Leakage degradation under DC stresses in epitaxially-grown Ba1−xSrxTiO3/SrRuO3 capacitors with various top electrodes was examined. Epitaxial capacitors employed in this study exhibit higher dielectric constant arising from optimized lattice deformation caused by lattice mismatch between Ba1−xSrxTiO3 and SrRuO3; dielectric constant for SrRuO3/30nm thick Bal-xSrxTiO3/SrRuO3 all oxide capacitor was 550, which corresponds SiO2 equivalent thickness of 0.21 nm. In addition, this type of capacitors have interfaces of higher cleanliness between dielectrics and electrodes, which are expected to provide opportunities of more simplified discussions on reliability issues for thin film capacitors. Dielectric breakdown properties and DC stress-induced leakage degradation properties were examined in room temperature and elevated temperatures. Various kinds of leakage degradation were observed and categorized in anode degradation and cathode degradation. The degradation in capacitors with oxide electrodes was markedly suppressed compared to that in capacitors with metal electrodes such as Pt or Ru. This higher degradation resistance yielded longer lifetime in capacitors of this type and the estimated life time at 458K for SrRuOS/ Bal-xSrxTiO3/SrRuO3 capacitor was 3E8 seconds, which exceeds required specification for DRAM application. These differences were discussed on the basis of a supposed degradation mechanism in which oxygen vacancy generation at anode interface is taken into account as well as vacancy accumulation at cathode interface.

We have investigated the intrinsic resistance degradation behavior of fiber-textured MOCVD (Ba,Sr)TiO3 thin films appropriate for use in advanced DRAMs and integrated decoupling capacitors, as a function of applied voltage polarity, thickness, temperature, and dc bias/field. The results suggest that there is a significant stoichiometry effect on the measured resistance degradation lifetimes. The measured degradation lifetime increases as the Ti content is increased from 51.0 to 52.0 at%Ti, and then decreases with higher at%Ti. Predicted resistance degradation lifetimes obtained from both temperature and voltage extrapolations to DRAM operating conditions of 85°C and 1.6 V exceed the current benchmark of 10 years for all of the films studied.

The correlation between the dielectric constant and dispersion is investigated for barium strontium titanate (BST) capacitors with platinum and iridium electrodes. For platinum electrode capacitors, dispersion decreases with increasing dielectric constant. In contrast, capacitors with iridium electrodes exhibit the reverse correlation. A simple model is proposed to provide a quantitative explanation for the observed correlation for both platinum and iridium electrodes. In addition, the dependence of the dielectric constant and dispersion on varying ratios of (Ba+Sr)/Ti is also reported.

Barium Strontium Titanate films have been deposited by rf magnetron sputtering and have been studied with respect to Ba/Sr ratio. Physical and electrical characterization has been done as a function of temperature, thickness, and composition, and results show that dielectric constant increases with increasing temperature, thickness (up to ∼80 nm), and Ba/Sr ratio for the compositions studied. The lattice parameters for the sputtered films are larger than those expected for powder samples and also increase with increasing Ba/Sr ratio.

We have used ion implantation to dope polycrystalline BaxSr(1−x)TiO3 (BST) thin films with Mn. Dopant concentrations were varied in the range of 0.1 at % to 2 at % Mn. X-ray diffraction and TEM studies show that the implantation process significantly damages the film leaving only short range order, but subsequent rapid thermal annealing heals the damage. The effect of the different Mn dopant concentrations on the electrical properties of the complex capacitance, relaxation currents, leakage, C-V, and resistance degradation was investigated. Our initial results show that the implanted films have significantly lower leakage (up to a factor of 10 lower) than the as deposited films for small (<0.5 at % Mn) implantation doses. The capacitance decreased with increasing Mn concentration while the relaxation currents and loss tangents increased.

