Yoshihisa Fujisaki

Low-voltage operation of ferroelectric poly(vinylidene fluoride-trifluoroethylene) copolymer capacitors and metal-ferroelectric-insulator-semiconductor diodes

Exceptionally low-voltage operation of organic ferroelectric capacitors and diodes was demonstrated. Ferroelectric polyvinylidene fluoride-trifluoroethylene [P(VDF-TrFE)] thin films were prepared by the solvent-cast method. Metal-ferroelectric-metal capacitors with 60-nm-thick P(VDF-TrFE) films exhibited well-saturated hysteresis curves whose coercive voltage (Vc) and remanent polarization (Pr) were 2.0V and 11.9μC∕cm2, respectively. The authors also fabricated metal-ferroelectric-insulator-semiconductor diodes with 100-nm-thick P(VDF-TrFE) films. Rectangular-shaped capacitance-voltage (C-V) hysteresis loops were obtained with a voltage sweep range narrower than 5V. The maximum memory window of 4.7V was achieved.

H2 DAMAGE OF FERROELECTRIC PB(ZR,TI)O3 THIN-FILM CAPACITORS : THE ROLE OF CATALYTIC AND ADSORPTIVE ACTIVITY OF THE TOP ELECTRODE

Large-scale integrated fabrication in a H2 containing atmosphere, for example, during the passivation process, can cause serious damage in metal/Pb(Zr,Ti)O3/metal capacitors (i.e., Pt/PZT/Pt capacitors). To reveal the cause of the H2 damage, we investigated the behavior of hysteresis curves and the leakage current of capacitors with a top electrode of Pt, Pd, Au, or Ag. Capacitors with a top electrode of Au or Ag are more resistant to the H2 annealing damage than those of Pt or Pd. We found that the H2 damage was strongly affected by the catalytic activity and adsorptive properties of the top electrode when exposed to H2.

Electrode‐induced degradation of Pb(ZrxTi1−x)O3 (PZT) polarization hysteresis characteristics in Pt/PZT/Pt ferroelectric thin‐film capacitors

One of the most serious forms of damage that occurs during the integration of Pt/PZT/Pt ferroelectric capacitors [where PZT is Pb(ZrxTi1−x)O3] is the disappearance of polarization hysteresis characteristics during the passivation process. The hydrogen content of the atmosphere during this process affects the ferroelectric capacitor characteristics. However, the PZT film itself is not damaged by annealing in a hydrogen‐containing atmosphere even at 400 °C, whereas the Pt/PZT/Pt ferroelectric capacitor loses its polarization hysteresis characteristics at 300 °C. The top Pt electrode was found to induce this damage. Possible mechanisms such as stress and a chemical reaction with the Pt catalyst are discussed.

Review of Emerging New Solid-State Non-Volatile Memories

The integration limit of flash memories is approaching, and many new types of memory to replace conventional flash memories have been proposed. Unlike flash memories, new nonvolatile memories do not require storage of electric charges. The possibility of phase-change random-access memories (PCRAMs) or resistive-change RAMs (ReRAMs) replacing ultrahigh-density NAND flash memories has been investigated; however, many issues remain to be overcome, making the replacement difficult. Nonetheless, ferroelectric RAMs (FeRAMs) and magnetoresistive RAMs (MRAMs) are gradually penetrating into fields where the shortcomings of flash memories, such as high operating voltage, slow rewriting speed, and limited number of rewrites, make their use inconvenient. For instance, FeRAMs are widely used in ICs that require low power consumption such as smart cards and wireless tags. MRAMs are used in many kinds of controllers in industrial equipment that require high speed and unlimited rewrite operations. For successful application of new non-volatile semiconductor memories, such memories must be practically utilized in new fields in which flash memories are not applicable, and their technologies must be further developed.

Current Status of Nonvolatile Semiconductor Memory Technology

In this report, an overview of the current status of nonvolatile semiconductor memory technology is presented. We are reaching the integration limit of flash memories, and many new types of memories to replace conventional flash memories have been proposed. Unlike flash memories, new nonvolatile memories do not require electric charge storing. The possibility of phase-change random access memory (PRAM) or resistive-change RAM (ReRAM) replacing ultrahigh-density NAND flash memories has been discussed; however, there are many issues to overcome, making the replacement difficult. Nonetheless, ferroelectric RAMs (FeRAMs) and MRAMs are gradually penetrating into fields where the shortcomings of flash memories, such as high operating voltage, slow rewriting speed, and limited number of rewrites, make their use inconvenient. For the successful application of new nonvolatile semiconductor memories, they must be practically utilized in new fields in which flash memories are not applicable, and the technology for them must be developed.

