Ferroelectric Na0.5K0.5NbO3 thin films by pulsed laser deposition

Abstract

Highly c-axis oriented single phase Na_0.5K_0.5NbO₃ (NKN) thin films have been deposited onto polycrystalline Pt₈₀lr₂₀ substrates and SiO₂/Si(001) wafers using pulsed laser ablation of stoichiometric ceramic target. Strong self-assembling of NKN films along the [001] direction has been observed. Properties of NKN/Pt thin film structures have been successfully tailored by oxygen pressure control from the ferroelectric state, characterized by the remnant polarization of 12 uC/cm², dielectric constant ? ～ 520 and tan δ ～ 0.024 @ 100 kHz, to superparaelectric state with tan δ as low as 0.003 and ? = 210 with very small 1.7% dispersion in the frequency domain 0.4–100 kHz and less than 10% variation in the temperature range 77–415 K. NKN films grown onto SiO₂/Si(001) substrates show quadrupled super-lattice structure along c-axis, loss tan δ less than 0.01, and ? ～ 110 @ 1 MHz. C-V measurements for Au/NKN (270nm)/SiO₂/Si MFIS-diode structure yield memory window of 3.26 V at the programmable voltage of 8 V.     

Comparative Characteristics of Na0.5K0.5NbO3 Films on Pt by Pulsed Laser Deposition and Magnetron Sputtering

Ferroelectric Na_0.5K_0.5NbO₃ (NKN) thin films were grown on the Pt₈₀Ir₂₀ polycrystalline substrates by pulsed laser deposition (PLD) and radio frequency-magnetron sputtering (RF) technique using the same stoichiometric Na_0.5K_0.5NbO₃ ceramic target. X-ray diffraction proved both PLD- and RF-made Na_0.5K_0.5NbO₃/Pt₈₀Ir₂₀ films are single phase and have preferential c-axis orientation. Temperature dependence of dielectric permittivity reveals the presence of two phase transitions around 210 and 410°C. Capacitance vs. applied voltage C-V @ 100 kHz, I-V, and P-E hysteresis characteristics recorded for the vertical capacitive structures yielded loss tanδ = 0.026 and 0.016, tunability about 44.5 and 30% @ 100 kV/cm, Ohmic resistivity 6.7 × 10¹² Ω·cm and 0.2 × 10¹² Ω·cm, remnant polarization 11.7 and 9.7 μC/cm², coercive field 28.0 and 94.6 kV/cm for PLD- and RF-films, respectively. Piezoelectric test carried out in hydrostatic conditions showed piezoelectric coefficient d _H = 21 for PLD-NKN and 15 pC/N for RF-NKN film.     

The resistance degradation of (Ba0.5Sr0.5)TiO3 thin films

Abstract

The leakage current and dielectric properties of (Ba_0.5Sr_0.5)TiO₃(BST) thin films prepared by pulsed laser deposition (PLD) were investigated. It was found that leakage currents for positive bias voltage were higher than that for negative bias voltage, which was attributed to the lattice mismatch between bottom Pt electrode and BST thin film. The time-dependent breakdown process under positive voltage was observed, which was interpreted as the increase of the internal electric field in the film near the bottom electrode. However, the internal electric field can be decreased and eventually recovered by applying negative bias voltage. It was found that internal electric field near the interface can influence the capacitance of the BST thin film capacitor. An explanation for the thickness effect of BST thin films was given.     

Structural evolution and dopant occupancy preference of yttrium-doped potassium sodium niobate thin films

Sodium potassium niobate (KNN) is the most promising candidate for lead-free piezoelectric material, owing to its high Curie temperature and piezoelectric coefficients among the non-lead piezoelectric. Numerous studies have been carried out to enhance piezoelectric properties of KNN through composition design. This research studied the effects of yttrium concentrations and lattice site occupancy preference in KNN films. For this research, the yttrium-doped KNN thin films (mol% = 0, 0.1, 0.3, 0.5, 0.7 and 0.9) were fabricated using the sol-gel spin coating technique and had revealed the orthorhombic perovskite structures. Based on the replacement of Y³⁺ ions for K⁺/ Na⁺ ions, it was found that the films doped with 0.1 to 0.5 mol% of yttrium had less lattice strain, while films with more than 0.5 mol% of Y³⁺ ions had increased strain due to the tendency of Y³⁺ to occupy the B-site in the perovskite lattice. Furthermore, by analysing the vibrational attributes of octahedron bonding, the dopant occupancy at A-site and B-site lattices could be identified. O-Nb-O bonding was asymmetric and became distorted due to the B-site occupancy of yttrium dopants at high dopant concentrations of >0.5 mol%. Extra conduction electrons had resulted in better resistivity of 2.153× 10⁶ Ω at 0.5 mol%, while higher resistivity was recorded for films prepared with higher concentration of more than 0.5 mol%. The introduction of Y³⁺ improved the grain distribution of KNN structure. Further investigations indicated that yttrium enhances the surface smoothness of the films. However, at high concentrations (0.9 mol%), the yttrium increases the roughness of the surface. Within the studied range of Y³⁺ _, the film with 0.5 mol% Y³⁺ represented a relatively desirable improvement in dielectric loss, tan δ and quality factor, Q_m.     

