S. Aggarwal

Science and technology of ferroelectric films and heterostructures for non-volatile ferroelectric memories.

We present in this article a review of the status of thin film ferroelectric materials for nonvolatile memories. Key materials issues relevant to the integration of these materials on Si wafers are discussed. The effect of film microstructure and electrode defect chemistry on the ferroelectric properties relevant to a high density nonvolatile memory technology are discussed. The second part of this review focuses on approaches to integrate these capacitor structures on a filled poly-Si plug which is a critical requirement for a high density memory technology. Finally, the use of novel surface probes to study and understand broadband polarization dynamics in ferroelectric thin films is also presented.

Effect of hydrogen on Pb(Zr,Ti)O3-based ferroelectric capacitors

The properties of ferroelectric films are known to degrade when subjected to hydrogen in forming gas anneals. Earlier studies have attributed this degradation to the loss of oxygen from these films during these anneals. In this study, we show that though oxygen is lost during forming gas annealing, hydrogen incorporation is the primary mechanism for the degradation of ferroelectric properties. Raman spectra obtained from the forming gas-annealed films show evidence of polar hydroxil [OH−] bonds in the films. The most probable site for hydrogen ions is discussed based on ionic radii, crystal structure, electrical properties, and Raman spectra. We propose that the hydrogen ion is bonded with one of the apical oxygen ions and prevents the Ti ion from switching. Pyroelectric measurements on forming gas-annealed capacitors confirm that the capacitors no longer possess spontaneous polarization.

Role of 90° domains in lead zirconate titanate thin films

We report observations of the ferroelectric domain structure in epitaxial lead zirconate titanate (PbZr0.2Ti0.8O3) ferroelectric thin films using piezoresponse microscopy. By manipulating the film thickness, a uniform two-dimensional grid of 90° domains (a domains, i.e., c axis in the plane of the film) has been induced. Our studies show that the out of plane polarization direction in the film is preferentially oriented. 90° domains have been observed as regions of low piezoresponse, as compared to the fully c axis oriented regions. We have studied the influence of these 90° domains and the domain walls on the nucleation of polarization reversal. We observe that the nucleation occurs preferentially at 90° domain interfaces. Polarization reversal is seen to occur through the nucleation and subsequent growth of “semicircular/elliptical” reverse domains, which eventually consume the entire region as a function of reversal time.

Vacancy formation in (Pb,La)(Zr,Ti)O3 capacitors with oxygen deficiency and the effect on voltage offset

Vacancy-related defect profiles have been measured for La0.5Sr0.5CoO3/(Pb0.9La0.1)(Zr0.2Ti0.8)O3/La0.5Sr0.5CoO3 ferroelectric capacitors using a variable-energy positron beam. By varying the layer thickness and the postgrowth processing in a reducing ambient, a capacitor showing oxygen deficiency dominantly in the top electrode and one with deficiency in both electrodes were produced. The capacitor with an asymmetric defect profile showed a voltage offset polarization–voltage hysteresis loop, that with a symmetric distribution of vacancy-related defects showed no offset. These results are discussed in the context of current models for imprint.

Effect of oxygen stoichiometry on the electrical properties of La0.5Sr0.5CoO3 electrodes

We report on the metal-insulator transition of La0.5Sr0.5CoO3 thin films deposited by pulsed laser ablation on LaAlO3 substrates. The films were cooled in oxygen partial pressures between 760 and 10−5 Torr and electrical resistivity of the films was measured as a function of cooling oxygen pressure. La0.5Sr0.5CoO3 films changed from metallic to insulating behavior depending on their oxygen content. A defect model has been proposed to explain this transition and the change in conductivity is related to the change in the oxidation state of the cobalt ions. The model explains the relationship between oxygen partial pressure and electrical conductivity in La0.5Sr0.5CoO3, which describes the experimental dependence reasonably well. Positron annihilation studies were also done on the same set of samples and the S parameter was seen to increase by 8% from a fully oxygenated sample to a sample cooled in 10−5 Torr.

