhibited well-defined hysteresis loops, and the values of saturation (Ps) and remanent (Pr) polarization were 4.0 and 1.2 μC/cm2, respectively. The room-temperature dielectric constant and dissipation factor were 214 and 0.04, respectively, at a frequency of 100 kHz. A phase transition from a ferroelectric to paraelectric state of the BBN thin film was observed at 220 °C. The dissipation factor of the film was observed to increase after the phase transition due to a probable influence of dc conduction at high temperatures. The real and imaginary part of the dielectric constant also exhibited strong frequency dispersion at high temperatures.

Anisotropic electrical transport property in La4BaCu5O13+δ and La4BaCu4NiO13+δ epitaxial thin films

Epitaxial films of La4BaCu5O13+δ and La4BaCu4NiO13+δ oxides are grown with a-b plane parallel to (100) of LaAlO3 and SrTiO3 by pulsed-laser deposition. The conductivity measurements performed along the c direction using LaNiO3 as the electrode show metallic behavior whereas they show semiconducting behavior in the a-b plane. Anisotropic transport property of these thin films is explained on the basis of nearly 180° connected Cu–O–Cu chains with an average Cu–O distance of 1.94 Å along the c direction and nearly 180° and 90° connected Cu–O–Cu chains in the a-b plane with short and long Cu–O distances ranging from 1.863 to 2.303 Å. YBa2Cu3O7−x has been grown along (00l) on La4BaCu5O13+δ and shows a Tc of 88 K.

Backward switching phenomenon from field forced ferroelectric to antiferroelectric phases in antiferroelectric PbZrO3 thin films

Antiferroelectric materials (example: lead zirconate and modified lead zirconate stannate), in which a field-induced ferroelectric phase transition is feasible due to a small free energy difference between the ferroelectric and the antiferroelectric phases, are proven to be very good candidates for applications involving actuation and high charge storage devices. The property of reverse switching from the field-induced ferroelectric to antiferroelectric phases is studied as a function of temperature, applied electric field, and sample thickness in antiferroelectric lead zirconate thin films deposited by pulsed excimer laser ablation. The maximum released charge density was 22 μC/cm2 from a stored charge density of 36 μC/cm2 in a 0.55 μ thick lead zirconate thin film. This indicated that more than 60% of the stored charge could be released in less than 7 ns at room temperature for a field of 200 kV/cm. The content of net released charge was found to increase with increasing field strength, whereas with increasing temperature the released charge was found to decrease. Thickness-dependent studies on lead zirconate thin films showed that size effects relating to extrinsic and intrinsic pinning mechanisms controlled the released and induced charges through the intrinsic switching time. These results proved that antiferroelectric PZ thin films could be utilized in high-speed charge decoupling capacitors in microelectronics applications.

Growth and characterization of SrBi2Nb2O9 thin films by pulsed-laser ablation

Polycrystalline films of SrBi2Nb2O9 were grown using pulsed-laser ablation. The ferroelectric properties were achieved by low-temperature deposition followed by a subsequent annealing process. The lower switching voltage was obtained by lowering the thickness, which did not affect the insulating nature of the films. The hysteresis results showed an excellent square-shaped loop with results (Pr = 6 μC/cm2, Ec = 100 kV/cm) in good agreement with earlier reports. The films also exhibited a dielectric constant of 250 and a dissipation factor of 0.02. The transport studies indicated an ohmic behavior, while higher voltages induced a bulk space charge.

Large reduction of leakage current by graded-layer La doping in (Ba0.5, Sr0.5)TiO3 thin films

A large reduction in the leakage current behavior in (Ba, Sr)TiO3 (BST) thin films was observed by graded-layer donor doping. The graded doping was achieved by introducing La-doped BST layers in the grown BST films. The films showed a large decrease (about six orders of magnitude) in the leakage current in comparison to undoped films at an electric field of 100 kV/cm. The large decrease in leakage current was attributed to the formation of highly resistive layers, originating from compensating defect chemistry involved for La-doped films grown in oxidizing environment. Temperature-dependent leakage-current behavior was studied to investigate the conduction mechanism and explanations of the results were sought from Poole–Frenkel conduction mechanism.

