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.
We report the spontaneous formation of uniformly distributed arrays of "tips" (tall conical hillocks) upon oxidation of palladium (Pd) thin films. The formation of the palladium oxide tips depended on the thickness and granularity of the Pd film and on annealing and oxidation conditions. As the Pd film thickness increased from 40 to 200 nanometers, the average height of the tips increased from 0.5 to 1.2 micrometers, their height distribution became broader, and their density decreased from 55 x 10(6) to 12 x 10(6) per square centimeter. Enhanced photoelectron emission from locations corresponding to the tips suggests their possible use in field emission 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.
We report on the recovery of fully integrated Pb(Nb, Zr, Ti)O3 ferroelectric capacitors damaged during forming gas (4% H2, balance N2) annealing. The capacitors were encapsulated using TiOx and SiO2 as interlevel dielectrics to prevent any loss of oxygen or lead. Hydrogen, however, diffused into the ferroelectric film leading to the loss of ferroelectricity. To recover the properties of the capacitor, the fully integrated structure was annealed in N2 ambient to drive the hydrogen out. Raman scattering experiments performed in the high frequency regime to detect the [OH−] stretching vibration mode confirmed the removal of hydrogen after annealing in N2. The ferroelectric properties, including polarization and resistivity of the capacitors, were restored to their initial values prior to damage. This shows that the process of hydrogen damage is reversible with the time to recovery being dependent on the amount of hydrogen in the forming gas.
The ferroelectric properties of Pb(Zr,Ti)O3 films are known to degrade when subjected to forming gas anneals. In an earlier publication we established that although there may be loss of oxygen and lead during forming gas anneal, the primary mechanism for loss of ferroelectricity is the incorporation of hydrogen and subsequent formation of [OH]−1 bonds between the ionized hydrogen and oxygen ions along the polarization axis in the octahedra. In this study, we show that (La,Sr)CoO3 oxide electrodes can act as a diffusion barrier to hydrogen during forming gas anneals. Forming gas anneal at lower temperatures such as 200 and 300 °C does not lead to a measurable loss of polarization. There is some loss of polarization during forming gas anneals at 450 °C for 12 h, however the capacitors still exhibit ferroelectric properties. The capacitors show no fatigue up to 1011 cycles, no imprint, good logic state retention characteristics, and similar slopes for the pulse width dependent polarization values before and after forming gas anneal in the measured range. More importantly, we have demonstrated that even a bare La0.5Sr0.5CoO3 top electrode can prevent the complete loss of ferroelectricity during forming gas treatment.
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