RESEARCH ARTICLE | JULY 02 2007

Large-area pulsed-laser deposition of dielectric and

ferroelectric thin films 
Shigeki Sakai; Mitsue Takahashi; Kennichi Motohashi; Yuji Yamaguchi; Naomasa Yui; Takichi Kobayashi

J. Vac. Sci. Technol. A 25, 903–907 (2007)

https://doi.org/10.1116/1.2748808

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31 January 2024 07:23:07

Large-area pulsed-laser deposition of dielectric and ferroelectric thin films
Shigeki Sakai,a兲 Mitsue Takahashi, Kennichi Motohashi, Yuji Yamaguchi,
Naomasa Yui, and Takichi Kobayashi
National Institute of Advanced Industrial Science and Technology, Central 2, 1-1-1, Umezono, Tsukuba,
Ibaraki, 305-8568, Japan
共Received 6 October 2006; accepted 21 May 2007; published 2 July 2007兲
The authors have developed a large-area pulsed-laser deposition 共PLD兲 technique, suited in
particular for depositing high-k dielectric and ferroelectric thin films of high quality on Si wafers of
8 in. diameter. By using this technique, 42- and 6-nm-thick HfO2 films were deposited on 8 and
6 in. Si wafers at room temperature, respectively. The standard deviations of thickness were 1.3%
and 1.6% of their respective means. Cross-sectional transmission-electron microscopy pictures of
the 6-nm-thick HfO2 film on Si showed that an interfacial layer between HfO2 and Si was thinner
than 1 nm. In order to measure the electrical properties, Pt top electrodes were deposited on the
HfO2 film and the Al bottom electrode was deposited on the Si. Capacitance-voltage measurements
of the Pt/ HfO2 / Si showed that the standard deviation of capacitances was as small as 1.9%. A
ferroelectric SrBi2Ta2O9 共SBT兲 film was also deposited on a 4 in. Si wafer at 400 ° C using the
large-area PLD technique. The standard deviation of the SBT film thickness was 1.2% of 94 nm, the
average thickness. The large-area PLD technique the authors developed can meet the industrial
needs for high and uniform quality over large-area high-k dielectric and/or ferroelectric thin films
for large-scale integrated circuits. © 2007 American Vacuum Society. 关DOI: 10.1116/1.2748808兴

I. INTRODUCTION same thickness were set in a target holder, which was tilted
30° against the substrate holder. Silicon wafers from
Pulsed-laser deposition 共PLD兲 is a successful method for
4 to 8 in. in diameter could be set in the substrate holder.

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obtaining high-quality films of various kinds of materials and
Since the incident laser beam was parallel to the substrate
has the advantage of clean deposition without impurities of
surface, the beam was not blocked off by this large substrate
an undesired element 共e.g., carbon兲 in the films. In recently
holder. A set of a mirror and lens outside the PLD vacuum
developed Pt/ SrBi2Ta2O9 / Hf– Al– O / Si ferroelectric-gate
chamber can be one-dimensionally moved, and correspond-
field-effect transistors with outstanding long data retention,
ingly the laser beam hit position X on the target was moved
PLD technology has been utilized for the deposition of ferro-
along the longer side direction 共the x axis direction兲 of the
electric SrBi2Ta2O9 and insulating Hf–Al–O layers.1 How-
target. To avoid digging the same point in the target, the
ever, commonly used PLD methods tend to show poor uni-
target was moved back and forth along the ␤ direction as
formity of film thickness, mainly due to small laser-ablation
plume.2,3 Although there have been several works for large-
area deposition,4–6 PLD has not been fully accepted as a
good method for large-area thin-film depositions. In order to
achieve thickness uniformity, we recently developed the PLD
technology using a prototype machine of the VPLD-8000
共Vacuum Products Co., Japan兲 and succeeded in depositing
large-area films of high-k dielectric HfO2 and ferroelectric
SrBi2Ta2O9 共SBT兲 on Si wafers. In this work, we demon-
strate good thickness uniformity of HfO2 films on 8 and 6 in.
Si wafers and of SBT films on a 4 in. Si wafer. One advan-
tage of our method is that the available Si wafer size is easily
extendable to 300 mm diameter.