CHARACTERIZATIONS OF W-DOPED (Ba0.5Sr0.5)TiO3 THIN FILMS USING LaNiO3 ELECTRODE

ABSTRACT

The (Ba_0.5Sr_0.5)TiO₃ thin films were deposited onto LaNiO₃ by RF-magnetron sputtering at 550°C. The influence of W content on microstructure and electrical properties of BST films were investigated. The surface and grain size become smoother and smaller as the W content increased. Besides, the dielectric constant, tunability, dissipation factor, and leakage current decreased when the W content increased. The 1% W is the optimal doping concentration. The resultant BST film, with proper dielectric constant and leakage current, has a tunability of 32%, a dissipation factor of 0.006, a FOM value of 53.3 under applied field of 450 kV/cm.     

Structure and dielectric properties of Ca-doped (Ba0.7Sr0.3) TiO3 thin films fabricated by sol–gel method

A wide range of Ca-doped (Ba_0.7Sr_0.3)TiO₃ (BST) thin films (from 0 to 20 mol%) have been prepared on Pt/Ti/SiO₂/Si (100) substrates by sol–gel technique. The structural and dielectric properties of BST thin films were investigated as a function of Ca dopant concentration. The results showed that the microstructure and dielectric properties of the BST films were strongly dependent on the Ca contents. With the Ca dopant concentration increasing, the grain size, dielectric constant and dielectric loss of the BST thin films decreased. As the content of Ca dopant reaches 10 mol%, the dielectric constant, dielectric loss, tunability, the value of FOM and the leakage current density are 281, 0.0136, 16.7%, 12.3 and 5.5?×?10^?6 A/cm², respectively.     

Characterization of Ba(Zr0.05 Ti0.95)O3 thin film prepared by sol-gel process

Ba(Zr_0.05Ti_0.95)O₃ (BZT) thin film (∼330 nm) was grown on Pt/Ti/SiO₂/Si(100) substrate by a simple sol-gel process. The microstructure and the surface morphology of BZT thin film were studied by X-ray diffraction and atomic force microscopy. The optical properties of BZT thin film were obtained by spectroscopic ellipsometry. The optical bandgap was found to be 3.74 eV of direct-transition type. Ferroelectric and dielectric properties of BZT thin film were also discussed. The electrical measurements were conducted on BZT films in metal-ferroelectric-metal (MFM) capacitor configuration. The results showed the film exhibited good ferroelectrity with remanent polarization and coercive electric field of 3.54 μC/cm² and 95.5 kV/cm, respectively. At 10 kHz, the dielectric constant and dielectric loss of the film are 201 and 0.029, respectively.     

PREPARATION AND PROPERTIES OF LITHIUM-DOPED K0.5Na0.5NbO3 THIN FILMS BY CHEMICAL SOLUTION DEPOSITION

ABSTRACT

Lithium-doped K_0.5Na_0.5NbO₃ (KLNN) films were fabricated by chemical solution deposition on Pt/TiO₂/SiO₂/Si substrates. Homogeneous and stable precursor solutions were prepared by controlling the reaction of starting metal alkoxides. Perovskite KLNN single-phase thin films were successfully synthesized on Pt/TiO _x /SiO₂/Si substrates. The 0.75-μ m-thick KLNN film annealed at 650°C exhibited ferroelectric polarization hysteresis loops at ?250°C. The loop at room temperature was round, indicating the film contained leakage components. The dielectric constant under zero bias was 490 at room temperature. A typical upside-down butterfly DC bias-capacitance curve was obtained in the KLNN film capacitors at room temperature, indicating that polarization reversal occurred in the obtained KLNN films.     

