Degradation mechanism of ferroelectric properties in Pt/Bi4-xLaxTi3O12/Pt

capacitors during forming gas annealing

Uong Chon, Ki-Bum Kim, and Hyun M. Jang
Citation: Appl. Phys. Lett. 79, 2450 (2001); doi: 10.1063/1.1402640
View online: http://dx.doi.org/10.1063/1.1402640
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APPLIED PHYSICS LETTERS

VOLUME 79, NUMBER 15

8 OCTOBER 2001

Degradation mechanism of ferroelectric properties in PtBi4- x Lax Ti3 O12 Pt

capacitors during forming gas annealing
Uong Chon,a) Ki-Bum Kim, and Hyun M. Jangb)
Department of Materials Science and Engineering, and National Research Laboratory (NRL) for
Ferroelecric Phase Transitions, Pohang University of Science and Technology (POSTECH), Pohang 790784, Republic of Korea

Received 12 March 2001; accepted for publication 13 July 2001

Degradation mechanism of ferroelectric properties in the Pt/Bi4-x Lax Ti3 O12 /Pt Pt/BLT/Pt
capacitors during forming gas annealing FGA was systematically investigated by examining
ferroelectric responses and spatial distributions of relevant species using secondary ion mass
spectrometry. It was shown that the degradation of ferroelectric properties during FGA was not
originated from the oxygen loss induced by a reducing atmosphere but was mainly caused by
protons catalytically dissociated from molecular hydrogen H2 by the top Pt electrode. The
following sequential mechanism has been identified from the present study: i the adsorption and
dissociation of H2 to produce protons and electrons by the top Pt electrode, ii the columnar
penetration of protons into the BLT film, accelerated by the region of negatively charged Bi-site
vacancies near the bottom electrode, and iii the decomposition of perovskite phase after FGA at
400 C. 2001 American Institute of Physics. DOI: 10.1063/1.1402640
The Bi4-x Lax Ti3 O12 BLT/ with x0.75 film capacitor
first reported by Park and co-workers1 has received a great
deal of attention2 because of its fatigue-free characteristics
up to 31010 read/write switching cycles. The fatigue-free
property, coupled with its relatively large remanent
polarization,3 makes the BLT one of the most promising candidates for the future nonvolatile ferroelectric random access
memories FRAM. More recently, we systematically deduced the optimum La content for the epitaxial BLT films.4
The optimized Pt/BLT/Pt capacitor with x0.85 showed improved remanent polarizations 2 P r 33 C/cm2 at 10 V and
40 C/cm2 at 15 V and fatigue-free behavior up to 6.5
1010 read/write switching cycles.
One of the most serious problems encountered in the
integration of ferroelectric capacitors to high-density FRAM
is i a disappearance of polarization hysteresis characteristics and ii a drastic increase in the leakage current during
the forming gas annealing FGA step in an H2 N2 atmosphere. Since this FGA step is necessary to passivate the
device and eliminate defects at the transistor interfaces, extensive works have been reported on this practically important subject.519
According to a series of works done by Fujisaki and
co-workers,79 the degradation of Pt/PZT/Pt capacitor, the
most widely used FRAM capacitor, is mainly originated
from the Pt/PZT-interfacial damage and the increase in the
leakage current due to the oxygen loss. More recently, Aggarwal and co-workers1012 proposed that the degradation of
ferroelectric properties during FGA was induced both by the
oxygen loss and by the formation of polar hydroxyl bonds. In
the case of the Pt/SrBi2 Ta2 O9 SBT/Pt capacitor, Im and coworkers13 suggested that the hydrogen-induced degradation

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-

Also at: Research Institute of Industrial Science and Technology RIST,

P.O. Box 135, Pohang 790-784, Republic of Korea.
b
Author to whom correspondence should be addressed; electronic mail:
hmjang@postech.ac.kr
a

0003-6951/2001/79(15)/2450/3/$18.00

2450

2001 American Institute of Physics

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Appl. Phys. Lett., Vol. 79, No. 15, 8 October 2001

Chon, Kim, and Jang

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.

