Phase compositions and ferroelectric properties of Pb(Zr0.52,Ti0.48)O3 thin films with different highly orientations prepared by a sol-gel route

It is shown that different highly oriented Pb(Zr_0.52,Ti_0.48)O₃ films can be obtained on Pt/Ti/SiO₂/Si substrate using a sol-gel technique. The effects of pyrolysis temperature on the orientation, phase composition and ferroelectric properties of the films are investigated. It is found the ferroelectric hysteresis loops of (1 1 1)-oriented film, (1 1 1) and (1 0 0) mix-oriented film can both be saturated when the external electric field is large enough, whereas the hysteresis loop of (1 0 0)-oriented film is difficult to saturate. The analysis of X-ray diffraction indicated the possibility of different phase composition in different oriented films under large film residual stress. Higher remnant polarization (53 μC/cm²) for (1 0 0)-oriented film can be attributed to its more tetragonal phase composition, which results in that the in-plane domain switching can continuously occur with external electric field increasing.     

Influence of the substrate on ferroelectric properties of 〈1 1 1〉 oriented rhombohedral Pb(Zr0.6Ti0.4)O3 thin films

〈1 1 1〉-oriented Pb(Zr_0.6Ti_0.4)O₃ thin films were elaborated in the same run by RF multitarget sputtering on Si/SiO₂/TiO₂/Pt(1 1 1) and LaAlO₃/Pt(1 1 1) substrates. PZT thin films were textured, exhibiting 〈1 1 1〉 fibre texture on silicon substrates whereas epitaxial relationships were found when grown on LaAlO₃/Pt(1 1 1). On the latter substrate, values of spontaneous polarization and of dielectric permittivity were measured close to that calculated previously along the 〈1 1 1〉 direction of PZT rhombohedral single crystal. On the contrary, spontaneous polarization and dielectric permittivity measured on PZT thin films deposited on platinized silicon were found deviating from calculated values. These different electrical results are attributed to different ferroelectric domain configurations.     

Structural and electrical properties of (Na0.85K0.15)0.5Bi0.5TiO3 thin films deposited on LaNiO3 and Pt bottom electrodes

(Na_0.85K_0.15)_0.5Bi_0.5TiO₃ thin films were deposited on LaNiO₃(LNO)/SiO₂/Si(1 0 0) and Pt/Ti/SiO₂/Si(1 0 0) substrates by metal-organic decomposition, and the effects of bottom electrodes LNO and Pt on the ferroelectric, dielectric and piezoelectric properties were investigated by ferroelectric tester, impedance analyzer and scanning probe microscopy, respectively. For the thin films deposited on LNO and Pt electrodes, the remnant polarization 2P_r are about 22.6 and 8.8 μC/cm² under 375 kV/cm, the dielectric constants 238 and 579 at 10 kHz, the dielectric losses 0.06 and 0.30 at 10 kHz, the statistic d_33eff values 95 and 81 pm/V. The improved piezoelectric properties could make (Na_1−xK_x)_0.5Bi_0.5TiO₃ thin film as a promising candidate for piezoelectric thin film devices.     

Influence of plasma pressure on the growth characteristics and ferroelectric properties of sputter-deposited PZT thin films

PZT thin films of thickness (320-1040) nm were synthesized on Si/SiO₂/Ti/Pt multilayered substrates by radio frequency magnetron sputtering. The influence of plasma pressure in the range of (0.24-4.9) Pa, during deposition, on the structural, electrical and ferroelectric properties of the PZT films was systematically studied. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and cross-sectional transmission electron microscopy (XTEM) were employed for structural study. Nano-probe Energy Dispersive (EDX) line scanning was employed to investigate the elemental distribution across the film-bottom electrode interface. I-V characteristics and polarization-electric field (P-E) hysteresis loop of the films were measured. The study reveals that the plasma pressure has a strong influence on the evolution and texture of the ferroelectric perovskite phase and microstructure of the films. At an optimum plasma pressure of 4.1 Pa, PZT films are grown with 93% perovskite phase with (1 1 1) preferred orientation and uniform granular microstructure. These films show a saturation polarization of 67 μC/cm², remnant polarization of 30 μC/cm² and coercive field of 28 kV/cm which, according to the literature, seem to be suitable for device applications.Transmission electron microscopy (TEM) study shows that at a plasma pressure of 4.1 Pa, the PZT/bottom Pt interface is sharp and no amorphous interlayer is formed at the interface. At a higher plasma pressure of 4.9 Pa, poor I-V and P-E hysteresis loop are observed which are interpreted as due to an amorphous interlayer at the film-bottom electrode interface which is possibly enriched in Pb, Zr, O and Pt.     