II. EXPERIMENT
Figure 1 shows a schematic picture explaining the concept
of our method. An incident beam of a KrF excimer laser
共␭ = 248 nm兲 was set to be parallel to a face-down substrate
holder and a 3 ⫻ 12 cm2 ceramic target with thickness of
8 mm for HfO2, and a 3 ⫻ 10 cm2 target for SBT with the
FIG. 1. Schematic top and side views of a large-area pulsed-laser-deposition
a兲
Electronic mail: shigeki.sakai@aist.go.jp system.

903 J. Vac. Sci. Technol. A 25„4…, Jul/Aug 2007 0734-2101/2007/25„4…/903/5/$23.00 ©2007 American Vacuum Society 903
904 Sakai et al.: Large-area pulsed-laser deposition of dielectric and ferroelectric thin films 904

FIG. 2. Contour map of HfO2 film thickness without the Si substrate rota-
tion. The numbers labeled at contour lines represent the deposition rate in
units of Å/min.

shown in Fig. 1. The substrate was rotated at a suitable

speed, which assured thickness distribution with a circular
symmetry around the substrate center.
The chamber was evacuated by an 800 l / s turbomolecular
pump and the background pressure was less than
1 ⫻ 10−6 Pa. During deposition, N2 or O2 gas was introduced
through a variable leak valve, connected to a flange at a
lower part in the chamber. The flow rate and the pressure
were monitored by a mass-flow meter and a diaphragm
gauge, respectively.
A simple idea for depositing a uniform-thickness film on a
rotating substrate gives us a model where the deposition time
t is proportional to R 共the distance on the substrate from the

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wafer center兲, because the circumference is 2␲R. This might
be suited for a case where the ablation plume is extremely
small, but this model does not bring a good result, since the
plume has a proper size that makes a strong thickness varia-
tion on a wafer. We chose a more practical method. That is,
we chose several points of X and tested a deposition for each
point beforehand. More precisely, to avoid the same position
digging of the target, the position was ±5 mm scanned
around X along the x axis by moving the set of the mirror
and lens at a constant speed. Simultaneously, the target was
moved in the ␤ direction as explained above. In this article,
stating a deposition at X means the inclusion of this ±5 mm
scan. After the test deposition, the thickness and deposition
rate as a function of R were characterized by an ellipsometer.
Finally, using the deposition rate at the several selected X
FIG. 3. Test HfO2 depositions on 8 in. Si wafers with the substrate rotation
at four laser-beam hit positions of X = 4.5, 6.5, 8.5, and 11.5 cm.
FIG. 4. Thickness distribution of HfO2 deposited by the large-area PLD
method on an 8 in. Si wafer. 共a兲 Contour map and 共b兲 thickness vs R.
points, the best deposition times at the respective X points for
obtaining each thickness we wanted were calculated by using
a special program 共PTUTBASIC兲 共Ref. 7兲 installed in the
VPLD-8000.
III. RESULTS AND DISCUSSION
A. Uniform-thickness depositions
The laser energy at the exit of the laser machine was
250 mJ/pulse. The repetition rate used was 3 – 10 Hz. The
HfO2 was deposited at room temperature in 13 Pa N2. First,
we deposited a HfO2 film without the substrate rotation. Fig-
ure 2 is a contour map of the thickness distribution, mea-
sured by an ellipsometer. Due to no substrate rotation, strong
thickness variation on the substrate was found. The shape
along the x direction was symmetric around x = 0, but along
the y direction, the shape was asymmetric because the target
surface was tilted to the substrate surface. The full width at
the half maximum 共FWHM兲 along x was nearly 50 mm.
By rotating a substrate, this strongly varied thickness can
be averaged on a circumference with the same diameter, and
thus a film with circularly symmetric thickness distribution
can be obtained. We made several HfO2 depositions on Si
wafers of 8 in. diameter at different laser-beam hit positions