Effects of the sol concentration on the texture of Pb0.3Sr0.7TiO3 thin films derived by sol–gel method

Pb_0.3Sr_0.7TiO₃ (PST) thin films were deposited on Pt coated Si (100) substrates by sol–gel techniques using a series of different sol concentrations (0.15, 0.20, 0.25, 0.30, and 0.40 M). Both structural and dielectric characteristics of PST films as a function of the sol concentration were investigated. PST thin films reveal typical crystalline structure with columnar texture when the sol concentration is lower than 0.30 M. With the concentration increasing up to 0.30 M, the columnar-grained structures can not be obtained. Among all the PST thin films, the thin film derived with 0.25 M sol has better dielectric characteristics. The dielectric constant, dielectric loss, tunability and FOM are 329, 0.011, 58.0% and 52.8, respectively.     

Electrical and optical properties of microwave dielectric thin films prepared by pulsed laser deposition

Abstract

Bi₂(Zn_1/3Nb_2/3)₂O₇, BiZN, materials possess high dielectric constant and low loss factor in microwave frequency region. They have good potential for device application, especially in the form of thin films. However, the microwave dielectric properties of a thin film are very difficult to be accurately measured. Evaluation on the dielectric behavior of the films through the performance of the microstrip line devices made of these films involves metallic conduction and stray field losses. A novel measuring technique, which can directly evaluate the microwave dielectric properties of a thin film is thus urgently needed.

In this paper, BiZN thin films were grown on [100] MgO single crystal substrates using pulsed laser deposition process. The high-frequency dielectric properties of thus obtained thin films were determined using optical transmission spectroscopy (OTS). The [100] preferentially oriented films with pyrochlore structure can be obtained for the thin films deposited at 400–600°C substrate temperature under 0.1 mbar oxygen pressure. OTS measurements reveal that the index of refraction (n=1.95–2.35) and absorption coefficient (k=0.28x10^?4-2.25 × 10^?4 nm^?1) of the films vary insignificantly with the crystallinity of the BiZN films.     

Effect of annealing temperature on the electrostrictive properties of 0.94(Na0.5Bi0.5)TiO3-0.06BaTiO3 thin films

0.94(Na_0.5Bi_0.5)TiO₃-0.06BaTiO₃ (NBT-BT6) thin films were fabricated by metal-organic decomposition (MOD) at the different annealing temperatures. Based on the electrostrictive effect and converse piezoelectric effect, the phenomenological approach is provided to characterize the electrostrictive properties of the perovskite relaxor, and it is used to determine the effective electrostriction coefficients $ Q_{33}^{\mathrm{eff}} $ and electrostrictive strains $ {S_3} $ of NBT-BT6 thin films annealed at the range of 650?C800?°C. After the microstructure, ferroelectric, dielectric and piezoelectric properties of the thin films were determined, the maximum values of $ Q_{33}^{\mathrm{eff}} $ and $ {S_3} $ of NBT-BT6 thin film annealed at 750?°C are respectively determined as 0.0289?m⁴/C² and 0.26?% under the bipolar driving field of 391?kV/cm. They are strongly influenced by annealing temperature due to the bismuth evaporation and crystallization of perovskite phase, and the enhanced electrostrictive properties could make NBT-based thin film a promising candidate to the design and application of stacked actuators, microangle-adjusting devices, and oil pressure servo valves.     

Characterization of PT ferroelectric thin films on porous silica for pyroelectric IR detectors

Ferroelectric PbTiO₃ thin films were deposited on Pt/DS/PS/SiO₂/Si substrates by sol–gel technique. Porous silica (PS) thin film was used as thermal-insulation layer and dense silica (DS) thin film was a buffer layer to reduce surface roughness of PS layer. Root mean square surface roughness can be effectively reduced from 9.7 to 3.5 nm after PS buffer layer was prepared. The average grain size of PT thin films decreased slightly with increasing thickness of porous silica. Dielectric constant of PT increased from 107 to 171 at 1 KHz as thickness of PS layer increased from 0 to 2,000 nm. PT thin film prepared on 2,000 nm porous silica exhibited good dielectric property. The leakage current density was less than 1.6?×?10^-6 A/cm² when the applied electrical field was 200 kV/cm. The composite film is suitable for preparing pyroelectric IR detectors.     