Comparison of the effect of PLT and PZT buffer layers on PZT thin films for ferroelectric materials applications

In order to study the effect of different buffer layers on the Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films, 10-nm thick (Pb_0.72La_0.28)Ti_0.93O₃ (PLT) and Pb(Zr_0.52Ti_0.48)O₃ buffer layers have been deposited on the Pt(1 1 1)/Ti/SiO₂/Si substrates by pulsed laser deposition, respectively. The top buffer layers were also deposited on PZT thin films with the same thickness of the seed layers in order to enhance the fatigue characteristics of PZT thin films. We compared the results of dielectric constant, hysteresis loops and fatigue resistance characteristics. It was found that the dielectric properties of PZT thin films with PLT buffer layers were improved by comparing with PZT thin films with PZT buffer layers. The polarization characteristics of PZT thin films with PLT buffer layers were observed to be superior to those of PZT thin films using PZT buffer layers. The remanent polarization of PZT thin films showed 36.3 μC/cm² and 2.6 μC/cm² each in the case of use PLT and PZT buffer layers. For the switching polarization endurance analysis, PZT thin films with PLT buffer layers showed more excellent result than that of PZT thin films with PZT buffer layers.     

Ferroelectric properties of bilayer structured Pb(Zr0.52Ti0.48)O3/SrBi2Ta2O9 (PZT/SBT) thin films on Pt/TiO2/SiO2/Si substrates

Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films with large remanent polarization and SrBi₂Ta₂O₉ (SBT) thin films with excellent fatigue-resisting characteristic have been widely studied for non-volatile random access memories, respectively. To combine these two advantages_, bilayered Pb(Zr_0.52Ti_0.48)O₃/SrBi₂Ta₂O₉ (PZT/SBT) thin films were fabricated on Pt/TiO₂/SiO₂/Si substrates by chemical solution deposition method. X-ray diffraction patterns revealed that the diffraction peaks of PZT/SBT thin films were completely composed of PZT and SBT, and no other secondary phase was observed. The electrical properties of the bilayered structure PZT/SBT films have been investigated in comparison with pure PZT and SBT films. PZT/SBT bilayered thin films showed larger remanent polarization (2P_r) of 18.37 μC/cm² than pure SBT and less polarization fatigue up to 1 × 10⁹ switching cycles than pure PZT. These results indicated that this bilayered structure of PZT/SBT is a promising material combination for ferroelectric memory applications.     

Enhanced ferroelectric property of (Pb0.95Ca0.05)(Nb0.02Zr0.80Ti0.20)O3 thin films prepared by RF magnetron sputtering

(Pb_0.95Ca_0.05)(Nb_0.02Zr_0.80Ti_0.20)O₃ [PCNZT] thin films were deposited on the Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by RF magnetron sputtering with and without a LaNiO₃ [LNO] buffer layer. Ca and Nb elements in PZT films enhance the ferroelectric property, LaNiO₃ buffer layer improves the crystal quality of the PCNZT thin films. PCNZT thin films possess better ferroelectric property than that of PZT films for Ca and Nb ion substitution, moreover, PCNZT thin films with a LNO buffer layer possess (1 0 0) orientation and good ferroelectric properties with high remnant polarization (P_r = 38.1 μC/cm²), and low coercive field (E_c = 65 kV/cm), which is also better than that of PCNZT thin films without a LNO buffer layer (P_r = 27.9 μC/cm², E_c = 74 kV/cm). The result shows that enhanced ferroelectric property of PZT films can be obtained by ion substitution and buffer layer.     

