T. Remmel a), M.

Schulberg b),
S. Fujimura I, H. Honma I, H. Kobayashi I, H. Kohno ),
S. Owens d), R. Deslattes d), J. Pedulla e,
a) Motorola Inc., Tempe, A5 b, Novellus Systems, Inc., San Jose, CA,
) Rigaku Industrial Corporation, Osaka, Japan,
4 NIST, Gaithersburg, MD,
e, J; Pedulla Associates, Silver Spring, MD,
ABSTRACT
Barium Strontium Titanate (BST) is under consideration as a high dielectric constant material for
a number of semiconductor applications. Because of its very large dielectric constant, BST is
seen as an enabling material that will allow the continual &inking of integrated circuits and
progression along the path of Moores Law [l]. The electrical behavior of BST is extremely
dependent upon its material properties, including its stoichiometry, crystal structure and
thickness. Therefore, successful implementation of BST into integrated circuits will require a
thorough understanding of, and the ability to control, its material properties.
Several x-ray methods are ideally suited for characterization and metrology of the material
properties of BST: XRF for stoichiometry, XRD for structure, and XRR for fihn thickness. This
paper focuses primarily on the application of the latter two methods toward characterization of
BST films. Analysis of BST films deposited using spin-on, sputtering and CVD methods are
included. In addition, part of the paper covers the results of a multi-laboratory round robin
comparing the application of XRF and XRR techniques on the same set of BST films.
INTRODUCTION
Over the past several years the semiconductor industry has shown increasing interest in Bariurn
Strontium Titanate due to its inherent high dielectric constant [2-121. BST is envisioned as an
enabling material in several integrated circuit (IC) applications, including DRAM (Dynamic
Random Access Memory), on-chip capacitors and integrated RF filters (Figure 1). Having a
dielectric constant in excess of 1000 in bulk form, a key challenge for the semiconductor industry
is to maintain the high dielectric constant properties of BST while integrating the material in thin
film form into ICs. An attribute of BST is the dependence of its electrical behavior upon its
physical and chemical properties, allowing the BST behavior to be tailored by the thin fihn
deposition process. However this attribute requires a thorough knowledge of these relationships
and the ability to measure and control the material properties. Among these relationships is the
dependence of dielectric constant on both Sr/Ba ratio and A/B [(Ba+Sr)/Ti] site ratio; for
example, a 10 % change in A/B site ratio has been shown to result in a 50% decrease in dielectric
Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.43 510
passive
layer
~~~~~...~~~~~. . ..-
metal
interconnect
: !
layers
. ..- ----. .*.------. . .
active
device
Si
layer
DRAM Capacitor
l-l
BST
Passive Components
1 I
FIGURE 1. Schematic depiction of potential applications of BST in integrated circuits.
constant, as shown in Figure 2 [ 131. Similarly, the leakage behavior of BST films has also been
shown to be dependent upon its A/B ratio.
Capacitance density, a key performance metric for
integrated capacitors, whether used as the charge storage element in a DRAM memory cell or as a
passive decoupling capacitor, is dependent upon both film thickness and dielectric constant,
which itself depends on the film thickness.
500 , , , , , , , 1 , I , I I I I ,I 1 , I I I I ,
/
-: 1 3
400
300
200 :
0.;
100 1
0.8 0.9
A/B Ratio
1.0
FIGURE 2. Variation in dielectric constant
with A/B ratio.
The successful development and subsequent
implementation of BST films into a wafer
manufacturing process will require methodologies
for precise measurement of the BST composition
and thickness. Thin film x-ray methods are
uniquely suited for the characterization of BST
films, including x-ray diffraction (XRD), x-ray
fluorescence (XRF) and x-ray reflectivity (XRR).
XRD is essential for identifying the phase(s)
present in the film, the crystal structure, film
stress and degree of crystallinity. XRD was used
extensively during the development of the BST
film deposition process and has been covered in
detail in a previous paper [ 141. To date XRD
remains primarily a laboratory method that has
not yet transitioned into a metrology or process
control tool for manufacturing.
Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.43 511
X-RAY REFLE-
The application of XRR in thin fihn measurement has experienced increasing use in many
laboratories; XRR was found to be invaluable for accurately measuring the thickness of BST
films during their development. XI& is currently transitioning into a fihn thickness metrology
role in many IC wafer manufacturing areas [15]. While XRR is capable of providing very precise
measurements of BST film thickness, it can also provide insight into the BST film density along
with surface and interface roughness.
Shown in Figure 3 is an XRR spectrum of a BST film sputter deposited onto a Pt fihn
underlayer. Both experimental data points and simulated best fit to the data are shown, revealing
excellent agreement between the raw data and the simulated fit. In this spectrum, the Kiessig
fringes [16] located between 0.3 and 0.6 degrees are attributable to the BST film, whereas the
fringes at higher angles (>1.5 degrees) are attributable to both the BST film and the Pt underlayer.
The precipitous drop in reflected intensity at about 0.3 degrees is associated with the critical
angle of the BST film. The absolute location of this angle is dependent upon the BST fihn
density; in this case it was measured to be 5.2 gm/cm3. The rate of intensity decrease with
increasing angle, along with the amplitude of the Kiessig fringes is a function of both the BST and
Pt film surface and interface roughness.
The sensitivity of the XRR method in accurately dete rmining BST film thickness is depicted in
Figure 4. In addition to the best fit to the experimental data, two other simulated spectra are
shown, one assuming a thickness 1 nm larger than the best fit, the other 1 nm smaller. As
evidenced by these data, the accuracy of the XRR method for determining the BST thickness
(when deposited onto Pt) is generally better than 1 nrn. In a similar manner, the sensitivity of the
XRR method to film density measurement is shown in Figure 5. In this case, in addition to the
best fit spectrum, two other fits with the density varied + and - 10% are shown. Based on this
and other results, the accuracy to which BST film density can be determined is generally better
than 5%.
Grazing Angle (deg)
Grazing Angle (de&
FIGURE 3. X-ray reflectivity spectrum of a
340 nm thick BST film on 25 nm Pt film.
FIGURE 4. XRR spectra showing sensitivity
of BST thickness measurement within +/- 1
mn for a BST/Pt film stack.
Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.43 512
Grazing Angle (deg)
FIGURE 5. XRR spectra showing sensitivity
of BST density measurement within +/- 10 %
for a BST/Pt film stack.
Comparison of the XRR method to other film
thickness measurement techniques, such as
spectroscopic ellipsometry (SE), Rutherford
Backscattering Spectrometry (RBS) and XRF,
has demonstrated the utility of XRR. While SE
can measure BST film thickness in the range of
10 to 100 run, its accuracy is dependent upon
thorough characterization of the underlying
layer(s). RBS and XRF can both provide a
reasonable measure of the mass thickness of BST
(gm/cm2). However to determine the physical
thickness, the fihn density must be known;
which for BST, is very much dependent upon
processing and thermal history.
Until recently, the task of simulating and fitting to experimental XRR data has been time
constuning, labor intensive and analyst dependent; optimal fits are not always achieved, even
after nearly an hour of effort. However recent developments in the use of genetic algorithms in
the XRR simulation/fitting software offer the promise of faster, more accurate results [ 171.
(Genetic algorithms utilize principles such as evolution, reproduction, mutation and survival of
the fittest to attain optimal fitting results). The development of rapid, operator independent
fitting software is deemed critical to the successful implementation of XRR as an IC wafer
manufacturing metrology tool.
X-RAY FLUORESCENCE
XRF of BST has been covered in some detail in several recent papers [18-l 91, where it has been
shown that the repeatability of this technique in measuring Ba, Sr and Ti stoichiometry is quite
good. For XRF analysis of Bai,Sr,TiOs, generally the oxygen levels are not measured and the
analysis focuses on dete rmining the stoichiometric ratios of Ba, Sr and Ti. Therefore the
procedure typically involves measurement of Ba, Sr and Ti x-ray net intensities in an unknown
film and comparison with net intensities from a set of reference or calibration films. A critical
aspect of the analysis involves determining net intensities (i.e. peak - background intensities).