Field-induced dielectric properties of laser ablated antiferroelectric (Pb0.99Nb0.02)(Zr0.57Sn0.38Ti0.05)0.98O3 thin films

Niobium-modified lead zirconate stannate titanate antiferroelectric thin films with the chemical composition of (Pb0.99Nb0.02)(Zr0.57Sn0.38Ti0.05)0.98O3 were deposited by pulsed excimer laser ablation technique on Pt-coated Si substrates. Field-induced phase transition from antiferroelectric to ferroelectric properties was studied at different fields as a function of temperature. The field forced ferroelectric phase transition was elucidated by the presence of double-polarization hysteresis and double-butterfly characteristics from polarization versus applied electric field and capacitance and voltage measurements, respectively. The measured forward and reverse switching fields were 25 kV/cm and 77 kV/cm, respectively. The measured dielectric constant and dissipation factor were 540 and 0.001 at 100 kHz, respectively, at room temperature.

Investigations on multimagnetron sputtered Zn1-xMgxO thin films through metal-ferroelectric-semiconductor configuration

The effect of Mg doping in ZnO is investigated through structural, electrical, and optical properties. Zn1−xMgxO (0<×<0.3) thin films were deposited on Si (100) and corning glass substrates using multimagnetron sputtering. Investigations on the structural properties of the films revealed that the increase in Mg concentration resulted in phase evolution from hexagonal to cubic phase. The temperature dependent study of dielectric constant at different frequencies exhibited a dielectric anomaly at 110 °C. The Zn0.7Mg0.3O thin films exhibited a well-defined polarization hysteresis loop with a remnant polarization of 0.2 μC/cm2 and coercive field of 8 kV/cm at room temperature. An increase in the band gap with an increase in Mg content was observed in the range of 3.3–3.8 eV for x = 0–0.3. The average transmittance of the films was higher than 90% in the wavelength region λ = 400–900 nm.

Reactive pulsed laser deposition and characterization of niobium nitride thin films

We present a systematic study to explore the effect of important process variables on the composition and structure of niobium nitride thin films synthesized by Reactive Pulsed Laser Deposition (RPLD) technique through ablation of high purity niobium target in the presence of low pressure nitrogen gas. Secondary Ion Mass Spectrometry has been used in a unique way to study and fix gas pressure, substrate temperature and laser fluence, in order to obtain optimized conditions for one variable in single experimental run. The x-ray diffraction and electron microscopic characterization have been complemented by proton elastic backscattering spectroscopy and x-ray photoelectron spectroscopy to understand the incorporation of oxygen and associated non-stoichiometry in the metal to nitrogen ratio. The present study demonstrates that RPLD can be used for obtaining thin film architectures using non-equilibrium processing. Finally the optimized NbN thin films were characterized for their hardness using nano-indentation technique and found to be similar to 30 GPa at the deposition pressure of 8 Pa. (C) 2011 Elsevier B.V. All rights reserved.

Simulation and experimental study on compositional evolution of Li-Co in LiCoO2 thin films during sputter deposition

The compositional evolution in sputter deposited LiCoO2 thin films is influenced by process parameters involved during deposition. The electrochemical performance of these films strongly depends on their microstructure, preferential orientation and stoichiometry. The transport process of sputtered Li and Co atoms from the LiCoO2 target to the substrate, through Ar plasma in a planar magnetron configuration, was investigated based on the Monte Carlo technique. The effect of sputtering gas pressure and the substrate-target distance (dst) on Li/Co ratio, as well as, energy and angular distribution of sputtered atoms on the substrate were examined. Stable Li/Co ratios have been obtained at 5 Pa pressure and dst in the range 5−11 cm. The kinetic energy and incident angular distribution of Li and Co atoms reaching the substrate have been found to be dependent on sputtering pressure. Simulations were extended to predict compositional variations in films prepared at various process conditions. These results were compared with the composition of films determined experimentally using x-ray photoelectron spectroscopy (XPS). Li/Co ratio calculated using XPS was in moderate agreement with that of the simulated value. The measured film thickness followed the same trend as predicted by simulation. These studies are shown to be useful in understanding the complexities in multicomponent sputtering.

