Effect of processing on the properties of Bi3.15Nd0.85Ti3O12 thin films

Various crystallization parameters were studied during the fabrication of Bi_3.15Nd_0.85Ti₃O₁₂ (BNdT) thin films on Pt/Ti/SiO₂/Si (100) by metal organic solution decomposition method. The effect of crystallization processes, crystallization ambients on the properties of BNdT thin films such as orientation, ferroelectric properties were examined. By adopting different fabrication processes, it is possible to get both highly c-axis oriented as well as randomly oriented thin films. Highly c-axis oriented BNdT thin film showed a large remnant polarization (2P_r) of 70 μC/cm² at an applied voltage of 10 V and exhibited a fatigue free behavior unto 2 × 10⁹ switching cycles. The improved ferroelectric properties of BNdT thin films suggest their suitability for high density ferroelectric random access memory applications.     

Modified (K0.5Na0.5)(Nb0.9Ta0.1)O3 ceramics with high Qm

Lead-free ceramics (K_0.5Na_0.5)(Nb_0.9Ta_0.1)O₃ (KNNT) + x mol% K₄CuNb₈O₂₃ (KCN) + y mol% MnO₂ have been prepared using the conventional solid-state reaction technique. Crystalline structures and Microstructures were analyzed by X-ray diffraction and scanning electron microscope (SEM) at room temperature. The low dielectric loss tanδ and relatively high piezoelectric properties were obtained when KCN and MnO₂ were added into KNNT ceramics. The ceramics with x = 1.0, y = 0.50 exhibited excellent piezoelectric properties: high mechanical quality factor Q_m = 1563, piezoelectric coefficient d₃₃ = 96pC/N, electromechanical coupling coefficient k_p = 42.2%, k_t = 44.5%, k₃₃ = 58.4%, relative dielectric constant ε′ = 308, tanδ = 0.4%. This material is a promising candidate for the lead-free piezoelectric transformer applications.     

Enhancement on effective piezoelectric coefficient of Bi3.25Eu0.75Ti3O12 ferroelectric thin films under moderate annealing temperature

Bi_3.25Eu_0.75Ti₃O₁₂ (BET) thin films were deposited on Pt/Ti/SiO₂/Si(111) substrates by a metal-organic decomposition method. The effects of annealing temperatures 600-800 °C on microstructure, ferroelectric, dielectric and piezoelectric properties of BET thin films were studied in detail. The spontaneous polarization (87.4 × 10^− 6 C/cm² under 300 kV/cm), remnant polarization (65.7 × 10^− 6 C/cm² under 300 kV/cm), the dielectric constant (992.9 at 100 kHz) and the effective piezoelectric coefficient d₃₃ (67.3 pm/V under 260 kV/cm) of BET thin film annealed at 700 °C are better than those of the others. The mechanisms concerning the dependence of the enhancement d₃₃ are discussed according to the phenomenological equation, and the improved piezoelectric performance could make the BET thin film a promising candidate for piezoelectric thin film devices.     

Enhancement on effective piezoelectric coefficient d33 of Bi3.15Dy0.85Ti3O12 ferroelectric thin films

Effects of annealing temperature (600-800 °C) on microstructure, ferroelectric and piezoelectric properties of Bi_3.15Dy_0.85Ti₃O₁₂ (BDT) thin films prepared by metal-organic decomposition were studied. The remnant polarization 2P_r and spontaneous polarization 2P_s (16.2 µC/cm² and 23.3 µC/cm² under 690 kV/cm), effective piezoelectric coefficient d₃₃ (63 pm/V under the bipolar driving field of 310 kV/cm) of BDT thin film annealed at 700 °C are better than those of others. The higher 2P_s and relatively permittivity ε_r induced by moderate annealing temperature should be responsible for the enhancement of piezoelectric properties. The improved d₃₃ may make BDT a promising candidate for piezoelectric thin film devices.     

Large electrocaloric effect of highly (100)-oriented 0.68PbMg1/3Nb2/3O3-0.32PbTiO3 thin films with a Pb(Zr0.3Ti0.7)O3/PbOx buffer layer

0.68PbMg_1/3Nb_2/3O₃-0.32PbTiO₃ (PMN-PT) thin films with a lead zirconate titanate Pb(Zr_0.3Ti_0.7)O₃ (PZT)/PbO_x buffer layer were deposited on Pt/TiO₂/SiO₂/Si substrates by radio frequency magnetron sputtering technique, and pure perovskite crystalline phase with highly (100)-preferred orientation was formed in the ferroelectric films. We found that the highly (100)-oriented thin films possess not only excellent dielectric and ferroelectric properties but also a large electrocaloric effect (13.4 K at 15 V, i.e., 0.89 K/V) which is attributed to the large electric field-induced polarization and entropy change during the ferroelectric-paraelectric phase transition. The experimental results indicate that the use of PZT/PbO_x buffer layer can induce the crystal orientation and phase purity of the PMN-PT thin films, and consequently enhance their electrical properties.     