XRF data analysis accuracy is prone to several uncertainties or sources of error. These include:
the accuracy of the standards or reference films used for calibration; precision issues due to
limited counting statistics; knowledge of the background intensities; and the methodology used to
convert x-ray intensities to BST stoichiometry. It has been demonstrated in previous papers that
knowledge of the background levels is critical to obtaining accurate results. In analysis of BST
films on Si wafers, background intensities include x-ray fluorescence contributions from the
underlying layers plus contributions due to diffraction of the radiation from the single crystal Si
substrate. In BST analysis using fixed position spectrometers (usually preferred due to the
higher efficiency in x-ray counting), measurement of the background intensities for the Ba, Sr and
Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.43 513
Ti peaks is not possible. Therefore background levels must be either assumed or measured using
separate, film-free, calibration substrates.
The effects of substrate diffraction on background levels of Ba, Sr and Ti are shown graphically
in Figure 6. In these plots, x-ray intensities at Ba, Sr and Ti wavelengths measured from a bare Si
wafer (no BST film) are plotted as a function of angular rotation of the substrate. The variation
in intensities with angular position is due to diffraction of the incident radiation by the Si
substrate. In this example, during the upgrade of a particular XRF tool through addition of fixed
position Ba and Sr spectrometers, it was apparent that the optimal positioning of the new
spectrometers was not achieved (Figure 6a). One desires to attain an angular position where the
background intensities are near minimum and invariant with angle for all three elements; this
condition was achieved after reversing the positions of the Ba and Sr spectrometers as seen in
Figure 6b. In this case an optimal measurement configuration was obtained at an angular rotation
of about 15 degrees theta. Of particular note in these plots is the very high background intensity
for the Sr peak. Such high levels are particularly problematic for BST film quantitation. Any
uncertainty in the Sr background level can propagate into significant errors in the relative Ba, Sr
and Ti stoichiometries.
One method that was established to minimize uncertainty associated with background levels was
to utilize a BST film-free substrate as a background reference. The procedure involves measuring
Ba, Sr and Ti x-ray intensities from a Si substrate without the BST f, and using those
intensities as background levels to derive net intensities for a BST fihn on a similar substrate.
This method worked particularly well for a rather difficult analysis case involving BST deposited
onto an underlying film stack of Pt/TiN/SiOJSi. In this case, differentiating between the Ti in the
BST and the Ti in the TiN is nearly impossible. However, by measuring the Ba, Sr and Ti levels
from a wafer having only the Pt/TiN/SiO#i fihn stack, and using them as background levels for
the complete BST/Pt/TiN/Si02/Si wafer, very accurate BST stoichiometry was obtained. An
example of the application of this method is shown in Figure 7, where XRF results of similarly
Theta
Theta
FIGURE 6a. X-ray intensities for Ba, Sr and
Ti from a bare Si wafer, as a function of
angular rotation of the substrate; Ba and Sr
spectrometer positions at initial installation.
FIGURE 6b. Similar to Figure 6a, however
data acquired with the Ba and Sr spectrometers
reversed from their initial installation
positions.
Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.43 514
deposited BST films are compared. In one case the BST was deposited on an underlayer of
SiO#i; in the other, on a PtlTiNISiOdSi stack. In the plots, A/B ratios are plotted as a function
of position across 200 mm wafers, measured along both x- and y-axes on the wafers. As can be
seen from the graphs, comparable results were obtained on both wafers.
-100 -80 -60 -40 -20 0 20 40 60 80 1
Distance from Wafer Center (mm)
FIGURE 7a. A/B ratios of a BST film in a
BST/SiO#i film stack, measured at various
locations across a 200 mm Si substrate.
-,oo -80 -60 -40 -20 0 20 40 60 80 1
Distance from Wafer Center (mm)
FIGURE 7b. A/B ratios of a BST film in a
BST/PtiTiN/SiOJSi film stack, measured at
various locations across a 200 mm Si substrate.
BST film was deposited under same conditions
as film in Figure 7a; background intensities
determined by analysis of Pt/TiN/SiO#i
stack.
