Structure and properties of sol-gel processed (Pb,La)TiO3 ferroelectric thin films

Abstract

The influence of heat treatment and substrate materials on PLT thin films by sol-gel processing has been researched. Epitaxial growth PLT thin films with perovskite-type structure on sapphire, SrTiO₃ and MgO single crystal substrates have been prepared. The epitaxial relations are (100)PLT28/(100)SrTiO₃, (111)PLT28//(0001)sapphire and (100)PLT14//(100)MgO. The PLT polycrystal thin films with perovskite-type structure on Si single crystal and quartz glass substrates have been prepared. The remanent polarization Pr and the coercive field Ec of PLT15 ceramic thin films are 7.7 μc/cm² and 34 kv/cm at 4 KHz respectively. The optical transmittance of PLT28 ceramic thin films within the wavelength range of λ = 500–1000 nm is approximately 80%.     

Epitaxial growth of multilayered (Bi,La)4Ti3O12/Pb(Zr,Ti)O3 ferroelectric thin films with different orientations

Epitaxial (Bi,La)₄Ti₃O₁₂ (BLT) thin films, epitaxial Pb(Zr,Ti)O₃ (PZT) thin films, and epitaxial multilayered BLT/PZT ferroelectric thin films with different orientations were prepared on SrTiO₃ (STO) single crystal substrates by pulsed laser deposition. From X-ray pole-figures and electron diffraction patterns, the epitaxial orientation relationships between BLT layers, PZT layers, and STO substrates were identified to be (1) BLT(001)//PZT(001)//STO(001), and BLT[110]//PZT[100]//STO[100] for the multilayered thin films on (001)-oriented STO substrates, and (2) BLT(118)//PZT(011)//STO(011), and $ {\text{BLT}}{\left[ {\overline{1} \overline{1} 0} \right]}//{\text{PZT}}{\left[ {100} \right]}//{\text{SrTiO}}_{3} {\left[ {100} \right]} $ for the multilayered films on (011)-oriented STO substrates. Tri-layered films of the same compositions showed well-defined hysteresis loops as well as a high fatigue resistance up to 1?×?10¹⁰ switching cycles.     

Pb(Zr,Ti)O3 thin film growth on yttrium-treated Si(100)

Abstract

Pulsed laser ablation has been used to deposit ferroelectric Pb(Zr, Ti)O₃ (PZT) thin films on Si(100) and on yttrium-treated Si(100) substrates. The yttrium (Y) treatment of a Si surface followed by oxidation resulted in formation of a very thin, Y-enhanced SiO₂ antidiffusion barrier layer, thereby suppressing the undesirable PZT/Si interdiffusion. The best PZT film grown on Y-treated Si(100) had a breakdown voltage of 0.6 MV/cm, a coercive field of 71 KV/cm, and a remanent polarization of 18 μC/cm².     

Bilayered Pb(Zr,Ti)O3/(Bi,Nd)4Ti3O12 thin films

Bilayered thin films consisting of Pb(Zr_0.52Ti_0.48) O₃ (PZT) and (Bi_3.15Nd_0.85)Ti₃O₁₂ (BNT) layers are successfully deposited on Si(100)/SiO₂/Ti/Pt substrate by a combined process involving sol-gel and RF-sputtering. Their dielectric properties cannot be described by the simple rule of mixture on the basis of the series connection model. There occurs a dielectric layer of lower dielectric permittivity in the bilayered thin film, which degrades the polarization behaviors. The bilayered film gives rise to an improvement in fatigue resistance up to 10¹⁰ switching cycles. Moreover, the domain pinning effect after polarization switching is reduced greatly as compared to that of single layered PZT and BNT thin films.     

Structural and improved electrical properties of rare earth (Sm, Tb and Ho) doped BiFe0.975Mn0.025O3 thin films

Pure BiFeO₃ (BFO) and rare earth (RE) ion co-doped (Bi_0.9RE_0.1)(Fe_0.975Mn_0.025)O₃ (RE?=?Sm, Tb and Ho, denoted by BSFM, BTFM and BHFM) thin films were prepared on Pt(111)/Ti/SiO₂/Si(100) substrates by using a chemical solution deposition method. Formations of distorted rhombohedral perovskite structure for the thin films were confirmed by using an X-ray diffraction and a Raman scattering analysis. Microstructural features for the thin films were examined by using a scanning electron microscopic analysis. Among the thin films, the lowest leakage current density of 1.22?×?10^?6 A/cm² (at 100 kV/cm), large remnant polarization (2Pr) of 72.4 μC/cm² and low coercive field (2E _c ) of 689 kV/cm (at 980 kV/cm) were measured for the BTFM thin film.     

