• Transactions on Electrical and Electronic Materials
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• v.6 no.5
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• pp.214-220
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• 2005

The ferroelectric properties of the $Pt/PZT(Pb(Zr,Ti)O_3)/Pt$ capacitors are severely degraded when they are annealed in hydrogen-containing environment. Hydrogen atoms created by the catalytic reaction of Pt top electrode during annealing in hydrogen ambient penetrate into PZT films and generate oxygen vacancies by the reduction of the PZT films, which is likely to cause the degradation. The degree of hydrogen-induced degradation and the direction of voltage shift in P-E curves of the pre-poled PZT capacitors after annealing in hydrogen ambient is dependent on the polarity of the pre-poling voltage. This implies that oxygen vacancies causing hydrogen induced degradation are generated by hydrogen ions having a polarity. The degraded ferroelectricity of the PZT capacitors can be effectively recovered by the shift of oxygen vacancies toward the Pt top electrode interface during post-annealing in oxygen environment with applying negative unipolar stressing.

• Korean Chemical Engineering Research
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• v.60 no.2
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• pp.202-207
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• 2022

The study on electrode degradation of Proton Exchange Membrane Fuel Cell (PEMFC) was mainly studied on the particle growth and active area reduction of Pt on the electrode. The degradation of the electrode catalyst Pt in contact with the membrane affects the deterioration of the polymer membrane, but there are not many studies related to this. In this study, the phenomenon of the deposition of deteriorated Pt inside the polymer membrane during the accelerated electrode catalyst degradation test and its effects were studied. The voltage change (0.6 V ↔ 0.9 V) was repeated up to 30,000 cycles to accelerate the platinum degradation rate. When the voltage change cycle was repeated while oxygen was introduced into the cathode, the amount of Pt deposited inside the film was larger than when nitrogen was introduced. As the number of voltage change cycles increased, the amount of Pt deposited inside the membrane increased, and Pt dissolved in the cathode moved toward the anode, showing a uniform distribution throughout the membrane at 20,000 cycles. In the process of the accelerated electrode catalyst degradation test, the hydrogen crossover current density of the membrane did not change, and it was confirmed that the deposited Pt did not affect the durability of the membrane.

• Journal of the Microelectronics and Packaging Society
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• v.10 no.2
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• pp.49-54
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• 2003

We have investigated the effects of hydrogen annealing on the physical and electrical properties of $SrBi_{2}Ta_{2}O_9(SBT)$ thin films in the Pt/SBT/Si (MFS) structure and Pt/SBT/Pt (MFM) one, respectively. The microstructure and electrical characteristics of the SBT films were deteriorated after hydrogen annealing due to the damage of the SBT films during the annealing process. To investigate the reason of the degradation of the SBT films in this work, in particular, the effect of the Pt top electrodes, SBT thin films deposited on Si, Pt, respectively, were annealed with the same process conditions. From the XRD, XPS, P-V, and C-V data, it was seen that the SBT itself was degraded after $H_2$ annealing even without the Pt top electrodes. In addition, the degradation of the SBT films after $H_2$ annealing was accelerated by the catalytic reaction of the Pt top electrodes which is so-called hydrogen degradation. To prevent this phenomenon, we proposed the alternative top electrode material, i.e. Ir, and the electrical properties of the SBT thin films were examined in the $Ir/IrO_2/SBT/IrO_2$ structures before and after the H$_2$ annealing and recovery heat-treatment processes. From the results of the P-V measurement, it could be concluded that Ir is one of the promising candidate as the electrode material for degradation resistance in the MFM structure using SBT thin films.

• Transactions of the Korean hydrogen and new energy society
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• v.23 no.3
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• pp.256-263
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• 2012

We studied the degradation phenomenon of Pt catalyst in PEMFC. We used the electron microscope analysis technique including the ultra-microtome pretreatment method, FEG-SEM and TEM analysis methods for analysis of Pt nanoparticles. The Pt catalyst degradation is observed not only in electrode site but also in membrane site. We investigated these various degradation phenomena. The cathode electrode layer thickness is reduced. The size of the catalyst is increased much larger than initial size in membrane site. The catalyst moved from electrode layer to the electrolyte membrane. The rounded shape of catalyst was changed to the polygon. As a result, we found that the catalyst degradation processes of migration and coarsening occurred by the followings mechanisms; (1) dissolution of Pt ; (2) diffusion of Pt ion ; (3) Pt ion chemical reduction in membrane; (4) Coarsening of Pt particles (Ostwald ripening) ; (5) polygon shape change of Pt by {111} plane growth.

• Korean Chemical Engineering Research
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• v.61 no.2
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• pp.189-195
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• 2023

As a PEMFC (Polymer Exchange Membrane Fuel Cell) cathode catalyst, Pt-Co/C has recently been widely used because of its improved durability. In a fuel cell, electrodes and electrolytes have a close influence on each other in terms of performance and durability. The effect on the electrochemical durability of the electrolyte membrane when Pt-Co/C was replaced in the Pt/C electrode catalyst was studied. The durability of Pt-Co/C MEA (Membrane Electrode Assembly) was higher than that of Pt/C MEA in the electrochemical accelerated degradation process of PEMFC membrane. As a result of analyzing the FER (Fluorine Emission Rate) and hydrogen permeability, it was shown that the degradation rate of the membrane of Pt-Co/C MEA was lower than that of Pt/C MEA. In the OCV (Open Circuit Voltage) holding process, the rate of decrease of the active area of the Pt-Co/C electrode was lower than that of the Pt/C electrode, and the amount of Pt deposited on the membrane was smaller in Pt-Co/C MEA than in Pt/C MEA. Pt inside the polymer membrane deteriorates the membrane by generating radicals, so the degradation rate of the membrane of Pt/C MEA with a high Pt deposition rate was higher than Pt-Co/C MEA. When the Pt-Co/C catalyst was used, the electrode durability was improved, and the amount of Pt deposited on the membrane was also reduced, thereby improving the electrochemical durability of the membrane.