J. Vac. Sci. Technol. A, Vol. 25, No. 4, Jul/Aug 2007

905 Sakai et al.: Large-area pulsed-laser deposition of dielectric and ferroelectric thin films
FIG. 5. 共a兲 Contour map of the thickness distribution and 共b兲 thickness vs R
of a HfO2 deposition on a 6 in. Si wafer by the large-area PLD method.
of X = 4.5, 6.5, 8.5, and 11.5 cm. Here, each value assigned
for X is the distance from a target holder edge, X0 in Fig. 1,
to the X position. Since the projection of this edge to the x
axis provides x = 0, each X corresponds to the x coordinate on
the x axis. The relationship between the deposition rate 共nm/
min兲 and the distance from the wafer center 共R兲 is shown in
Fig. 3. There might be an assumption that a deposition at an
X would provide a thickness distribution with its maximum
at R = X, but actually the deposition rates monotonically de-
creased at X = 4.5 cm and increased at 11.5 cm as R in-
creased. The curve at X = 4.5 cm can be understood as fol-
lows: At R = 0, some constant amount is always deposited.
On the other hand, on a point in the R = 4.5 cm circumfer-
ence, the rate becomes very large when the point comes near
the laser-hit position, but very small when the point stays far
from the hit position. As a result of the rate distribution of
Fig. 2 共FWHM⬇ 5 cm along x兲, the average deposition rate
at R = 0 was larger than the point in the R = 4.5 cm circum-
ference. At the intermediate X = 6.5 and 8.5 cm, the rate
maxima exist in the estimated R range.
By using the deposition rate curves at the four X points in
Fig. 3, a deposition on an 8 in. Si wafer was performed. A
JVST A - Vacuum, Surfaces, and Films
905
31 January 2024 07:23:07
FIG. 6. 共a兲 Contour map of the thickness distribution and 共b兲 thickness vs R
of a SrBi2Ta2O9 deposition on a 4 in. Si wafer by the large-area PLD
method.
deposition time was calculated for each X position for real-
izing a uniform film thickness over the entire area of the
wafers. Both curves decreasing and increasing monotoni-
cally, such as those for X = 4.5 and 11.5 cm in Fig. 3, are
necessary to calculate the best deposition times for obtaining
uniform-film thickness.
Figure 4 shows the thickness-distribution result of
42-nm-thick HfO2 deposited on an 8 in. Si wafer. The thick-
ness of over 300 points with the interval 共⌬x and ⌬y兲 of
10 mm on the entire wafer was characterized. Figures 4共a兲
and 4共b兲 are the contour map and the R dependence, respec-
tively. The standard deviation was 1.3% of the averaged
thickness, 42 nm. Figure 5 shows the thickness distribution
of 6-nm-thick HfO2 deposited on a 6 in. Si wafer. The tech-
nology of this thickness range is significant for applications
to the next-generation metal-insulator-semiconductor 共MIS兲
field-effect transistors 共FETs兲 and nonvolatile metal-
ferroelectric-insulator-semiconductor memory FETs. The
distribution was measured on over 300 points with ⌬x = ⌬y
= 7.5 mm. The standard deviation was 1.6% of the averaged
thickness. The X positions used for this deposition on the
6 in. wafer were 3.8, 5.0, 7.0, and 11.0 cm.
906 Sakai et al.: Large-area pulsed-laser deposition of dielectric and ferroelectric thin films
FIG. 7. Cross-sectional TEM images after the deposition of a 6-nm-thick
HfO2 film on the 6 in. Si wafer 共a兲 at R = 1.3 cm and 共b兲 at R = 5.6 cm.
The SBT was deposited on a 4 in. Si wafer. According to
a well-known deposition condition,1 the substrate tempera-
ture was set at 400 ° C and the O2 gas pressure was kept at
13 Pa. Before the uniform-thickness deposition, the test
depositions were performed at X = 3.5 and 7.0 cm, respec-
tively, and the thickness and the deposition rate were char-
acterized by the measurement using the ellipsometer. By us-