Spray-pyrolysis Cd2SnO4 films for electrochemical applications

Conductive cadmium stannate (Cd₂SnO₄,) films were grown by a simple spray-pyrolysis technique using aerosols ultrasonically generated from solutions containing Cd(thd)₂(TMEDA) and ⁿBu₂Sn(AcAc)₂, and monoglyme as solvent (thd = 2,2,6,6-tetramethyl-3,5-heptanedionate, TMEDA = N,N,N′,N′-tetramethylethylenediamine, AcAc = acethylacetonate). The overall film growing procedure was carried out at or below 400 °C thus allowing low-melting temperature materials like glass to be used as film substrates. Typical resistivity values of Cd₂SnO₄ films were found to be ∼ 2 · 10 ⁻³ Ωcm. The films exhibit excellent electrochemical activity with comparable or higher electron transfer rates than cadmium stannate films obtained via sol-gel methods at high annealing temperature.     

Electric-field-induced strain and piezoelectric properties of a high Curie temperature Pb(In1/2Nb1/2)O3-PbTiO3 single crystal

The temperature dependence of dielectric and piezoelectric properties, electric-field-induced strains of 0.66 Pb(In_1/2Nb_1/2)O₃-0.34 PbTiO₃ single crystals, which were grown directly from melt by using the modified Bridgman technique with the allomeric Pb(Mg_2/3Nb_1/3)O₃-PbTiO₃ seed crystals, were determined as a function of crystallographic orientation with respect to the prototypic (cubic) axes. Ultrahigh piezoelectric response (d₃₃∼2000 pC/N, k₃₃∼94%) and strain levels up to 0.8%, comparable to rhombohedral (1−x)Pb(Mg_2/3Nb_1/3)O₃-xPbTiO₃ and (1−x)Pb(Zn_2/3Nb_1/3)O₃-xPbTiO₃ single crystals, were observed for the 〈0 0 1〉-oriented crystals. Strain levels up to 0.47% and piezoelectric constant d₃₃∼1600 pC/N could be achieved being related to an electric-field-induced rhombohedral-orthorhombic phase transition for the 〈1 1 0〉-oriented crystals. In addition, high electromechanical coefficients k₃₃ (∼88%) can be achieved even heating to 110 °C. High T_C (∼200 °C), large electromechanical coefficients k₃₃ (∼94%) and low dielectric loss factor (∼1%), along with large strain make the crystals promising candidates for a wide range of electromechanical transducers.     

The influence of annealing temperatures on the properties of Bi2VO5.5/LaNiO3/Si thin films

Bi₂VO_5.5 ferroelectric thin films were fabricated on LaNiO₃/Si(100) substrate via chemical solution deposition. Ferroelectric and dielectric properties of the thin films annealed at 500-700 °C were studied. The thin film annealed at 700 °C exhibited more favorable ferroelectric and dielectric properties than those annealed at lower temperatures. The values of remnant polarization 2P_r and coercive field E_c for the film annealed at 700 °C are 10.62 µC/cm² and 106.3 kV/cm, respectively. The leakage current of the film is about 1.92 × 10^− 8 A/cm² at 6 V. The possible mechanism of the dependence of electrical properties of the films on the annealing temperature was discussed.     

The synthesis of lead-free ferroelectric Bi0.5Na0.5TiO3-Bi0.5K0.5TiO3 thin films by sol-gel method

(1 − x)Bi_0.5Na_0.5TiO₃-xBi_0.5K_0.5TiO₃ [BNT-BKT-100x] thin films have been successfully deposited on Pt/Ti/SiO₂/Si substrates by a sol-gel process together with rapid thermal annealing. A morphotropic phase boundary (MPB) between Bi_0.5Na_0.5TiO₃ and Bi_0.5K_0.5TiO₃ was determined around x ∼ 0.15. Near the MPB, the film exhibits the largest grain size, the highest ε value (360) and the largest P_r value (13.8 μC/cm²). The BNT-BKT thin film system is expected to be a new and promising candidate for lead-free piezoelectric applications.     