• Korean Chemical Engineering Research
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• v.61 no.3
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• pp.341-347
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• 2023

In PEMFC, PtCo/C alloy catalysts are widely used because of good performance and durability. However, few studies have been reported on the durability of carbon supports of PtCo/C evaluated at high voltages (1.0~1.5 V). In this study, the durability of PtCo/C catalysts and Pt/C catalysts were compared after applying the accelerated degradation protocol of catalyst support. After repeating the 1.0↔1.5V voltage change cycles, the mass activity, electrochemical surface area (ECSA), electric double layer capacitance (DLC), Pt dissolution and the particle growth were analyzed. After 2,000 cycles of voltage change, the current density per catalyst mass at 0.9V decreased by more than 1.5 times compared to the Pt/C catalyst. This result was because the degradation rate of the carbon support of the PtCo/C catalyst was higher than that of the Pt/C catalyst. The Pt/C catalyst showed more than 1.5 times higher ECSA reduction than the PtCo/C catalyst, but the corrosion of the carbon support of the Pt/C catalyst was small, resulting in a small decrease in I-V performance. In order to improve the high voltage durability of the PtCo/C catalyst, it was shown that improving the durability of the carbon support is essential.

• Journal of the Microelectronics and Packaging Society
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• v.11 no.4 s.33
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• pp.87-91
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• 2004

We have investigated the effects of W-N/Pt bottom electrode on the ferroelectric degradation of $Sr_{0.8}Bi_{2.4}Ta_2O_9(SBT)/Pt$ due to hydrogen annealing at $350^{\circ}C$ in $N_2$ gas atmosphere containing $5{\%}\;H_2$ gas for 1hr. As a result, inserting the W-N thin films between SBT and Pt, this W-N thin film prevents hydrogen molecules to be chemisorbed at the Pt electrode surface of at the electrode/ferroelectric interface during hydrogen annealing. These hydrogen atoms can diffuse into the SBT and react with the oxide causing the oxygen deficiency in the SBT film, which will result in the ferroelectric degradation. Experimental results show that W-N thin film is a good diffusion barrier during the hydrogen annealing.

• Korean Chemical Engineering Research
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• v.51 no.1
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• pp.68-72
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• 2013

Until a recent day, degradation of PEMFC MEA (membrane and electrode assembly) has been studied, separated with membrane degradation and electrode degradation, respectively. But membrane and electrode were degraded coincidentally at real PEMFC operation condition. During simultaneous degradation, there was interaction between membrane degradation and electrode degradation. The effect of electrode degradation on membrane degradation was studied in this work. We compared membrane degradation after electrode degradation and membrane degradation without electrode degradation. I-V performance, hydrogen crossover current, fluoride emission rate (FER), impedance and TEM were measured after and before degradation of MEA. Electrode degradation reduced active area of Pt catalyst, and then radical/$H_2O_2$ evolution rate decreased on Pt. Decrease of radical/$H_2O_2$ reduced the velocity of membrane degradation.

• Korean Chemical Engineering Research
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• v.45 no.4
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• pp.345-350
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• 2007

During PEMFC operation, OCV(open circuit voltage) and low humidity conditions accelerate the degradation of perfluorosulfonic acid membrane. There have been no studies that clearly explain why these conditions accelerate the membrane degradation. In this study, the hydrogen permeability through the membrane, I-V polarization of MEA, fluoride emission rate(FER) and $H_2O_2$ concentration in condensed water were measured during cell operation under OCV and low relative humidity(RH). The experimental results were evaluated with oxygen radical mechanism the most commonly known for membrane degradation. It seems that low RH of anode is a good condition for $H{\cdot}$ radical formation on the Pt catalyst and the OCV condition accelerate the $H{\cdot}$ to form $HO_2{\cdot}$ radical attacking the polymer membrane.

• Korean Journal of Materials Research
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• v.8 no.11
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• pp.1048-1054
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• 1998

The effects of deposition temperature of Pt top electrodes on the electrical properties of Pb(Zr,Ti))$O_3$, (PZT) thin film were investigated. When the Pt top electrodes were deposited at substrate temperatures of $200^{\circ}C$ or above,the ferroelectric properties of the PZT thin film under the Pt electrode were severely degraded. Whereas those of the PZT film where the Pt electrodes were not deposited were not degraded. Water vapors which remained in the vacuum chamber were dissociated into hydrogen atoms by the catalysis of Pt top electrode, and those hydrogen atoms diffused into the PZT film and produced oxygen vacancies at high substrate temperature, resulting in the degradation of the ferroelectric properties of the PZT film located under the Pt electrode. Since the water vapors could not be dissociated into hydrogen atoms without the catalysis of Pt. the degradation of the PZT film did not take place where the Pt electrode were not deposited. The degraded feroelectric properties could be recovered by rapid thermal annealing (RTA) treatment. On the other hand. leakage current characteristics were improved with increasing the deposition temperature of Pt top electrodes.