Beruflich Dokumente
Kultur Dokumente
Downloaded 28 Jun 2013 to 147.47.241.104. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://apl.aip.org/about/rights_and_permissions
8 OCTOBER 2001
mainly stemmed from the depletion of Bi in the surface region of the SBT layer. All these previous studies suggest that
the actual mechanism of the hydrogen-induced degradation
varies with the type of a ferroelectric capacitor involved.
In view of these, it is necessary to clearly understand the
degradation mechanism of ferroelectric properties in the Pt/
BLT/Pt capacitors during the FGA process and to establish a
convenient recovery method before they can be successfully
implemented in the practical FRAM integration process. In
this study, the degradation mechanism of the Pt/BLT/Pt capacitor was elucidated by carefully monitoring the changes
in the ferroelectric responses, the phase evolution, and the
depth profile of the capacitor before and after FGA.
The epitaxially oriented BLT thin films x0.85 were
prepared on Pt/TiO2 /SiO2 /Si substrates by metalorganic sol
deposition. Details of the sol preparation and coating procedure are described elsewhere.20 The dried films were crystallized by thermal annealing in an oxygen atmosphere at
650 C for 1 hr. The film thickness, as examined using a
field effect scanning electron microscopy was 260 nm. The
BLT film-based capacitors were fabricated by depositing top
Pt electrodes having a diameter of 100 m.
Figure 1 compares the polarizationvoltage P V hysteresis loops of the Pt/BLT/Pt capacitors before and after the
FGA 4% H2 N2 treatment. To find the roles of reducing
gases CO and N2, we also measured P V hysteresis curves
of the capacitors thermally annealed at 400 C for 10 min in
a N2 atmosphere as well as in a 4% CON2 mixture. As
presented in Fig. 1, the Pt/BLT/Pt capacitor before FGA
shows a well-saturated P V hysteresis loop. For the three
FGA temperatures above 150 C 200, 300, and 400 C, the
hysteresis loops changed drastically after FGA. The loops
after FGA show more than 104 -fold increase in the chargedisplacement susceptibility for instance, 8105 C/cm2 after FGA versus 17 C/cm2 before FGA at zero field, Fig. 1,
and the capacitor essentially becomes a conductor.
Contrary to the FGA-treated capacitor, both the BLT ca-
0003-6951/2001/79(15)/2450/3/$18.00
2450
Downloaded 28 Jun 2013 to 147.47.241.104. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://apl.aip.org/about/rights_and_permissions
2451
FIG. 1. Polarizationvoltage PV hysteresis loops of the Pt/BLT/Pt capacitors before and after FGA 4% H2 N2 mixture gas at four different
temperatures for 10 min. For the purpose of comparison, two polarization
hysteresis loops of the capacitors that are thermally annealed at 400 C for
10 min either in a pure N2 atmosphere or in a 4% CON2 gas mixture are
also presented.
FIG. 2. XRD patterns of the Pt/BLT/Pt capacitors before and after FGA: a
XRD patterns before and after thermal annealing in three different atmospheres, and b XRD patterns before and after FGA at three different temperatures for 10 min.
with K T, P
H i 2 n 2
P H2
n4
,
P H2
where K(T, P) denotes the equilibrium constant of the dissociation reaction, and the last equality in Eq. 1 comes
from the fact that H i n. Because the resistivity is
inversely proportional to the conductivity thus to n, a plot
of log() vs log(PH2) should give a linear line with a slope of
1/4. The electrical resistivity of the BLT capacitor was
measured at three different temperatures 200, 250, and
300 C as a function of the partial pressure of H2 in a H2
N2 forming gas. Although the resistivity varied substantially
with the temperature change more than one order from 200
to 300 C, the slope of the plot for log() vs. log(PH2) was
essentially independent of the equilibrium temperature and
Downloaded 28 Jun 2013 to 147.47.241.104. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://apl.aip.org/about/rights_and_permissions
2452
was 0.250.03. This indicates that the electrical degradation of the capacitor during FGA is caused by either protons
or electrons catalytically liberated from H2 by the top Pt
electrode. We are now in a position to write down the following overall degradation reaction at 400 C or above that
satisfies the results given in Fig. 2 and the resistivity data
6Bi4x Lax Ti3 O1238H 38e 6 Bi2x Lax Ti2 O7
Ti6 O1112Big19H2 Og.
FIG. 4. Depth profiles and SIMS images of the Pt/BLT/Pt capacitor: a the
depth profiles for Bi and Pt, and the mapped images b for Pt distribution
and c for Bi distribution.
Downloaded 28 Jun 2013 to 147.47.241.104. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://apl.aip.org/about/rights_and_permissions