Enhanced ferroelectric properties of Mg doped (Ba,Sr)TiO3 thick films grown on (001) SrTiO3 substrates

Highly (001)-oriented 1 mol% Mg doped (Ba_0.67,Sr_0.33)TiO₃ (BST) films with a thickness of 1.25 μm were grown on (110) SrRuO₃/(001) SrTiO₃ substrates by pulsed laser deposition. X-ray diffraction measurements reveal that the BST thick films have very high crystalline quality, and have a distorted lattice with a large tetragonality a/c = 1.012. The BST thick films have a remanent polarization (P_r) value as large as 10.1 μC/cm² and a coercive electric field (E_c) value of 65.0 kV/cm. The films possess dielectric constant and loss values of ε_r = 385.36 and tgδ = 0.038 at 1 kHz and room temperature. The leakage currents of the films are on the order of 10^− 5 A/cm² at ± 150 kV/cm. The mechanism for enhancing electric properties of the Mg doped BST films was also discussed.     

Ag and O ion irradiation induced improvement in dielectric properties of the Ba(Co1/3Nb2/3)O3 thin films

We present the preliminary results of temperature and frequency dependent dielectric measurements on Ba(Co_1/3Nb_2/3)O₃ (BCN) thin films. These films were prepared on indium tin oxide (ITO) coated glass substrates by the pulse laser deposition (PLD) technique. It exhibits single-phase hexagonal symmetry. These films were irradiated with Ag¹⁵⁺ (200 MeV) and O⁷⁺ (100 MeV) beams at the fluence 1 × 10¹¹, 1 × 10¹², and 1 × 10¹³ ions/cm². On irradiating these films, its dielectric constant (?′) and dielectric loss (tan δ) parameters improve compared to un-irradiated film. Compared to O⁷⁺ irradiation induced point/cluster defects Ag¹⁵⁺ induced columnar defects are more effective in reducing/pinning trapped charges within grains. The present paper highlights the role of swift heavy ion irradiation in engineering the dielectric properties of conductive samples to enable them to be useful for microwave device applications.     

Distribution of pyrochlore phase in Pb(Mg1/3Nb2/3)O3-PbTiO3 films and suppression with a Pb(Zr0.52Ti0.48)O3 interfacial layer

Thin films of the relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (PMN-PT) on Pt/Ti/SiO₂/Si (Pt/Si) substrates both with and without a Pb(Zr_0.52Ti_0.48)O₃ (PZT) interfacial layer were investigated. Perovskite and pyrochlore coexistence was observed for PMN-PT thin films without a PZT interfacial layer. Interestingly, most of the pyrochlore phase was observed in single-coated films and in the first layer of multi-coated films. The pyrochlore phase exhibited grains with an average size of about 25 nm, which is smaller than those of the perovskite phase (about 90 nm). In contrast, for PMN-PT thin films grown on a PZT interfacial layer, the formation of a pyrochlore phase at the interface between PMN-PT layers and the substrate is completely suppressed. Moreover, small grains are not observed in the films with a PZT interfacial layer. The measured polarization-electric field (P-E) hysteresis loops of PMN-PT films with and without PZT layers indicate that enhanced electrical properties can be obtained when a PZT interfacial layer is used. These enhanced properties include an increase in the value of remanent polarization P_r from 2.7 to 5.8 μC/cm² and a decrease in the coercive field E_c from 60.5 to 28.0 kV/cm.     

Antimony sulfide thin films in chemically deposited thin film photovoltaic cells

Antimony sulfide thin films of thickness ≈ 500 nm have been deposited on glass slides from chemical baths constituted with SbCl₃ and sodium thiosulfate. Smooth specularly reflective thin films are obtained at deposition temperatures from − 3 to 10 °C. The differences in the film thickness and improvement in the crystallinity and photoconductivity upon annealing the film in nitrogen are presented. These films can be partially converted into a solid solution of the type Sb₂S_xSe_3 − x, detected in X-ray diffraction, through heating them in contact with a chemically deposited selenium thin film. This would decrease the optical band gap of the film from ≈ 1.7 eV (Sb₂S₃) to ≈ 1.3 eV for the films heated at 300 °C. Similarly, heating at 300 °C of sequentially deposited thin film layers of Sb₂S₃-Ag₂Se, the latter also from a chemical bath at 10 °C results in the formation of AgSb(S/Se)₂ with an optical gap of ≈ 1.2 eV. All these thin films have been integrated into photovoltaic structures using a CdS window layer deposited on 3 mm glass sheets with a SnO₂:F coating (TEC-15, Pilkington). Characteristics obtained in these cells under an illumination of 850 W/m² (tungsten halogen) are as follows: SnO₂:F-CdS-Sb₂S₃-Ag(paint) with open circuit voltage (V_oc) 470 mV and short circuit current density (J_sc) 0.02 mA/cm²; SnO₂:F-CdS-Sb₂S₃-CuS-Ag(paint), V_oc ≈ 460 mV and J_sc ≈ 0.4 mA/cm²; SnO₂:F-CdS-Sb₂S_xSe_3 − x-Ag(paint), V_oc ≈ 670 mV and J_sc ≈ 0.05 mA/cm²; SnO₂:F-CdS-Sb₂S₃-AgSb(S/Se)₂-Ag(paint), V_oc ≈ 450 mV and J_sc ≈ 1.4 mA/cm². We consider that the materials and the deposition techniques reported here are promising toward developing ‘all-chemically deposited solar cell technologies.’     