(Ba, Sr)TiO3 films were deposited on Pt-coated SiO2/Si wafers by the MOCVD method. Experiments were conducted to investigate the mechanisms of nucleation and growth. It was observed that the diameter of the (Ba, Sr)TiO3 grains is established in the early stages of nucleation and does not increase substantially during the growth of the film. By controlling the process conditions, it is possible to control the final microstructure and improve the electrical properties of (Ba, Sr)TiO3 films. I-V and C-V measurements show that (Ba, Sr)TiO3 films with a thickness of approximately 15nm can produce a charge storage density of >120 fF/μm2 with a leakage current density of < 10 nA/cm2 at IV, making them suitable for Gigabit-scale DRAM applications.

BST thin films have been fabricated by RF magnetron sputtering onto Ir layer as a bottom electrode. When the substrate temperature was maintained at 600 °C during deposition, BST films deposited at that temperature showed very small oxide equivalent thickness of 0.36nm as well as very low leakage current density of about 10−8A/cm2 at 1.5V. But as substrate temperature was increased to 700 °C in order to obtain high dielectric constant, oxide equivalent thickness exhibited very low value of about 0.3nm, however, leakage current density drastically increased to 10−4/cm2. BST thin films were fabricated by two step process, which consists of bottom layer deposited at high substrate temperature of 700 °C and top layer deposited at low substrate temperature. In the case of BST thin films which are composed of 20nm thick bottom layer deposited at 700 °C and 30nm thick top layer deposited at 500 °C, we obtained very small oxide equivalent thickness of 0.31nm and low leakage current density of 4 × 10−8 A/cm2. at 1.5V.

The mechanism and control of ferroelectric domain formation in heteroepitaxial (Pb1−xLax)(ZryTi1-y)O3 (PLZT) thin films grown on MgO(001) substrates have been investigated as a function of composition and temperature. Pulsed laser deposition and RF magnetron sputtering techniques were used and optimized to fabricate epitaxial thin films with varying La and/or Zr concentrations. Periodic 9° domain structures were developed when the film transformed from the cubic phase to the tetragonal phase during cooling after deposition. As a result of the tetragonality of the films, the domain formation induced slightly tilted twin structures. All films were grown highly c axis oriented and the degree of c axis orientation was improved with increasing La or Zr concentration. Experimental observations of the 90° domain evolution in films have been carried out in-situ and ex-situ using conventional and synchrotron X-ray diffraction and demonstrated that the most important parameter affecting the domain structure and its abundance is the transformation strain at the Curie temperature, which can be varied systematically by changing the concentration of La and/or Zr in the PLZT system.

Scanning force microscopy (SFM) was applied to direct nanoscale investigation of the mechanism of retention loss in ferroelectric thin films. Experiments were conducted by performing local polarization reversal within an individual grain with subsequent imaging of a resulting domain structure at various time intervals. A conductive SFM tip was used for domain switching and imaging in the SFM piezoresponse mode.

In ferroelectric thin films for capacitive and piezoelectric applications, it is important to understand which mechanisms contribute to the observed dielectric constant and piezoelectricity. In soft PZT (PbZr1−xTixO3) ceramics, over half the room temperature response is associated with domain wall contributions to the properties. However, recent studies on bulk ceramics have demonstrated that the number of domain variants within grains, and the mobility of the twin walls depend on the grain size. This leads to a degradation in the dielectric and piezoelectric properties for grain sizes below a micron. This has significant consequences for thin films since a lateral grain size of 1 μm is often the upper limit on the observed grain size. In addition, since the pertinent domain walls are ferroelastic, the stress imposed on the film by the substrate could also clamp the piezoelectric response. To investigate these factors, controlled stress levels were imposed on PZT films of different thickness while the dielectric and electromechanical properties were measured. It was found that for undoped sol-gel PZT 40/60, 52/48, and 60/40 thin films under a micron in thickness, the extrinsic contributions to the dielectric and electromechanical properties make very modest contributions to the film response. No significant enhancement in the properties was observed even when the film was brought through the zero global stress condition. Comparable results were obtained from laser ablated films grown from hard and soft PZT targets. Finally, little twin wall mobility was observed in AFM experiments. The consequences of this in terms of the achievable properties in PZT films will be presented. Work on circumventing these limitations via utilization of antiferroelectric phase switching films and relaxor ferroelectric single crystal films will also be discussed.

