Recent progress in sputtering PZT thin films for ferroelectric memories

Abstract

This paper describes amorphous Pb(Zr, Ti)O₃ (PZT) thin films deposited by cosputtering Pb(Zr_0.5 Ti_0.5)O₃ and PbO targets. By optimizing the amount of the excess Pb and the deposition temperature, PZT thin films with a single perovskite phase were obtained successfully on Ir substrates and Pt substrates at 520°C. 250-nm-thick PZT films crystallized by rapid thermal annealing (RTA) at 600°C for 20 s exhibited excellent ferroelectric properties: a coercive voltage of 1.0 V, a remanent polarization density of about 40 μC/cm², and a polarization switching endurance over 1x109 cycles. Although a heat treatment in a reductive ambient causes degradation of ferroelectric properties of PZT thin films, their degraded ferroelectric properties can be easily recovered from by a 1-min RTA in an oxygen at 400°C.     

Fatigue properties of Sb doped PZT thin films deposited by dc reactive sputtering

Abstract

Sb doped reactive sputtering-derived Pb(Zr, Ti)O₃ (Zr/Ti=48/52) thin films were investigated with the intention of improving ferroelectric properties. Also, the atomic valence of Sb in PZT thin film was confirmed as trivalent cation (Sb³⁺) by x-ray photoelectron spectroscopy (XPS). According to the tolerance factor t, Sb³⁺ tends to occupy the B-site of ABO₃ perovskite structure and acts as an acceptor that generates oxygen vacancies and holes. Transmission Electron Microscope(TEM) was used to observe the structural changes of PZT thin films by Sb addition. The leakage current densities and P_r of PZT thin films increased as the Sb contents increased. 0.7at% Sb doped PZT(PZST07) thin films exhibited improved fatigue properties (about 10% degradation of the remanent polarization after 10¹⁰ switching cycles).     

Effect of ion damage on the crystallization of PZT thin films

Abstract

Effects of Ar ion damage prior to the phase transformation from pyrochlore to perovskite structure of PZT thin films have been investigated. As the degree of damage increased by increasing the acceleration voltage in the ion mass doping system, the phase transformation temperature decreased such that the temperature could be lowered down to 550°C when the film was damaged at 15kV for 5 minutes. When the films were damaged prior to the heat treatment, the final grain size of the perovskite thin films became less than 300Å. The microstructure showed the granular type rather than columnar structure after ion damage treatment and annealing. It turned out that relatively high value of the remanent polarization (about 30 μC/cm²) as well as improvement of the fatigue characteristics to a large extent are closely related to the fine grain size of thus obtained PZT films.     

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.     

Sol-gel PZT thin films on nickel alloy electrodes

Abstract

The Ni alloy electrode was used for a bottom electrode of PZT thin films prepared by sol-gel process. Although PZT films were crystallized on soda–lime glass substrates with the alloy electrodes at a relatively low temperature of 500°C, second phases of Pb₃O₄ and ZrTiO₄ were produced on the electrode in addition to the perovskite PZT phase. In order to prevent the second phases forming, the heat treatment time of the electrode was increased to obtain the thicker Al₂O₃ layer on the alloy electrode. The second phases decreased with increasing the heat treatment time; however, the phases did not disappear. When BaTiO₃ films were inserted between the electrodes and PZT films, the PZT single phase was obtained. The tan δ of the films decreased with decreasing the amount of the second phases, finally it became 3.9%, the film of which possessed a remanent polarization of 20 μC/cm².     

A study of phase transformations in rapid thermal processed sol gel PZT using glancing angle x-ray diffraction

Abstract

A technique is established for depth profiling of thin film PZT using glancing angle x-ray diffraction. The transformation of PZT from the pyrochlore to perovskite phase is monitored throughout the thickness of the films. Thin film PZT was deposited using the sol gel technique. The effects of substrate, linear ramp rate, hold temperature and hold time on crystal nucleation and growth were investigated using rapid thermal annealing. The films crystallized on platinum into the perovskite phase through a highly textured interfacial region to a non-textured region at the surface, while films on ITO showed a random texture. Transforming the PZT films to perovskite and limiting the texture to the interfacial region was achieved using a ramp rate of 50°C/s and a hold time of 650°C/30s.     