Effect of CuO and MnO2 on sintering temperature, microstructure, and piezoelectric properties of 0.95(K0.5Na0.5)NbO3-0.05BaTiO3 ceramics

In this letter we report the effect of CuO and MnO₂ additives on the sintering behavior of 0.95(Na_0.5K_0.5)NbO₃-0.05BaTiO₃ ceramics. It was found that the composition corresponding to 0.95(Na_0.5K_0.5)NbO₃-0.05BaTiO₃ + 2.0 mol% CuO + 0.5 mol% MnO₂, sintered at 950 °C for 10 h, exhibited excellent piezoelectric properties corresponding to: k_p = 0.41, d₃₃ = 248 pC/N, Q_m = 305, ε₃^T/ε₀ = 1258, and T_c = 280 °C. These results indicate the prominence of this composition in lead-free systems.     

Effect of TiOx seed layer on the texture and electric properties in La and Ca modified PbTiO3 thin films

Lanthanum-and calcium-modified PbTiO₃ (PLCT) ferroelectric thin films were successfully prepared on Pt(111)/Ti/SiO₂/Si substrates by pulsed laser deposition. Influence of TiO_x seed layer on texture and electric properties of PLCT films was investigated. It is found the PLCT films without seed layer exhibited highly (100)-textured, while using about 9 nm TiO_x as seed layer lead to highly (301)-textured. The PLCT film with TiO_x seed layer possess higher remnant polarization (Pr = 26 µC/cm²), better pyroelectric coefficient and figure of merit at room temperature (p = 370 µC/m²k, F_d = 190 × 10^− 5 Pa^− 1/2) than that of film without seed layer. The mechanism of the enhanced electric properties was also discussed.     

Multiferroic properties of BiFeO3/Bi4Ti3O12 double-layered thin films fabricated by chemical solution deposition

Multiferroic BiFeO₃/Bi₄Ti₃O₁₂ (BFO/BTO) double-layered film was fabricated on a Pt(111)/Ti/SiO₂/Si(100) substrate by a chemical solution deposition method. The effect of an interfacial BTO layer on electrical and magnetic properties of BFO was investigated by comparing those of pure BFO and BTO films prepared by the same condition. The X-ray diffraction result showed that no additional phase was formed in the double-layered film, except BFO and BTO phases. The remnant polarization (2P_r) of the double-layered film capacitor was 100 μC/cm² at 250 kV/cm, which is much larger than that of the pure BFO film capacitor. The magnetization-magnetic field hysteresis loop revealed weak ferromagnetic response with remnant magnetization (2M_r) of 0.4 kA/m. The values of dielectric constant and dielectric loss of the double-layered film capacitor were 240 and 0.03 at 100 kHz, respectively. Leakage current density measured from the double-layered film capacitor was 6.1 × 10^− 7 A/cm² at 50 kV/cm, which is lower than the pure BFO and BTO film capacitors.     