The ferroelectric polarization of thin films of BaxSr1−xTiO3 is imaged using confocal scanning optical microscopy (CSOM). The thin films are grown by pulsed laser deposition (PLD) on SrTiO3 substrates. Ferroelectric domain structure is imaged by applying a small ac electric field across interdigitated electrodes, and measuring induced reflectivity changes in the film, which are directly related to the polarization. Domain re-orientation is observed by acquiring CSOM images as a function of the dc electric field. Local hysteresis loops are obtained by sweeping the dc electric field at fixed positions on the sample. Micrometer-sized regions exhibit both ferroelectric and paraelectric response, indicating that thermal broadening of the phase transition is largely due to inhomogeneities in the thin films.

We present evidence for grain-boundary pinning of domain walls as controlling the electric field poling behavior of KNbO3 thin films. Two epitaxial film systems are compared: (I) film on MgO (100) substrate with KNbO3 (110)// 120Å SrTiO3 (100) //MgO(lOO) and (II) film on SrTiO3 (100) substrate with KNbO3 (110)// SrTiO3 (100). Quantitative measurement of the area fractions of four domain variants in each film system was made using in-situ second harmonic generation measurement while applying an external electric field at room temperature. While the film system (I) showed reversible domain wall motion, the film system (II) snowed some permanent poling after the removal of the external field. Transmission Electron Microscopy revealed a network of low angle grain boundaries of ∼ 1.5–2° misorientation along the substrate cubic axes in the growth plane of the film system (I) and also a network of 6° and 120° walls intersecting these grain boundaries at 45° in the film growth plane. These features were found to be absent in the film system (II). We propose that the observed electric field poling phenomena is due to the pinning of 60° and 120° domain walls by low angle grain boundaries.

Lead zirconate titanate (PZT) thin films are currently employed in non-volatile ferroelectric memories (FRAM's) and are intended to be used as the active material in a number of microelectromechanical systems (MEMS). Several groups have reported that both the piezoelectric and dielectric characteristics of ferroelectric thin films improve with an increase of film thickness, though the reasons for those improvements are unclear. Previous investigations on the effects of biaxial mechanical stress indicate that non-180° domain wall motion is limited in PZT 52/48 films less than 0.5 μm thick. It is possible that some of the improvements of the dielectric and piezoelectric characteristics reported for thicker films (i.e. films thicker than 0.5 μm) are associated with an increase of extrinsic contributions to the properties. To evaluate domain wall mobility in thicker films, the high and low-field stress response of sol-gel PZT fabricated with either rapid thermal processing or conventional furnace annealing were investigated. Films with thicknesses ranging from 0.6 to 5.0 μm thick were measured as a function of applied biaxial stress (±110 MPa). It was found that for all films tested the changes of capacitance were on the order of 2–3%. High-field measurements showed: (1) the coercive field to be insensitive to applied stress, (2) remanent polarizations to decrease about 20% at the maximum applied tension, (3) remanent polarizations to increase less than 10% with applied compression, and (4) all changes to be reversible over the stress range investigated. These results suggest that extrinsic contributions are limited for the films tested.

Thin platinum layer was used for the modification of the interface state between (Ba,Sr)TiO3 (BST) thin films and RuO2 bottom electrodes. Pt/RuO2 hybrid bottom electrodes were fabricated with various platinum deposition temperatures by a conventional dc magnetron sputtering method. Although the surface morphology and XRD patterns of BST thin films were not changed, the electrical properties of BST films deposited on Pt/RuO2 hybrid electrodes were improved compared to the films on RuO2 electrodes. Dielectric constant (εr) and leakage current density of BST thin films on Pt/RuO2 hybrid electrodes prepared at the platinum deposition temperature of 400°C were 498 and 8.6 × 10−8 A/cm2 at 1.5V, respectively.