Dielectric properties of c-axis oriented Zn1-xMgxO thin films grown by multimagnetron sputtering

Zn1−xMgxO (x = 0.3) thin films have been fabricated on Pt/TiO2/SiO2/Si substrates using multimagnetron sputtering technique. The films with wurtzite structure showed a (002) preferred orientation. Ferroelectricity in Zn1−xMgxO films was established from the temperature dependent dielectric constant and the polarization hysteresis loop. The temperature dependent study of dielectric constant at different frequencies exhibited a dielectric anomaly at 110 °C. The resistivity versus temperature characteristics showed an anomalous increase in the vicinity of the dielectric transition temperature. The Zn1−xMgxO thin films exhibit well-defined polarization hysteresis loop, with a remanent polarization of 0.2 μC/cm2 and coercive field of 8 kV/cm at room temperature.

Enhancement of charge and energy storage in sol-gel derived pure and La-modified PbZrO3 thin films

Antiferroelectric lanthanum-modified PbZrO3 thin films with La contents between 0 and 6 at. % have been deposited on Pt(111)/Ti/SiO2/Si substrate by sol-gel route. On the extent of La-modification, maximum polarization (Pmax) and recoverable energy density (W) have been enhanced followed by their subsequent reduction. A maximum Pmax ( ∼ 0.54 C/m2 at ∼ 60 MV/m) as well as a maximum W ( ∼ 14.9 J/cc at ∼ 60 MV/m) have been achieved on 5% La modification. Both Pmax and W have been found to be strongly dependent on La-induced crystallographic orientations.

Growth and ferroelectric properties of Bi2VO5.5 thin films with metallic LaNiO3 electrodes

Novel ferroelectric bismuth vanadate, Bi2VO5.5 (BVO), thin films have been grown between lattice matched metallic LaNiO3 (LNO) layers deposited on SrTiO3 (STO) by the pulsed laser deposition technique. LNO/BVO/LNO/STO and Au/BVO/LNO/STO trilayer structures exhibited c‐oriented (001) growth of BVO. LNO has been found to be a good metallic electrode with sheet resistance ∼20 Ω in addition to aiding c‐axis oriented BVO growth. The dielectric constant, ϵr of LNO/BVO/LNO/STO, at 300 K was about 12. However, when an Au electrode was used on top of BVO/LNO/STO film, it showed a significant improvement in the dielectric constant (ϵr=123). The ferroelectric properties of BVO thin films have been confirmed by hysteresis behavior with a remnant polarization, Pr=4.6×10−8 C/cm2 and coercive field, Ec=23 kV/cm at 300 K.

Dielectric properties of (110) oriented PbZrO3 and La-modified PbZrO3 thin films grown by sol-gel process on Pt(111)/Ti/SiO2/Si substrate

Highly (110) preferred orientated antiferroelectric PbZrO3 (PZ) and La-modified PZ thin films have been fabricated on Pt/Ti/SiO2/Si substrates using sol-gel process. Dielectric properties, electric field induced ferroelectric polarization, and the temperature dependence of the dielectric response have been explored as a function of composition. The Tc has been observed to decrease by ∼ 17 °C per 1 mol % of La doping. Double hysteresis loops were seen with zero remnant polarization and with coercive fields in between 176 and 193 kV/cm at 80 °C for antiferroelectric to ferroelectric phase transformation. These slim loops have been explained by the high orientation of the films along the polar direction of the antiparallel dipoles of a tetragonal primitive cell and by the strong electrostatic interaction between La ions and oxygen ions in an ABO3 perovskite unit cell. High quality films exhibited very low loss factor less than 0.015 at room temperature and pure PZ; 1 and 2 mol % La doped PZs have shown the room temperature dielectric constant of 135, 219, and 142 at the frequency of 10 kHz. The passive layer effects in these films have been explained by Curie constants and Curie temperatures. The ac conductivity and the corresponding Arrhenius plots have been shown and explained in terms of doping effect and electrode resistance.