Structure and electrical properties of trilayered BaTiO3/(Na0.5Bi0.5)TiO3–BaTiO3/BaTiO3 thin films deposited on Si substrate

Highly (110)-oriented trilayered BaTiO₃ (25 nm) /(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ (300 nm) / BaTiO₃ (25 nm) thin films were deposited on Pt/Ti/SiO₂/Si substrates via chemical solution deposition. It was found that the inserted bottom BaTiO₃ layer between Pt and (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ is very effective for promoting the crystallinity and (110)-oriented growth of NBT-BT films. Meanwhile, the BaTiO₃ layers also provide better interfaces between the ferroelectric thin film and the electrodes in terms of reducing leakage current. The trilayered films showed enhanced dielectric and ferroelectric properties compared with the pure NBT-BT films. Well saturated hysteresis loops were obtained due to good electrical insulating properties in the high electric field region.     

Thickness effect in Pb(Zr0.2Ti0.8)O3 ferroelectric thin films grown by pulsed laser deposition

Epitaxial Pb(Zr_,Ti)O₃ (PZT) thin films with thicknesses in the range of 50-200 nm and with 0.2 Zr/(Zr + Ti) ratio, were grown by pulsed laser deposition (PLD).The substrates used for PLD deposition are single crystalline 0.5% Nb-doped (1 0 0) SrTiO₃ (STON). SrRuO₃ (SRO) thin films were deposited as bottom and top electrodes in order to have minimum structural misfit, to insure on one side high quality growth, and on the other side to minimize the influence of the extended structural defects. Structural and electrical characterization was performed. The epitaxial PZT films are c-axis oriented and have an average roughness of 0.4 nm. The ferroelectric behavior was proved in all investigated films by the presence of the hysteresis loops and by the butterfly shape of the capacitance-voltage (C-V) characteristics. The ferroelectricity was present even in the samples with relative high leakage currents, down to a thickness of 50 nm. These results are essential when small thickness is needed for miniaturization of ferroelectric devices using PZT.     

Piezoelectric evaluation of ion beam etched Pb(Zr,Ti)O3 thin films by piezoresponse force microscopy

The evolution of piezoelectric properties of Pb(Zr,Ti)O₃ (PZT) thin films after ion beam etching have been investigated at the nanoscale level by piezoelectric force microscopy. A comparison of the piezoelectric properties on etched and unetched films is realized. Piezoelectric contrasts imaging evidences a modification of the domain architecture at the film surface. Local piezoelectric hysteresis loops measurements on grains indicate that the coercive voltage for switching is much higher for the etched films (2.3 V) compared to the unetched ones (1.0 V) while the average piezoelectric activity is slightly lower. The results are explained in terms of grain-damaging during etching and domain-wall pinning.     

A comparative study of fibre-textured and epitaxial Nb-doped Pb(Zr0.53Ti0.47)O3 thin films on different substrates

Fibre-textured and epitaxial Nb-doped Pb(Zr_0.53Ti_0.47)O₃ (PNZT) thin films were grown on the different substrates by a sol-gel process. The [1 0 0]- and [1 1 1]-fibre-textured polycrystalline PNZT films were obtained on platinized silicon substrates by introducing PbO and TiO₂ seeding layers, while the [0 0 1]- and [1 1 1]-oriented epitaxial PNZT films were formed directly on Nb-doped SrTiO₃ (Nb:STO) single-crystal substrates with (1 0 0) and (1 1 1) surfaces, respectively. The preferential orientation and phase structure of the fibre-textured and epitaxial PNZT films, as well as their influences on the electrical properties were investigated. Higher remnant polarization (P_r) and piezoelectric coefficient (d₃₃) were obtained for the epitaxial PNZT films on Nb:STO substrates than that for the fibre-textured ones on platinized silicon substrates. For both fibre-textured and epitaxial cases, the PNZT films with [1 0 0]/[0 0 1] orientations show higher piezoelectric responses than [1 1 1]-oriented ones, whereas better ferroelectric properties can be obtained in the latter. The intrinsic and extrinsic contributions were discussed to explain the difference in electrical properties for differently oriented fibre-textured and epitaxial PNZT films on different substrates.     