Enhancement of ferroelectricity in gadolinium (Gd) and transition metal (Ni, Co, Cr) Co-doped BiFeO3 thin films via a chemical solution deposition technique

The BiFeO₃ (BFO) and the gadolinium and transition metal ions co-doped (Bi_0.9Gd_0.1)(Fe_0.975 TM _0.025)O_3-δ (TM?=?Ni, Co and Cr, BGFNi, BGFCo and BGFCr) thin films were prepared on Pt(111)/Ti/SiO₂/Si(100) substrates by using a chemical solution deposition method. Compared to the pure BFO, improved electrical and ferroelectric properties were observed in the co-doped (Bi_0.9Gd_0.1)(Fe_0.975 TM _0.025)O_3-δ thin films. Among the thin films, the BGFCr thin film exhibited large remnant polarization (2P _r ), low coercive field (2E _c ), and reduced leakage current density, which are 136 μC/cm², 1360 kV/cm at 1470 kV/cm, and 5.14?×?10^-6 A/cm² at 100 kV/cm, respectively.     

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.     

Dielectric characteristics investigation of (Ba0.7Sr0.3)(Ti0.9Zr0.1)O3 ferroelectric thin films

By the radio frequency (RF) magnetron sputtering methods, (Ba_0.7Sr_0.3)(Ti_0.9Zr_0.1)O₃ (BSTZ) ferroelectric thin films were deposited on the Pt/Ti/SiO₂/Si(100) substrates. The crystal structural and microstructure of these thin films were analyzed by means of the XRD, SEM, and AFM. Moreover, the dielectric characteristics were also investigated by the C-V and J-E analyses. The optimal deposition parameters for these BSTZ thin films were: RF power is 160 W, oxygen concentration is 25%, substrate temperature is 580°C, and chamber pressure is 0.075 mPa. Under these optimal deposition conditions, the (111) and (110) oriented polycrystalline of the BSTZ thin films grow easily. And under a bias voltage of 0.5 MV/cm, the dielectric constant and leakage current density of the BSTZ thin films are 191 and 3×10^?8 A/cm², respectively. In addition, under various measured temperatures (0 ～ 80°C) and frequencies (100 kHz ～ 1 MHz), all the dielectric constants remain almost unchanged. Compared to BSTZ thin films reported previously, in this study, the deposited thin films have the advantage of lower leakage current and hence are suitable for the applications of dynamic random access memory.     

Effects of transition metal (Ni, Mn, Cu) doping on ferroelectric properties of Bi0.9Nd0.1FeO3 thin films prepared by chemical solution deposition method

Transition metal (Ni, Mn, Cu) doped Bi_0.9Nd_0.1FeO₃ thin films were prepared on Pt(111)/Ti/SiO₂/Si(100) substrates by using a chemical solution deposition method. Compared to pure BiFeO₃ (BFO) thin film, improved ferroelectric and leakage current properties were observed in the transition metal doped thin films. The values of remnant polarization (2P _r ) and coercive electric field (2E _c ) of the transition metal doped thin films were 59 μC/cm² and 690 kV/cm at 700 kV/cm for the Ni-doped Bi_0.9Nd_0.1FeO₃ thin film, 57 μC/cm² and 523 kV/cm at 670 kV/cm for the Mn-doped thin film, and 85 μC/cm² and 729 kV/cm at 700 kV/cm for the Cu-doped thin film, respectively. The 2P _r values observed in the transition metal doped thin films were much larger than that of the BFO thin film, 21 μC/cm² at 660 kV/cm. Also the 2E _c values of in the transition metal doped thin films were lower than that of the BFO thin film, 749 kV/cm at 660 kV/cm. The reduced leakage current density was observed in the transition metal doped thin films, which is approximately two orders of magnitude lower than the BFO thin film, 2.6?×?10^?3 A/cm² at 100 kV/cm.     

Effects of Heating Process on Crystalline Orientation and Electrical Properties of (Bi,La)4Ti3O12 Thin Films Derived by Chemical Solution Deposition Method

(Bi,La)₄Ti₃O₁₂ (BLT) thin films were prepared on Pt-coated Si (Pt/Ti/SiO₂/Si(100)) substrates by chemical solution deposition method. The effect of heating process on structural and electrical properties of BLT thin films was investigated. The c-axis preferentially oriented films were obtained by lower drying temperature with heating from bottom by a hot plate or IR lamp heater. On the other hand, randomly oriented films were obtained by higher drying temperature with heating from top of films by IR lamp heater or with heating substrate all around by tube type furnace. The orientation of BLT thin films deposited on Pt-coated substrates can be controlled by heating process.     