Role of substrate on the dielectric and piezoelectric behavior of epitaxial lead magnesium niobate-lead titanate relaxor thin films

The effect of various substrates on the electrical and electromechanical properties of 100-nm-thick epitaxial 0.9[Pb(Mg1/3Nb2/3)O3]–0.1[PbTiO3](0.9PMN–0.1PT) thin films is investigated. (001) 0.9PMN–0.1PT films are grown on (001)LaAlO3(LAO), (La, Sr)(Al, Ta)O3(LSAT), SrTiO3(STO), and MgO substrates with 40-nm-thick top and bottom La0.5Sr0.5CoO3 electrodes by pulsed laser deposition. X-ray diffraction results indicate that the films on LAO, LSAT, and STO are stressed biaxially in compression in the film-substrate interface whereas the films on MgO are stressed in tension. A decrease in the temperature of dielectric maximum (Tm) together with an increase in the dielectric constant and the longitudinal piezomodulus is observed with decreasing in-plane epitaxial stresses for LAO, LSAT, and STO substrates. The films on MgO substrates have the highest dielectric constant and piezomodulus with Tm below room temperature. The variation in Tm may be attributed to the shift in the transformation temperature from the...

Scaling of ferroelectric and piezoelectric properties in Pt/SrBi2Ta2O9/Pt thin films

Scaling of the ferroelectric and piezoelectric properties in Pt/SrBi2Ta2O9/Pt thin films was studied. Focused ion beam milling was used to fabricate submicron devices (1×1, 0.5×0.5, 0.25×0.25, 0.09×0.09, and 0.07×0.07 μm2) and scanning force microscopy was used to examine their piezoelectric response. It was found that capacitors as small as 0.09×0.09 μm2 exhibit good piezoelectric/ferroelectric properties and that submicron (0.25×0.25 μm2) capacitors show resistance to bipolar fatigue with up to at least 109 cycles. The results were compared with similar capacitor structures milled in the Pb1.0(Nb0.04Zr0.28Ti0.68)O3 system where structures as small as 0.07×0.07 μm2 were analyzed.

Influence of contact electrodes on leakage characteristics in ferroelectric thin films

Electrodes can impact the device performance of ferroelectric capacitors in several ways. The present controlled studies on Pb (Nb, Zr, Ti)O3 with Pt, (La, Sr)CoO3 and SrRuO3 is a clear demonstration of the role of electrodes in impacting the leakage current mechanism of the ferroelectric capacitors and their reliability properties. The oxide electrode capacitors show predominantly nonblocking contact and good fatigue and imprint properties. Pt electrode capacitors show blocking contacts, long term leakage current relaxation, and poor fatigue and imprint properties. The nature of the temperature and voltage dependence of leakage current relaxation in Pt capacitors indicates trapping of charge carriers to be the cause for the observed relaxation. A good correlation between leakage current relaxation and the rate of polarization loss during fatigue and the similarity in their voltage and temperature dependence suggests trapping (of charged carriers/domains, respectively) as common to both phenomena.

Effect of mechanical constraint on the dielectric and piezoelectric behavior of epitaxial Pb(Mg1/3Nb2/3)O3(90%)–PbTiO3(10%) relaxor thin films

The effect of heteroepitaxy-induced constraint on the structure and piezoelectric properties of the relaxor ferroelectric lead magnesium niobate–lead titanate (PMN–PT) were investigated. Relaxor PMN–PT epitaxial thin films with oxide electrodes were grown by pulsed-laser deposition on (100) LaAlO3 substrates. We observe a systematic decrease in the phase transition temperature (temperature at which a maximum in dielectric response occurs), from around 250 to around 60 °C as the relaxor thickness is increased from 100 to 400 nm. This is accompanied by an increase in the relative dielectric constant (er), measured at room temperature and 10 kHz, from 300 to 2000. The piezoelectric coefficient d33 measured using a scanned probe microscope, increase by almost an order of magnitude with increasing film thickness.

(Ba,Sr)TiO3 thin films with conducting perovskite electrodes for dynamic random access memory applications

Interfaces and hence electrodes determine the performance of (Ba,Sr)TiO3 (BST) capacitors for ultralarge scale integration dynamic random access memories. Electrode materials forming a rectifying contact on BST drastically reduce the dielectric constant and hence the capacitance and charge storage density of the capacitor, when the dielectric thickness is reduced. This can limit the role of Pt as an electrode material for gigabit dynamic random access memories (DRAM). The conducting oxide, La0.5Sr0.5CoO3 (LSCO) with its perovskite structure, has structural and chemical compatibility with BST. Our results in LSCO/BST/LSCO capacitor show that the mechanism of conduction is not interface limited but predominantly bulk limited. A 75 nm BST film with LSCO electrodes shows a leakage current density of 1×10−7 A/cm2 at 1 V, 85 °C. The dielectric constant at 1 V, 105 Hz is 350, making LSCO a potential contact electrode for DRAM memories.