Morphotropic phase boundary in high temperature ferroelectric xBi(Zn1/2Ti1/2)O3 − yPbZrO3 − zPbTiO3 perovskite ternary solid solution

A bismuth and lead oxide based perovskite ternary solid solution xBi(Zn_1/2Ti_1/2)O₃ − yPbZrO₃ − zPbTiO₃ (xBZT − yPZ − zPT) was investigated as an attempt to develop a high T_C ferroelectric material for piezoelectric sensor and actuator applications. A morphotropic phase boundary (MPB) between rhombohedral and tetragonal phases was determined through an XRD study on a pseudobinary line 0.1BZT − 0.9[xPT − (1 − x)PZ] for composition 0.1Bi(Zn_1/2Ti_1/2)O₃ − 0.5PbZrO₃ − 0.4PbTiO₃. Enhanced piezoelectric and ferroelectric activities were observed for MPB composition with dielectric constant ε_r′ ~ 23,000 at Curie temperature (T_C) ≈ 320 °C, remanent polarization (P_r) = 35 μC/cm², piezoelectric coefficient (d₃₃) = 300 pC/N, unipolar strain = 0.15%, and electromechanical coupling coefficient (k_P) = 0.45.     

Growth and characterization of (Pb,La)(Zr,Ti)O3 thin film epilayers on SrTiO3-buffered Si(001)

Ferroelectric Pb_0.92La_0.08Zr_0.4Ti_0.6O₃ (PLZT) thin films were deposited on SrTiO₃-buffered Si(001) substrate by on-axis radio frequency magnetron sputtering. X-ray diffraction analysis revealed epitaxial growth of monocrystalline PLZT films, with an (001) rocking curve full width at half maximum of ∼ 0.3°. φ-scans showed 45° in-plane orientation of the perovskite unit cell relative to that of silicon. The elemental composition of the thin film heterostructure was examined by Auger sputter depth profiling measurements. The recorded profiles suggest that the SrTiO₃ buffer layer serves not only as a template for epitaxial growth, but also as a barrier suppressing Pb-Si interdiffusion between the PLZT layer and the Si substrate. The surface roughness of the PLZT layer was measured at ∼ 4 nm for films with ∼ 500 nm thickness. Wavelength dispersions for the refractive index (n) and the extinction coefficient (k) were obtained from spectroscopic ellipsometry measurements, with n ∼ 2.48 at the main communication wavelength λ = 1550 nm and k < 0.001 for λ > 650 nm. Recorded polarization vs. electric field loops for the PLZT epilayer, with a SrRuO₃ electrode layer interposed between PLZT and SrTiO₃, showed a remnant polarization P_r ≈ 40 µC/cm² and coercive field E_c ≈ 100 kV/cm. These findings suggest that the sputter-deposited PLZT thin films retain the functional properties critical to ferroelectric and electro-optic device applications, also when integrated on a semiconductor substrate.     

Highly a-oriented SrBi2Ta2O9 thin film on (111) Pt/TiO2/SiO2/Si substrate by eclipse pulsed laser deposition

A highly a-oriented SrBi₂Ta₂O₉ thin film with a polycrystalline structure was deposited on a preferentially oriented (111) Pt/TiO₂/SiO₂/Si substrate by eclipse pulsed laser deposition (PLD) method. The SrBi₂Ta₂O₉ thin film exhibited flat and smooth surface with the surface roughness of about 0.5 nm resulting from reducing particulates generated by on-axis PLD. The SrBi₂Ta₂O₉ thin film showed a good ferroelectric property with the high remanent polarization of 12 μC/cm² and the low coercive electric field of 140 kV/cm. For the highly a-oriented SBT thin film, domain switching and reading were performed by Kelvin probe force microscope (KFM). The KFM data indicate a good ferroelectric property of the highly a-oriented SrBi₂Ta₂O₉ thin film with high KFM signals that reflect ferroelectric polarizations.     

Grazing incidence X-ray study of Ge-nanoparticle formation in (Ge:SiO2)/SiO2 multilayers

We present the study of formation of Ge-nanoparticles (Ge-NP) in germanosilicate (Ge:SiO₂) multilayer (ML) films under thermal treatment. In anticipation of controllable formation of Ge-NP, ML films were prepared by magnetron deposition at room temperature as 20 bi-layer stacks, each bi-layer comprised of a 7 nm thick layer of (Ge + SiO₂) (molar ratio: 60:40) succeeded by a 7 nm thick layer of pure SiO₂, and then annealed for 1 h, up to T_a = 900 °C. Formation and morphology of Ge-NP were analyzed by combining the information obtained from the grazing incidence small angle X-ray scattering and X-ray diffraction. It was found that precipitation of Ge-NP starts at T_a = 600 °C, while high degree of in-plane confinement and lateral ordering of rather uniform precipitated particles is achieved at T_a =  700-800 °C range. At still higher annealing temperature T_a > 800 °C, volume fraction of precipitated Ge-NP in SiO₂ matrix diminishes due to the out-diffusion of Ge atoms from the film, while Ge-NP are no more well confined to (Ge + SiO₂) layers.