The effects of the catalytic nature of capacitor electrodes on the degradation of ferroelectric Pb(Zr,Ti)O3 thin films during reductive ambient annealing

The disappearance of ferroelectricity in Pb(Zr0.52,Ti0.48)O3 (PZT) thin-film capacitors, which is caused by heat treatment in a reductive ambience, is investigated. Bare PZT films are not damaged by annealing in a hydrogen-containing atmosphere (H2 annealing) up to 400 °C, whereas a PZT capacitor with Pt electrodes loses its ferroelectricity during annealing at less than 300 °C. We have found that the degradation of ferroelectricity depends upon the metal used for the top electrode of the PZT capacitor. The increased degradation in the case of a PZT capacitor with Pt electrodes can be explained by a catalytic reaction on the Pt surface. We have made the ferroelectricity of a Pt/PZT/Pt capacitor retained even after the H2 annealing at 300 °C, or above, simply by oxidizing it before the H2 annealing.

The flexible non-volatile memory devices using oxide semiconductors and ferroelectric polymer poly(vinylidene fluoride-trifluoroethylene)

We demonstrated flexible ferroelectric gate thin-film transistors (Fe-TFTs) with ferroelectric polymer poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] and amorphous indium gallium zinc oxide (a-IGZO) channel on the polyethylene-naphthalate (PEN) substrate. First, we confirm basic ferroelectric properties of the P(VDF-TrFE) film on the PEN substrate with various bending radius. Next, we fabricated Fe-TFTs with Al/120 nm-P(VDF-TrFE)/40 nm-IGZO top gate structure. Excellent electrical characteristics are demonstrated and nonvolatile memory function was confirmed with a memory window of 8.4 V. A subthreshold voltage swing of 400 mV/decade, Ion/Ioff ratio of more than 107 and the field-effect mobility of ∼1 cm2/Vs were obtained.

Post-annealing effects on antireduction characteristics of IrO2/Pb(ZrxTi1−x)O3/Pt ferroelectric capacitors

Antireduction characteristics of IrO2/Pb(ZrxTi1−x)O3(PZT)/Pt ferroelectric capacitors are improved by post annealing. When an as-processed capacitor receives a 3% hydrogen annealing at 300 °C (a process condition for fabricating the interlayer dielectric), capacitor characteristics are heavily degraded. This is because Ir that is produced by IrO2 reduction plays a catalytic role in PZT reduction. By contrast, if the IrO2/PZT/Pt capacitor is post annealed in O2 atmosphere at 600 °C for 1 h, the capacitor characteristics can be maintained even if it undergoes the hydrogen annealing. The O2 annealing improves the crystallinity of the IrO2 top electrode and excess PbOx in sol-gel derived PZT diffuses into the IrO2 film. As a result, antireduction characteristics of the IrO2 top electrode itself are drastically improved and the PZT film becomes stoichiometric at the same time. Exclusion of excess PbOx in PZT results in an increase in spontaneous polarization of the IrO2/PZT/Pt ferroelectric capacitor. Furtherm...

Hydrogen-related degradation and recovery phenomena in Pb(Zr,Ti)O3 capacitors with a platinum electrode

Pb(Zr,Ti)O3 capacitors with top platinum electrodes area subjected to hydrogen annealing from 300°C to 450°C. Both the remnant polarization and breakdown voltage were drastically degraded after hydrogen annealing, whereas the dielectric constant was found to be relatively stable. Capacitors recovered their characteristics before annealing after re-oxidation treatment. An interfacial degradation model with a platinum-catalysis reduction is proposed to explain these notable degradation phenomena.

Organic Ferroelectric Diodes with Long Retention Characteristics Suitable for Non-Volatile Memory Applications

Retention performance of organic metal–ferroelectric–insulator–semiconductor (MFIS) diodes composed of random copolymer poly(vinylidene fluoride)-trifluoroethylene [P(VDF-TrFE)] was drastically improved by introducing poly(methyl methacrylate) (PMMA). Only a small amount of PMMA blended to P(VDF-TrFE) copolymer improved the insulating property of thin ferroelectric films. The MFIS diode with 1.65 wt % PMMA-blended P(VDF-TrFE) film achieved the retention time longer than 106 s until now and it showed no obvious degradation of switching charge. Precise control of PMMA composition and the crystallization condition made it possible to achieve the above mentioned performance.