NON-COLUMNAR GRAINED MICROSTRUCTURE IN FERROELECTRIC PZT THIN FILMS VIA CONCENTRATION GRADED CSD

ABSTRACT

A new kind of PZT film with non-columnar grained structure was prepared by chemical solution deposition, where PZT layers with increasing and decreasing precursors' concentration were deposited layer by layer. XRD analysis revealed the formation of perovskite phase in both thin films. However, C-V curves and P-E loops reflected different dielectric and ferroelectric properties. Different microstructures were observed in the upper part and lower part of the as prepared thin films during TEM investigation, which was attributed to different mechanisms of grain nucleation and growth process due to varied precursor concentration.     

Antiferroelectric thin and thick films for high-strain microactuators

Abstract

Niobium-doped or lanthanum-doped lead zirconate titanate stannate antiferroelectric thin and thick films have been prepared on platinum-buffered silicon substrates by a modified sol-gel method and their electric properties were characterized, with emphasis on the field-induced phase transition strains. All the films demonstrate zero remanent polarization and a maximum polarization of more than 30 μC/cm². By choosing the appropriate compositions, the films can have either “square” hysteresis loops with very sharp phase transition or “slanted” hysteresis loops with gradual phase transition. The strain levels of the thin films can reach 0.32% with smaller hysteresis or 0.42% with moderate hysteresis. The thick films can either have a strain level of 0.38% with very small hysteresis or have a strain level of 0.48% with clear digital actuator response. Hence the strain levels of these antiferroelectric films are comparable to that of bulk materials and double that of PZT ferroelectric films, and they are very promising for actuation applications in microelectromechanical systems.     

Raman,X-ray and electrical properties of MOD PZT/PLZT thin films

Abstract

Ferroelectric PZT/PLZT thin films have been fabricated using the metallo-organic precursor compounds. The structural development, spectroscopic and dielectric properties of these films have been investigated using atomic force microscopy (AFM), X-ray diffraction, Raman scattering and dielectric measurements. Experimental results show that Raman spectroscopy is an effective tool of monitoring the structural development of the small sized PZT films in the tetragonal phase field. Dielectric characteristics have been improved by the rapid thermal processing approach. A rosette growth model is proposed to explain the observation of the tri-intersection of the perovskite phase in PZT films.     

Preparation of BaPbO3 Electrode Thin Films by RF Magnetron Sputtering

For electrode materials of Pb(Zr,Ti)O₃ (PZT) thin films in ferroelectric random access memory (FeRAM), various materials have been studied. As new electrode material with which the polarization and fatigue properties are improved, we take notice of barium metaplumbate BaPbO₃ (BPO). Because the BPO contained lead (Pb) and oxygen is conductor that adopted same perovskite structure as PZT. BPO thin films were prepared by rf magnetron sputtering on various substrates. (SiO₂/Si, MgO, Al₂O₃ and Pt-coated substrates), and influence of growth conditions (sputtering gas, rf power, the substrate-heating temperature and post anneals) on crystallization and conductivity were investigated. In case of post anneal after sputtering at room temperature, perovskite single phase was obtained above 400°C. In case of substrate heating while sputtering, without post anneal, perovskite single phase was obtained at 350–500°C on SiO₂/Si substrates (110) preferred orientation BPO films obtained at low temperature, and resistivity of the films decreased at decreasing sputtering temperature. Resistivity of the film at substrate temperature 350°C was 3 × 10^?3 Ω cm. In the case of single crystal substrate, the BPO films were epitaxially grown. Orientation of the films was varied with the sputtering condition. The epitaxial PZT thin films were also grown on the BPO, revealing that PZT(111)[011] //BPO(111)[011] //Pt(100)[011] //MgO(100)[011] and PZT(111)[011] //BPO(111)[011] //Pt(111)[011] //Al₂O₃(001)[100] structures were obtained, and their ferroelectric properties were also evaluated.     

Improvement of the electrical properties of PZT thin films using TiO2 buffer layer

Abstract

Thin TiO₂ layers were sputter-deposited on Pt/Ti/SiO₂/Si wafers, as buffer layers for PZT thin film capacitors. It was found that TiO2 buffers of less than 4-nm-thickness could assist in obtaining highly uniform PZT thin films with no second phase. The leakage current behaviors of the PZT based capacitor are improved, while retaining the ferroelectric properties of PZT thin films such as remanent polarization and coercive field. In addition, the uniform distribution of oxygen in PZT on TiO₂/Pt indicates that the TiO₂ buffer layer act as a barrier for lead-platinum reaction, as well as for oxygen diffusion.     