pacitors and the films without the top Pt electrode annealed

in a reducing gas atmosphere of pure N2 or 4% CON2 mixture maintained characteristic well-saturated P V curves
even after the thermal treatment at 400 C for 10 min. This
clearly shows that the oxygen loss induced by the thermal
annealing in a reducing atmosphere is not likely to be the
cause of the degradation in the P V curves. From the result
shown in Fig. 1, one can conclude that the degradation of
ferroelectric properties after FGA mostly stemmed from the
effect of hydrogen contained in a forming gas.
Having identified the roles of various reducing atmospheres on the ferroelectric response, we now examine the
effects of these reducing gases on the stability of perovskite
phase. Figure 2a shows the x-ray diffraction XRD patterns of the capacitors after thermal annealing at 400 C for
10 min in three different reducing atmospheres. The Pt/
BLT/Pt capacitors after the annealing either in a pure N2 or
in a 4% CON2 atmosphere exhibit diffraction patterns that
correspond to the layered perovskite phase with the absence
of minority phases, and their XRD patterns are exactly the
same as that of the capacitor before FGA. Contrary to this,
the decomposition of perovskite phase and the formation of
pyrochlore Bi,La2Ti2O7 and oxygen-deficient Ti6O11 or
Ti6O12- are evident in the capacitor after FGA at 400 C for
10 min. This clearly indicates that, unlike other reducing
gases, hydrogen interacts with the Pt electrode specifically
and acts subsequently on the capacitor in such a unique way
that it not only degrades the ferroelectric response Fig. 1
but also expedites a complete decomposition of the perovskite phase Fig. 2.
The XRD patterns of the Pt/BLT/Pt capacitors before
and after FGA at three different temperatures for 10 min are
compared in Fig. 2b. The XRD patterns show that the perovskite phase does not decompose into Bi-deficient pyrochlore Bi,La2Ti2O7 and oxygen-deficient Ti6O11 and remains apparently stable with a negligible oxygen loss upon
the FGA treatment up to, at least, 300 C. However, as
shown in Fig. 1, the PV hysteresis curve is completely destroyed after FGA at a temperature as low as 200 C. This
clearly supports the previously made conclusion that the degradation of ferroelectric properties after FGA is not origi-

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.

nated from the oxygen loss but is mostly caused by hydrogen.

Having established the unique role of hydrogen on the
degradation of the BLT capacitor, we are going to identify
the chemical reaction that leads to the decomposition of perovskite BLT by examining the electrical resistivity of the
capacitor. Considering the well-known catalytic activity of Pt
on hydrogen molecules, we propose that protons H produced by the catalytic dissociation of hydrogen are primarily
responsible for the ferroelectric degradation in the Pt/BLT/Pt
capacitor. Then, the following equation can be established:
H2 2H i 2e

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

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2452

Appl. Phys. Lett., Vol. 79, No. 15, 8 October 2001

Chon, Kim, and Jang

FIG. 3. Three-dimensionally mapped SIMS images of protons before and

after FGA at three different temperatures for 10 min, in addition to the
image of Pt in the Pt/BLT/Pt capacitor before FGA: a Pt distribution at top
and bottom electrodes, b proton image before FGA, and proton images
after FGA c at 200 C, d at 300 C, and e at 400 C. The upper row
shows three-dimensional birds-eye views while the lower row presents the
images along the direction normal to the surface of capacitors. The area
employed in the SIMS mapping was (300300) m2.

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.

This equation predicts a loss of volatile Bi that inevitably

leaves charged vacancies at the Bi site.
We now examine the penetration characteristics of dissociated protons into the capacitor by visualizing their spatial
distribution with the help of a three-dimensional mapping
technique using a secondary ion mass spectrometer SIMS
equipped with a cesium source and a sputtering apparatus.

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.

As shown in Figs. 3c, 3d, and 3e, hydrogen species

were observed only in the columnar region covered by the
top Pt electrode, not at all in the uncovered bare BLT region.
This lucidly demonstrates the well-known catalytic dissociative adsorption of H2 by Pt8 10,13,14 and the subsequent diffusion of protons H through the film layer. The most striking feature of Fig. 3 is that the penetration of protons into the
film region has a columnar nature and that the columnar
diffusion characteristics are maintained up to 400 C. This
suggests that the penetrating protons are not disturbed by
thermal agitation but are strongly attracted by a countercharged region near the bottom electrode. In cases of
Bi4Ti3O12 /Pt and SBT/Pt films, it is well known that a substantial degree of the Bi loss occurs during the crystallization
step.21,22 In view of this, it is not unreasonable to assume that
a negatively charged region is formed near the bottom electrode by the evaporation of volatile Bi during the crystallization 650 C for 1 h and thus is characterized by the va.
cancies at the Bi site, V Bi
As presented in Fig. 4, the depth profile and the threedimensionally mapped SIMS images clearly support our
proposition that the observed unusual columnar diffusion of
protons is caused by the existence of the Bi-deficient region
and thus by the negatively charged Bi-site vacancies near the
bottom electrode. For the SIMS depth profiling, we used
as-prepared Pt/BLT/Pt capacitors without FGA to minimize a
possible disturbance in the spatial distribution of Bi and Pt.
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