Polarization Switching in (100)/(001) Oriented Epitaxial Pb(Zr, Ti)O3 Thin Films

Thin films made of (100)/(001)-oriented Pb(Zr, Ti)O₃ (PZT) were deposited by liquid-delivery metal-organic chemical vapor deposition on Ir/MgAl₂O₄/SiO₂/Si(100) substrates. For comparison, PZT thin films were also deposited on Ir/MgO(100) substrates. The X-ray scan spectra for the (202) reflections revealed that the PZT films have four-fold symmetry. It indicates that the PZT films were epitaxially grown as a cube-on-cube structure on both substrates. The switchable polarization (Q_sw) of the PZT capacitors on the silicon substrate was only 23 C/cm² at 1.8 V; however, Q_sw of PZT capacitors on MgO was 99 C/cm². In the case of PZT films deposited on silicon, the volume fraction of (001)-oriented domains (which contribute to polarization switching) was 15.1% (calculated from an XRD pattern). This result is due to the lower Q_sw of PZT capacitors on silicon. By piezoresponse-force microscopy, switchable and unswitchable domains could be identified by imaging color contrast, namely, (001) and (100) domains, respectively. Consequently, domain distribution of the PZT film on a silicon substrate indicates that the (001) domain exists in the (100) domain matrix.     

Epitaxial thin film heterostructures of relaxor ferroelectric Pb(Mg1/3Nb2/3)O3-PbTiO3

Abstract

We have grown stoichiometric pure perovskite phase Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (PMN-PT) thin films and PMN-PT/SrRuO₃ heterostructures on miscut (100) SrTiO₃ substrates by pulsed laser deposition. X-ray diffraction θ–2θ scans show that the PMN-PT films are purely c-axis oriented. The off-axis Φ scans show that the heterostructures grow “cube-on-cube” with an in-plane epitaxial arrangement of PMN-PT[100], [010] // SrRuO₃[001] // SrTiO₃[100] and PMN-PT[010], [100] // SrRuO₃[110] // SrTiO₃[010]. The crystalline quality of the films found to be comparable to that of bulk single crystals. The AFM images show that the SrRuO₃ and PMN-PT layers have smooth surfaces with root mean square roughness of 9Å. These epitaxial heterostructures can be used for the fabrication of piezoelectric devices.     

Structural and Electrical Properties of Ba(ZrxTi1-x)O3 Films Prepared by RF-magnetron Sputtering Using Metal Targets

Ba(Zr_xTi_1-x)O₃ (BZT) thin films with different Zr contents were deposited on (100)MgO and (100)Pt/(100)MgO substrates by RF-magnetron sputtering using metal targets. The BZT thin films had a single perovskite phase with only (001)/(100) orientation. In all cases, the ratio of Ba/Ti was stoichiometry and BZT films possess a dense microstructure. The grain size was decreased and BZT thin films showed ferroelectric-to-paraelectric properties with increasing Zr content. At room temperature, the tunability of nearly 30% was achieved at 1 MHz; meanwhile, a relatively low dielectric loss was obtained. These results indicated that we succeeded in depositing high-quality and potential tunable ferroelectrics.     

Characterization of Pb(Zr,Ti)O3 thin films on SOI prepared by excimer laser deposition

Abstract

Ferroelectric Pb(Zr,Ti)O₃ (PZT) thin films were prepared by pulsed excimer laser deposition on Silicon-on-Insulator (SOI) substrates with and without an electrode. Their properties can be improved by rapid thermal annealing, based on the structural and interfacial characteristics analysis by X-ray diffraction, Rutherford backscattering spectroscopy and automatic spreading resistance measurements. The thin films were revealed of to be polycrystalline perovskite structure with mainly ?100? and ?110? orientations; the crystallite size and the structure are dependent on the annealing time. The PZT thin films did not interact with the top silicon layers of SOI, and the composition was on the tetragonal side of the morphotropic phase boundary in the PbTiO₃-PbZrO₃ phase diagram.     