Dielectric Characteristics of In-Plane Polarized Lead Zirconate Titanate Thin Films on Oxide Layers

Sol-gel derived lead zirconate titanate (PZT) films have been prepared on STO-passivated silicon substrates. The STO buffer layer of thickness about 55 nm is prepared by rf-magnetron sputtering. XRD results reveal that the PZT film has well-crystallized perovskite phase, indicating that the thin STO layer can effectively prevent reaction and inter-diffusion between the PZT film and silicon substrate. Interdigitated electrodes (IDEs) have then been deposited on the PZT film by magnetron sputtering and patterned using the standard photolithography. With the IDEs, the dielectric and ferroelectric properties of the PZT film under transverse or in-plane electric fields have been investigated. By assuming a uniform distribution of electric field (in-plane electric field model), the estimated relative permittivity of the PZT film is about 2100, while the dielectric loss is less than 1%. Good in-plane polarization hysteresis loop is observed, showing an observed remanent polarization value of 21 μC/cm², which is comparable to that of a PZT film with both top and bottom electrodes. The in-plane polarized PZT/STO/SiO₂/Si film can be used to fabricate d₃₃-mode unimorph bending transducers, which will have much better performance than the conventional bending transducers driven electromechanically through the piezoelectric d₃₁ mode.     

Electrical and optical properties of PZT ferroelectric films fabricated by the PVP-assisted sol-gel method

Lead zirconate titanate (PZT) films were deposited on platinized silicon substrates by spin coating using organic macromolecule polyvinylpyrrolidone (PVP) as an additive, which has the hybrid effects, was dispersed uniformly into the sol-gel precursor solution of PZT. The films were coated by spin-coating and then annealed at a proper temperature by repaid thermal processing. PZT ferroelectric films were polycrystalline and perovskite phase structure. The Coercive Field and remnant polarization of the PZT films annealed at 600 °C were 91 kV/cm and 19 μC/cm² respectively. The fatigue resistance properties were improved and the polarization value decreased only 8% of the initial polarization at 10⁸ cycles. The optical properties were measured by spectrophotometer and the band energy was calculated about 3.59eV.     

Comparing macroscopic and microscopic properties of seeded ferroelectric thin films

The comparison of macroscopic and microscopic properties of ferroelectric thin films in the systems of lead zirconate titanate (PZT) and strontium bismuth tantalate (SBT) with and without seeds is carried out. Microscopic properties were studied by piezo-response force microscopy (PFM). The local piezoelectric properties with and without seeds are compared with their macroscopic electric properties measured by conventional techniques. Previous microstructure analysis of PZT thin films showed that an intermetallic Pt _x Pb layer between PZT and Pt, formed during the annealing process, was reduced and even eliminated in seeded PZT films. In SBT films, the addition of SBT seeds suppressed the interdiffusion of Pt and film components. Hence, the interfaces of PZT/substrate and SBT/substrate are modified by the presence of seeds, and their electrical properties are improved. In both PZT and SBT films, the remanent polarization values are higher in seeded films than in unseeded ones. Similarly, local piezo-response signal of single grain showed higher longitudinal piezoelectric coefficient d ₃₃ in seeded films than in unseeded ones. The critical voltage in which the ferroelectric domain starts to switch is lower in seeded films than in unseeded ones. The analysis of nanoscale switching in PZT and SBT films by PFM is presented and related to the corresponding macroscopic electric properties.     

Electrical properties of Pb(Zr0.53Ti0.47)O3 thin film capacitors with modified RuO2 bottom electrodes

Abstract

Growth of Pb(Zr_0.53Ti_0.47)O₃ (PZT) thin films on RuO₂ electrodes by the sol-gel process is usually accompanied by the formation of second phases. The resulting RuO₂/PZT/RuO₂ capacitors are fatigue-free up to nearly 10¹¹ switching cycles, but they have high leakage currents (J～10^?3 A/cm² at 1 volt) and large property variation. We have developed several modifications of the RuO₂ bottom electrode which enhance nucleation of the perovskite phase, eliminate or reduce the second phases, and control film orientation and properties. The PZT films deposited on the modified RuO₂ electrodes have leakage current densities which are two to four orders of magnitude lower than those of PZT films deposited on the unmodified RuO₂ electrodes. In most cases, the excellent resistance to polarization fatigue which is characteristic of the RuO₂/PZT/RuO₂ capacitors, is maintained.     