Properties of K0.5Bi0.5TiO3 thin films deposited on different substrates

K_0.5Bi_0.5TiO₃ thin films were deposited on fused quartz, n-type Si(100) and Pt/TiO₂/SiO₂/Si substrates by repeated coating/dying cycles. X-ray diffraction analysis shows that the films annealed at 700 °C for 10 min present perovskite phase. Atomic force microscopy reveals that the surface morphology is smooth, the grain sizes of the films on Si(100) are quite larger than on fused quartz. The capacitance-voltage hysteresis loops at various sweeping speed are collected as are polarization types. The films in the ON and OFF states are relatively stable. The films also exhibit a hysteresis loop at an applied voltage of 4 V, with a remanent polarization of 9.3 μC/cm² and a coercive voltage of 2 V. The insulating property of negative bias voltage is better than that of positive bias voltage. The transmittance of the films is between 74 and 82% in the wavelength range of 200-2000 nm.     

Substrate and orientation influence on electrical properties of sputtered La-doped PZT thin films

Pb_1−2y/3La_yZr_xTi_1−xO₃ (PLZT) thin films have been prepared “in situ” by multi-target sputtering on Silicon, LaAlO₃ (LAO) and MgO substrates covered with a Pt bottom electrode. The purpose was to grow tetragonal PLZT films (Zr/Ti = 28/72 with different La contents) on these various substrates and to compare their electrical properties. To this aim, Pt was first deposited on the three different substrates to get (1 1 1)Pt/Si, (1 1 1)Pt/LAO and (2 0 0)Pt/MgO. Then PLZT was deposited in a same run on these three kinds of substrates and the influence of La contents and film orientation on electrical properties was investigated. The La content was varied from y = 0 to y = 32 in order to explore the phase transition between ferroelectric and paraelectric phases as a function of the substrate. For large amount of Lanthanum, relaxor behavior has been observed and studied.     

Lead-free ferroelectric BaTiO3 doped-(Na0.5Bi0.5)TiO3 thin films processed by pulsed laser deposition technique

The difficulties in synthesizing phase pure BaTiO₃ doped-(Na_0.5Bi_0.5)TiO₃ are known. In this work, we reporting the optimized pulsed laser deposition (PLD) conditions for obtaining pure phase 0.92(Na_0.5Bi_0.5)TiO₃-0.08BaTiO₃, (BNT-BT_0.08), thin films. Dielectric, ferroelectric and piezoelectric properties of BNT-BT_0.08, thin films deposited by PLD on Pt/TiO₂/SiO₂/Si substrates are investigated in this paper. Perovskite structure of BNT-BT_0.08 thin films with random orientation of nanocrystallites has been obtained by deposition at 600 °C. The relative dielectric constant and loss tangent at 100 kHz, of BNT-BT_0.08 thin film with 530 nm thickness, were 820 and 0.13, respectively. Ferroelectric hysteresis measurements indicated a remnant polarization value of 22 μC/cm² and a coercive field of 120 kV/cm. The piezoresponse force microscopy (PFM) data showed that most of the grains seem to be constituted of single ferroelectric domain. The as-deposited BNT-BT_0.08 thin film is ferroelectric at the nanoscale level and piezoelectric.     

Phase evolution and effect of pre-heating temperature on the characteristics of PZT thin films grown by using a triol sol--gel route

Lead zirconate titanate (PZT) films were fabricated on Pt(111)/Ti/SiO₂/Si(100) using the triol sol--gel method. The effect of the pre-heating temperature on the phase transformations, microstructures, electrical properties and ferroelectric properties of the PZT thin films was investigated. Randomly-oriented PZT thin films pre-heated at 400°C for 10?min and annealed at 600°C for 30?min showed well-defined ferroelectric hysteresis loops with a remanent polarization of 26.57?µC?cm^?2 and a coercive field of 115.42?kV?cm^?1. The dielectric constant and dielectric loss of the PZT films were 621 and 0.0395, respectively. The microstructures of the thin films are dense, crack-free and homogeneous with fine grains about 15–20?nm in size.     