Microstructures and pyroelectric properties of (Pb,La)TiO3 thin films grown on MgO and ON Pt/MgO

Abstract

Comparison has been made between the microstructures and electrical properties of Pb_0·95La_0·05TiO₃ (PLT) thin films deposited on bare (100)MgO and on Pt/(100)MgO. Nearly perfect epitaxial PLT was grown on (100)MgO. (100)-oriented Pt film was obtained via coalescence of Pt islands formed on MgO. Highly c-axis oriented PLT thin film was successfully grown on the Pt bottom electrode with an electrically conductive network structure. High detectivity of 3·5 × 10⁸ and 2·6 × 10⁸ cm√Hz/W was obtained at 30 Hz without any poling treatments from the PLT/MgO- and PLT/Pt/MgO-based infrared detectors, respectively.     

Phase Formations and Electrical Properties of Various (Bi, La)4Ti3O12 Thin Films by Chemical Solution Deposition

The phase formation and electrical properties of (Bi, La)₄Ti₃O₁₂ (BLT) thin film and V-, Sm-doped BLT thin films prepared by the chemical solution deposition method on Pt/TiO₂/SiO₂/Si substrates have been investigated. It was observed that the microstructure and electrical properties of BLT thin films dramatically varied with V- and Sm-doping. The crystallinity and grain size of BLT thin films were definitely increased by V- and Sm-doping into BLT films, which resulted in the enhancement of remanent polarization in doped BLT films. The remanent polarization (Pr) of Sm-doped BLT films annealed for 3 min by an RTA system was about 9 C/cm². The V- and Sm-doped BLT films also exhibited good fatigue characteristics under bipolar stressing to 10¹⁰ cycles.     

Preparation of Textured Growth Pb(Zr,Ti)O3 Thin Films on Si Substrate Using SrTiO3 as Buffer Layers

PZT thin films are deposited on SiO₂/Si substrate by metallo-organic decomposition (MOD) process, using SrTiO₃ (STO) as buffer layer for textured growth. The STO layers deposited on SiO₂/Si substrate by pulsed laser deposition process show (100)/(200) preferred orientation, whereas the STO buffer layer deposited on silica substrate using spin-coating technique show random orientation behavior. The use of STO as buffer layers enhanced the crystallization and the preferred orientations of the PZT films. The PZT on STO buffered SiO₂/Si substrates thus obtained possess high refractive index, (n)_PZT/STO = 2.1159, and are of good enough quality for optical waveguide applications.     

Growth and electrical properties of (211) BaTiO3 thin films on Pt-coated Si(100) substrates

Abstract

Barium titanate (BaTiO₃) thin films with high (211) orientation have been prepared on Pt(111)/Si(100) substrates by R. F. magnetron sputtering at a substrate temperature between 550°C and 580°C in an Ar/O₂ atmosphere. The I-V curve of a thin film capacitor (Ag-BaTiO_3-Pt) has been measured and the C-V curves are obtained for frequencies between 100Hz and 1MHz. Neither the I-V curve nor the C-V curves are symmetrical and a very large change in the slope of all curves is found to occur at ～+0.5v.     

Synthesis and properties of ferroelectric Si-doped (Bi, Nd)4Ti3O12 thin films by chemical solution deposition

Ferroelectric Si-doped (Bi,Nd)₄Ti₃O₁₂ thin films have been prepared on Pt/TiO_x/SiO₂/Si substrates through metal-organic compounds by the chemical solution deposition. The Bi_3.25Nd_0.75Ti_2.9Si_0.1O₁₂ (BNTS) precursor films were found to crystallize into the Bi-layered perovskite Bi₄Ti₃O₁₂ single-phase above 600^∘C. The synthesized BNTS films revealed a random orientation having a strong 117 reflection. The BNTS thin films prepared between 600^∘C and 700^∘C showed well-saturated P-E hysteresis loops with P _r of 13–14 μ C/cm² and E _c of 100–110 kV/cm at an applied voltage of 5 V. The surface roughness of the BNTS thin films was improved by Si doping compared with that of undoped Bi_3.35Nd_0.75Ti₃O₁₂ films.     

Fabrication and Characterization of Ba(Ti,Zr)O3 Thin Films Through the Chemical Solution Deposition Process

Lead- and bismuth-free Ba(Ti_{1 ? x} Zr _x )O₃ (BTZ) thin films were fabricated on Pt(111)/Ti/SiO₂/Si(100) substrates by the chemical solution deposition (CSD) process. The single phase BTZ thin films were obtained at 650°C by conventional process and the control of lattice parameter a was possible by Zr substitution. As the D-E hysteresis loops and J-V characteristics depended on the precipitates on film surface, the fabrication process was reexamined by 2-step sintering process. Consequently the decreasing of first sintering time was able to prevent the precipitates, and the larger grain of about 40–50 nm were obtained by additional sintering for 2 hour.