EFFECTS OF PZT BUFFER LAYERS ON PZFNT FERROELECTRIC THIN FILMS

ABSTRACT

PZFNT thin films were fabricated on 5-inch Pt/Ti/SiO₂/Si and PZT/Pt/Ti/SiO₂/Si substrates by RF magnetron sputtering method and rapid thermal annealing process. By investigating the two thin films at various annealing temperatures, the results show that the annealing temperature of PZFNT thin films without PZT buffer layers is about 730°C, which is higher than that of PZFNT films with PZT buffer layers. By use of PZT buffer layers, the annealing temperature of PZFNT films is decreased greatly, and the dielectric and ferroelectric properties are improved. In the optimum process, the thin films with PZT buffer layers have a dielectric constant of 1199 and dielectric loss of 3.0% at 1 KHz. The remanent polarization and coercive field of the thin films are 21.1 μC/cm² and 53.5 KV/cm respectively. The films have the significant potential for FRAM and pyroelectric infrared detectors.     

Pyroelectric properties of sol-gel derived PZT thin films with various Zr/Ti ratios

Abstract

Integrated pyroelectric arrays are receiving serious attention for the next generation of room temperature uncooled IR cameras. Such pyroelectric arrays are based on monolithic ferroelectric(FE) thin films. FE films with large values of reported pyroelectric coefficients include PbTiO₃, Ca-doped PbTiO₃, La-doped PbTiO₃, PZT 53/47 and Pb(Sc_0.5Ta_0.5)O₃. The present paper reports a systematic study of the compositional dependence of PZT thin films on their pyroelectric properties. A series of sol-gel derived PZT (lead zirconate titanate) thin films with various Zr/Ti ratios, namely, PbTiO₃, PZT 20/80, PZT 35/65, PZT 53/47, PZT 65/35, PZT 92/8 and PbZrO₃, were prepared on platinized Si substrates. The films were fired to 650 – 700°C to crystallize them into single-phase perovskite. The degree of preferred orientation, grain size and firing temperature affect the pyroelectric responses. Pyroelectric coefficients as large as 2.5 × 10^?8 C/cm²-K were obtained, making such PZT thin films attractive in pyroelectric arrays.     

Comparison of the Electrical Characteristics of PZT and SBT Thin Films

The electrical properties of lead zirconate titanate (PZT) and strontium bismuth tantalate (SBT) thin films are compared for nonvolatile random access memory applications. PZT thin films have high switchable polarization with poor fatigue resistance and higher leakage current densities as compared to SBT thin films deposited on platinized silicon substrates. Characterization of these films in terms of their domain dynamics under application of sub-switchable and switchable electric fields give valuable insight about the observed differences in the electrical behavior. In the present work the dielectric behaviors of SBT and PZT thin films at sub-switchable electric field were analyzed in terms of Rayleigh law. The reversible and irreversible polarization component of switchable polarization was separated by the measurement of capacitance-voltage (C-V) and polarization hysteresis loops. The conduction mechanisms in these films were evaluated by measuring field dependence of leakage current densities at various temperatures. The observed differences in electrical properties are explained in terms of the intrinsic defects and defect-domain interaction of these two materials.     

Studies on piezo coefficients of PLD and sol-gel grown PZT thin film for devices

Abstract

The effect of electrical (DC) contact poling processes on the ferroelectric and piezoelectric properties of sol–gel and pulsed laser-deposited PZT thin films has been investigated as a function of the poling field, temperature and time. The remnant polarization and piezoelectric coefficient are found to increase with and saturate at dc-poling field of 100- 300?kV/cm, temperature of 100–120?°C and poling time of 10–20?min. as compared with un-poled PZT thin films. The P-E hysteresis loops of poled PLD grown PZT films shows sharper switching behaviour as compared to imbalanced loop in sol-gel grown films. An improvement of piezoelectric and ferroelectric properties of sol–gel PZT thin films is found, as compared to those deposited using pulsed laser deposition (PLD), indicating that a poling process is required for sol–gel PZT thin films.     

Single-grained PZT thin films for high level FRAM integration—fabrication and characterization

Abstract

A new method for formation of large single grains as large as 40 μm in length of the sputter-deposited PZT(65/35) thin films has been developed in this research group. Crystallized PZT dots were used as a seed and the grains were laterally grown to form a square pattern on the Pt substrate. It turned out that the electrical characteristics of the single grained PZT thin films were much superior to those of the poly-grained PZT thin films. The leakage current was measured to be less than 8x10^?8 A/cm², the breakdown field more than 1,240 kV/cm, the value of saturation polarization and remanent polarization as high as 42 μC/cm², 30 μC/cm², respectively. No degradation of the polarization properties was observed even after the 2×10¹¹ cycles at 1 MHz using a ± 10 V wave form in Pt/PZT/Pt structure. The accelerated retention test revealed that it takes more than 6×10⁷ years for the remanent polarization to be reduced down to 80% of the original value.