The Effect of Stress on the Microwave Dielectric Properties of Ba0.5Sr0.5TiO3 Thin Films

Single phase, (1 0 0) epitaxial Ba_0.5Sr_0.5TiO₃ (BST) films have been deposited onto (1 0 0) LaAlO₃ and MgO substrates by pulsed laser deposition (PLD). The capacitance and dielectric losses of as-deposited and annealed films have been measured from 1–20 GHz as a function of electric field (0–80 kV/cm) at room temperature. The dielectric properties are strongly affected by the substrate type, post-deposition annealing time (6 h) and temperature (1200°C). For epitaxial BST films deposited onto MgO, it is observed that, after a post-deposition anneal the dielectric constant and the dielectric loss decreases. For epitaxial BST films deposited onto LAO, a post-deposition anneal (1000°C) results in an increase in the dielectric constant and an increase in the dielectric loss. The dc electric field induced change in the dielectric constant tends to increase with the dielectric constant and is largest for as-deposited films on MgO and post-deposited annealed films on LAO. In general, for epitaxial BST films, a large electric field effect is observed in films that have a large dielectric loss and a small electric field effect in films that have a low dielectric loss. High resolution X-ray diffraction measurements indicate that deposited film exhibit a significant tetragonal distortion which is strongly affected by a by a post deposition anneal. The observed differences in dielectric properties of the epitaxial BST films on MgO and LAO are attributed to the differences in film stress which arise as a consequence of the lattice mismatch between the film and the substrate and the differences in the thermal coefficient of expansion between the film and the substrate. A thin amorphous buffer layer of BST has been used to relieve stress induced by the lattice mismatch between the film and the substrate. Unlike epitaxial films, stress relieved films do not show an inverse relationship between dielectric tuning and Q (1/tan) and may be superior materials for tunable microwave devices.     

Preparation and properties of Pb(Zr, Ti)O3 ferroelectric thin films and compositionally graded thin films on LaNiO3/Si substrates

LaNiO₃ (LNO) thin films were prepared on Si (100) wafer by MOD method. Pb(Zr, Ti)O₃ ferroelectric thin films and their compositionally graded thin films were prepared on LNO/Si (100) substrates by a modified sol–gel method. The composition depth profile of a graded film was determined by using a combination of Auger electron spectroscopy and Ar ion etching. The results confirmed that the processing method produces graded composition change. XRD analysis showed that the graded thin film possessed a composite structure of tetragonal and rhombohedral. The dielectric constant of the graded thin films was higher than that of each thin film unit, but the loss tangent was near to each other at 10 kHz. The temperature characteristics of the dielectric constant of the graded thin films at different frequencies showed three peaks and ferroelectric relaxor feature to some extent. Hysteresis loops showed that graded thin film had higher remanent polarization, smaller coercive field than each thin film unit. The pyroelectric coefficient of the graded thin films increased gradually with temperature, and was higher than that of each thin film unit.     

Frequency and Voltage Dependent Dielectric Properties of Ni-doped Ba0.6Sr0.4TiO3 Thin Films

Highly (100) preferred undoped and 1–5% Ni-doped Ba_1–xSr_xTiO₃ (BST) thin films were deposited onto MgO (100) single crystal substrate at 750°C using pulsed laser deposition. BST thin film-based interdigital capacitors (IDC) were prepared by standard photolithography process. The microwave properties of BST films were measured at 10 GHz. Ni-doped BST films showed better dielectric properties by exhibiting improved dielectric Q while retaining an appropriate capacitance tuning compared to undoped BST films. 1% Ni-doped BST film showed the maximum figure of merit of 2896.1. It is suggested that 1 mol% Ni doped BST film is an effective candidate for high performance tunable device applications.     

Ferroelectric properties of heterolayered lead zirconate titanate thin films

Heterolayered Pb(Zr_{1 − x} Ti _x )O₃ thin films consisting of alternating PbZr_0.7Ti_0.3O₃ and PbZr_0.3Ti_0.7O₃ layers were successfully deposited via a multistep sol-gel route assisted by spin-coating. These heterolayered PZT films, when annealed at a temperature in the range of 600–700^∘C show (001)/(100) preferred orientation, demonstrate desired ferroelectric and dielectric properties. The most interesting ferroelectric and dielectric properties were obtained from the six-layered PZT thin film annealed at 650^∘C, which exhibits a remanent polarization of 47.7 μC/cm² and a dielectric permittivity of 1002 at 100 Hz. Reversible polarization constituents a considerably high contribution towards the ferroelectric hysteresis of the heterolayered PZT films, as shown by studies obtained from C-V and AC measurement.     