ing these data, deposition for a uniform-thickness film was
carried out. The average obtained thickness was 94 nm and
the standard deviation over this average was 1.2% 共Fig. 6兲.
The results of these three deposition examples certify that
the proposed deposition technique can provide films with a
standard deviation of less than or nearly 1.5% over the whole
4 – 8 in. wafers.
B. Film characterizations
Reducing an equivalent silicon-dioxide thickness is very
important for MIS FETs with ultrathin gate insulators. HfO2
films were deposited in N2 gas ambience to suppress
SiO2-like layer formation8 between the Si surface and HfO2
films. The PLD is advantageous for preventing the SiO2
layer formation, compared to the magnetron sputtering.9 The
6-nm-thick HfO2 film on the 6 in. Si wafer shown in Fig. 5
was used for characterization. Figure 7 shows the cross-
sectional transmission-electron microscopy 共TEM兲 images
after deposition. Figures 7共a兲 and 7共b兲 are the images of the
film positions at R = 1.3 and 5.6 cm, respectively. From the
figures, the uniform thickness of HfO2 共nearly 6 nm兲 can be
J. Vac. Sci. Technol. A, Vol. 25, No. 4, Jul/Aug 2007
906
FIG. 8. Capacitance vs R for the Pt/ HfO2 / Si MIS diodes on a 6 in. Si wafer.
confirmed. A SiO2-like layer is found between the HfO2
layer and Si substrate, but it is less than 1 nm for both
共a兲 and 共b兲.
To characterize electrical properties of the 6-nm-thick
HfO2 on the 6 in. Si wafer, MIS diodes were formed: Pt
electrode dots of 2 mm diameter were electron-beam evapo-
rated, after the annealing of the film in N2 at 700 ° C for
10 min. At the backside of the Si wafer, Al was deposited by
the evaporation. The capacitance versus gate voltage 共C-V兲
relationship was measured along one direction from the cen-
ter to the periphery of the wafer. By taking the accumulation-
mode capacitance for each Pt/ HfO2 / Si MIS diode, Fig. 8
was obtained, showing the standard deviation of 1.9%. The
HfO2 films deposited by this large-area PLD showed uniform
31 January 2024 07:23:07
electrical properties.
IV. CONCLUSION
In order to achieve the thickness uniformity, we recently
developed the PLD technology and succeeded in depositing
large-area films of high-k dielectric HfO2 and ferroelectric
SBT on Si wafers. We demonstrated good thickness unifor-
mity of 8 and 6 in. HfO2 and 4 in. SBT films. Standard de-
viations of the thicknesses all over the 42-nm-thick 8 in.
HfO2, 6-nm-thick 6 in. HfO2, and 94-nm-thick 4 in. SBT
were 1.3%, 1.6%, and 1.2%, respectively. Cross-sectional
TEM showed that an interfacial layer between HfO2 and Si
was thinner than 1 nm in the 6-nm-thick 6 in. HfO2. The
standard deviation of accumulation-mode capacitances was
1.9% for Pt/ HfO2 / Si MIS diodes, which were fabricated by
evaporating Pt top electrodes on a diametrical line of the
6-nm-thick 6 in. HfO2 and annealing at 700 ° C in N2 for
10 min. In our PLD technique, the KrF laser beam was
aligned parallel to a face-down substrate surface and a
3 ⫻ 12 cm2 ceramic target was set to be inclined to the sub-
strate surface by 30°. Since the substrate does not block off
the incident laser beam, the available Si wafer size is easily
extendable to 300 mm in diameter. Therefore, PLD tech-
nique we developed meets the industrial needs for high and
uniform quality over large-area high-k dielectric and/or
ferroelectric thin films for large-scale integrated circuits.
ACKNOWLEDGMENTS
The authors thank Tetsuo Ishida, Toshihiro Sato, and
Hisao Hojoh for valuable discussions.
907 Sakai et al.: Large-area pulsed-laser deposition of dielectric and ferroelectric thin films 907

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