Influence of MgO and ZrO2 buffer layers on dielectric properties of Ba(Zr0.20Ti0.80)O3 thin films prepared by sol-gel processing

Ba(Zr_0.20Ti_0.80)O₃ (BZT) thin films are deposited on Pt(1 1 1)/Ti/SiO₂/Si, MgO and ZrO₂ buffered Pt(1 1 1)/Ti/SiO₂/Si substrates by a sol-gel process. The BZT thin films directly grown on Pt(1 1 1)/Ti/SiO₂/Si substrates exhibit highly (1 1 1) preferred orientation, while the films deposited on Pt(1 1 1)/Ti/SiO₂/Si substrates with MgO and ZrO₂ buffer layers show highly (1 1 0) preferred orientation. At 100 kHz, dielectric constants are 417, 311 and 321 for the BZT thin films grown on Pt(1 1 1)/Ti/SiO₂/Si, MgO and ZrO₂ buffered Pt(1 1 1)/Ti/SiO₂/Si substrates, respectively. The difference in dielectric properties of three BZT films can be attributed to the series capacitance effect, interface conditions and their orientations.     

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.     

Annealing effect of platinum-based electrodes on physical properties of PZT thin films

This study examined the crystal structure and surface morphology, including the Ti segregation mechanism on the surface due to the inter-diffusion between Pt, Ti and TiO_x as a glue layer, according to the annealing temperature and growth orientation of a Pt film. In addition, the fatigue mechanism of ferroelectric PZT thin films deposited on a Pt-based electrode was also investigated. The nano-structure, orientation mapping, and micro-morphologies of the triangular Pt hillocks were investigated by scanning electron microscopy with an electron backscatter diffraction (EBSD) function. The D–E hysteresis loop of the ferroelectric films was measured using a Sawyer–Tower circuit at 1 kHz to obtain the remanent polarization and coercive field.     

Investigation the effects of the excess Pb content and annealing conditions on the microstructure and ferroelectric properties of PZT (52-48) films prepared by sol-gel method

The effects of the PbO volatilization, excess Pb content of PbZr_0.52Ti_0.48 (PZT) precursor, PbTiO₃ (PT) seeding layers and annealing condition on the microstructures, surface morphologies, preferred orientation and ferroelectric properties of PbZr_0.52Ti_0.48 films were systematically investigated. PZT films with a variety of excess Pb (0-20%) were spin-deposited on Si(1 0 0) and Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by sol-gel technique. The films composition, Pb/Zr/Ti/O atom rate and Pb loss were semiquantitative analyzed by X-ray photoelectron spectrometer (XPS). When the excess Pb of PZT precursor was 10%, the Pb/Zr/Ti/O atomic rate of the fabricated films was very close to the designed rate of 1:0.52:0.48:3. The XRD and AFM investigations confirmed that PT seeding layer promoted the PZT films perovskite phase transformation and grains growth with (1 1 0) plane preferred orientation, accordingly lowered perovskite phase crystallization temperature and reduced Pb loss. The PZT films annealed in O₂ flow demonstrated better microstructure and ferroelectric properties comparing with films annealed in air by double remnant polarization increase and 8% coercive field increase. The underlying mechanism was also investigated.     

Transverse piezoelectric properties of Mn-doped Bi0.5Na0.5TiO3 thin films

Lead-free (Bi_0.5Na_0.5)(Ti_1-xMn_x)O₃ (BNTMn-x; x = 0, 0.0025, 0.0050, 0.0100) thin films were fabricated using a chemical solution deposition method on Pt/TiO₂/SiO₂/Si substrate. The effect of Mn substitution on crystal structures, surface morphologies, and ferroelectric and transverse piezoelectric properties of BNTMn-x thin films was investigated. The 0.5 mol% Mn-doped (Bi_0.5Na_0.5)(Ti_0.995Mn_0.005)O₃ thin film exhibited a well-saturated ferroelectric P-E hysteresis loop at room temperature. A remnant polarization (P_r) of 16 μC/cm² was obtained for the BNTMn-0.0050 film at an applied electric field of 400 kV/cm. In addition, a 1.12-μm-thick BNTMn-0.0050 film was applied as a cantilever. The Pt/BNTMn-0.0050/Pt/TiO₂/SiO₂/Si unimorph cantilever exhibited a high transverse piezoelectric coefficient ($e_{31}^1$) of 2.43 C/m².