Rf Sputtered Na0.5K0.5NbO3 Films on Oxide Substrates as Optical Waveguiding Material

Highly crystalline Na_0.5K_0.5NbO₃ (NKN) thin films of 1–2 μm thickness were deposited by rf-magnetron sputtering of a stoichiometric, ceramic target on single crystal LaAlO₃(001) and Al₂O₃(0112) substrates. X-ray diffraction measurements revealed epitaxial quality of NKN/LaAlO₃ film structures, whereas NKN films on sapphire substrates were found to be preferentially c-axis oriented. A prism-coupling technique was used to characterize optical and waveguiding properties. A bright-line spectrum at λ = 632.8 nm, revealed sharp peaks, corresponding to transverse magnetic (TM) and electric (TE) waveguide propagation modes in NKN/LaAlO₃ and NKN/Al₂O₃ thin films. Using a least mean square fit the refractive index for the films and film thickness were calculated. The extraordinary and ordinary refractive indices were determined to n _e = 2.207 ± 0.002 and n _o = 2.261 ± 0.002, and n _e = 2.216 ± 0.002 and n _o = 2.247 ± 0.002 at λ = 632.8 nm for 2.0 μm thick NKN films on LaAlO₃ and Al₂O₃, respectively. This corresponds to a birefringence Δn = n _e ? n _o = ?0.054 ± 0.003 and Δn = ?0.031 ± 0.003 in the films, where the larger Δn for the NKN/LaAlO₃ structure can be explained by the superior crystalline quality compared to NKN/Al₂O₃. Atomic force microscopy images of the film surfaces revealed rms roughnesses of 2.5 nm and 8.0 nm for 1.0-μm thick NKN/LaAlO₃ and NKN/Al₂O₃ films, respectively. We believe surface scattering is one of the main sources of waveguide losses in the thin films.     

Scaling Effect on the Dielectric Constant in Ba(Ti x Zr1−x )O3 Thin Films

Recent work on PZT and BST thin films reveal a thickness dependence of the dielectric constant for a film thickness below 100 nm. This effect is commonly attributed to an interfacial layer between the electrode and the dielectric film (dead layer). In this contribution we report on the influence of the film thickness on the dielectric constant of Ba(Ti_xZr_{1 – x})O₃ thin films with different Zr-contents (x = 0–30 at.%). The films were prepared by chemical solution deposition (CSD) with thickness between 30 and 350 nm.The electrical characterization was performed in a temperature range between 25 and 200C. Results were interpreted with respect to the formation of a serial dead layer capacitance.     

Dielectric properties for Tantalum-doped strontium barium titanate thin films prepared by sol-gel method

In this work, Sr_0.5Ba_0.5Ti_1-zTa_zO₃ (SBT) thin films were prepared on a Pt/SiO₂/Si substrate by sol-gel process. The microstructures of SBT thin films were examined by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM). The influences of Ta on the microstructure and dielectric properties of SBT thin films were studied. It is found that tetragonal perovskite crystal grains existed in SBT thin films. Ta⁵⁺ doping fines the grain of SBT thin films. It is found that Ta⁵⁺ doping decreases dielectric loss for SBT thin films.     

Processing and properties of nanocrystalline Pb(Sc0.5Ta0.5)O3, Pb(Sc0.5nb0.5)O3 and Pb(Mg1/3Nb2/3)O3 films produced by RF-sputtering from ceramic targets

Abstract

Nanocrystalline thin films of different relaxor materials, namely Pb(Sc_0.5Ta_0.5)O₃ (PST), Pb(Sc_0.5Nb_0.5)O₃(PSN), Pb(Mg_1/3Nb_2/3)O₃(PMN) have been produced by RF-sputtering to investigate whether it will affect their dielectric properties if their grain size is reduced to the dimensions known from their nanodomains. The XRD shows that the amorphous film crystallizes in pyrochlore structure at lower temperatures and short times. Annealing at higher temperatures and far longer time intervals leads to an increasing amount of perovskite phase with a grain size in the nanometer range. These results including dielectric measurements will be presented and discussed.