Epitaxial YBa2Cu3O7/Ba0.5Sr0.5TiO3 (YBCO/BST) and YBCO/BaTiO3 (BTO) heterostructures were prepared by dc and rf sputtering on SrTiO3 and MgO substrates. The YBCO/BTO bilayers exhibit an inductive superconducting transition temperature of 85 K and the ferroelectric phase transition of BST shows a Curie-Weiss temperature of 310 K. Microstructure was investigated by x-ray-diffraction and atomic force microscopy. In this work we also studied the insulator's conductivity and the contribution of domain walls to permittivity.

The macroscopic polarization of ferroelectric thin films was studied by Monte Carlo simulations using a Transverse Ising Model Hamiltonian with four-spins interactions. The dependence of the ferroelectric phase transition temperature, Tc, on the thickness of the film was obtained resulting in a shifting of Tc towards lower temperatures and a change from first-order to second-order phase transition as the thickness of the film is reduced. Comparison between the surface and internal order was carried out by the calculation of layer-averaged polarizations as a function of the sample temperature and the surface interaction parameters. These comparisons show that increasing disorder at the surface can be reverted by increasing the four-spins surface interactions.

We have formed Bi-based ferroelectric films, such as Bi2WO6, Bi2VO5.5(n=1), Bi2SrTa2O9, Bi3TiNbO9(n=2) and Bi4Ti3O12(n=3) using a pulsed laser deposition technique. Especially, the Bi2VO5.5 film shows an atomically smooth surface with a flat 2000-3000Å wide terrace and steps of 8 Å and 16Å which correspond to a half and one unit cell, respectively. The dielectric constant, remanent polarization and coercive field of the Bi2VO5.5 thin films formed on Nb-SrTiO3(100) are 8, 3.0 μ C/cm2 and 16.0 kV/cm, respectively. The Bi2VO5.5 film formed on SiO2/Si(100) shows memory windows of 0.35V against a±2V gate bias during C-V measurements‥

A PbTiO3(001) film grown on MgO(001) by pulsed laser deposition is examined as an example to demonstrate the applications of the domain stability map for epitaxial perovskite films which shows regions of stable domains and fractions of domains in a polydomain structure. X-ray diffraction studies indicate that the film has a …c/a/c/a… domain structure in a temperature range of °C to 400°C with the fraction of c-domains decreasing with increasing temperature. These experimental results are in excellent agreement with theoretical predictions based on the stability map.

Reactive ion etching of PbZrxTi1−xO3 (PZT) and Pt thin films was studied by using chlorine and fluorine gas chemistry in an Inductively Coupled Plasma (ICP). PZT films were etched by varying the etching parameters including coil RF power, dc-bias voltage to substrate, and gas pressure. Etching characteristics of PZT films were investigated in terms of etch rate, etch selectivity, etch profile. Etch profile along with etch anisotropy was observed as a function of etching parameter by field emission scanning electron microscopy (FESEM). For the understanding of etching mechanism, X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma (ICP) analysis for the film composition were utilized. Platinum thin films have been etched by using Cl2/Ar in an ICP for the development offence-free etching. The redeposited materials formed on the pattern sidewall by using Cl2/Ar gas combination were analyzed by X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS). We found that the redeposited material was mainly PtCh compound. Based on this result, SiCl4/Cl2/Ar gas chemistry has been proposed as a new etching gas and demonstrated good etching profile of Pt films without unwanted redeposition.

Ferroelectric PZT thin films on thin RuO2 (10, 30, 50nm)/Pt hybrid bottom electrodes were successfully prepared by using a modified chemical solution deposition method. It was observed that the use of a lOnm RuO2Pt bottom electrode reduced leakage current, and gave more reliable capacitors with good microstructure compare to the use of thicker RuO2/Pt bottom electrodes. Typical P-E hysteresis behavior was observed even at an applied voltage of 3V, demonstrating greatly improved remanence and coercivity. Fatigue and breakdown characteristics, measured at 5V, showed stable behavior, and only below 13-15% degradation was observed up to 1010 cycles. Thicker RuO2 layers resulted in high leakage current density due to conducting lead ruthenate or PZT pyrochlore-ruthenate and a rosette-type microstructure.