COMPARISON OF INTER-LABORATORY RFSULTS
Because of the opportunity for error in x-ray analysis of BST thin films, an inter-laboratory
comparison of identical BST films was undertaken to assess the variability of analysis results
between laboratories. A set of 68 wafers having BST fihns which included the following
variables was assembled: underlying layer (Pt/SiO,/Si and SiO,/Si); Ba/Sr ratios (nominally
0.25/0.75 to 0.7/0.3); A/B ratios (0.8 to 1.4); and BST film thickness (nominally 0 nm to 200
nm)-
To date, three different laboratories have analyzed these films using XIG and shared their results.
In addition, three laboratories have also analyzed these same BST films using XRR. As
discussed earlier, XRF is not a first principles method, thus calibration of the tool is critical to
obtaining accurate results. Since BST film standards are very difficult to acquire (thin ftis of
BaF2, SrFZ and TiOZ are typically used for calibration), the above wafer set included a subset of
BST films that could be used as standards for analysis. As part of the inter-laboratory
comparison, each participant was asked to first analyze all wafers using their own internal
Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.43 515
method of BST calibration; then a second analysis was sought using the common subset of BST
fihns.
Because of the large amount of data obtained during this inter-laboratory comparison (3 element
compositions x 68 wafers x 3 laboratories x 2 different calibrations), a method was employed to
compare the overall results in a compact manner Since the exact stoichiometry of each fihn is not
known, the average elemental composition, standard deviation and relative standard deviation
(RSD) were calculated. The RSDs for each element were viewed as a gauge of the degree of
agreement between laboratories on the elemental composition of a particular film.
Shown in Figure 8 are the relative standard deviations for Ba, Sr and Ti for each of the BST films,
plotted versus BST film thickness. Thickness was chosen because it was expected that for
thinner BST films, less material is present and therefore the disagreement (RSD) should increase.
The results shown in Figure 8a are based on each laboratories in-house calibration, whereas the
results shown in Figure 8b are based on calibration using the common subset of reference films
included in the wafer set. As evident in the plots, the general agreement between laboratories
improves about 5X when a common set of films is used for calibration and a slight dependence of
RSD on fihn thickness is apparent for calibration based on the common set of reference films
(Figure 8b). However over the range of 10 to 100 mu, the correlation between RSD and thickness
is minimal.
Shown in Figure 9 are the same RSD results from XRF analsyses, in this case plotted versus Ba
stoichiometry. Evident in the Figure 9a plot is the larger disagreement for the nominal Ba/Sr of
0.25/0.75. After reducing the results based on a common set of reference films, the agreement
between the laboratories becomes relatively insensitive to BST film stoichiometry. The larger
disagreement at the 0.25/0.75 stoichiometry was due
1000.0%
8
2
b
100.0%
n
E
g
8
10.0%
v)
?
P
S 1 .O%
t
0.1%
1 10 100 1001
BST Thickness (nm)
FIGURJZ 8a. RSD of XRR results for Ba, Sr
and Ti, based on each laboratories in-house
method of calibration, plotted versus BST film
thickness.
s
g 100.0%
2
0
E
$ 10.0%
9
ti
L
;, 1 .O%
2
1 10 100
BST Thickness (nm)
FIGURE 8b. Similar to Figure 8a, however in
this case the XRF calibration was performed
using the common set of BST films.
Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.43 516
E
g
2
10.0%
02
2
.-
x
1.0%
I
8
i:
2 100.0%
t
c1
B
t
B
10.0%
v)
t
=
m
1.0%
B
0.1% I
0.000 0.200 0.400 0.600 0.60
BST Stolchlometry (Ba)
0.200 0.400 0.600
BST Stoichiometry (BE)
0.60
FIGURE 9a. RSD of XRJ? results for Ba, Sr
and Ti, based on each laboratories in-house
method of calibration, plotted versus Ba
FIGURE 9b. Similar to Figure 9a, however in
this case the XRF calibration was performed
using the common set of BST films
stoichiometry.
to the range over which one laboratory calibrated their XRF tool (attention was focused on a
different portion of the stoichiometry range).
Finally, in a similar manner, the agreement between XRR results of the three laboratories for BST
film thickness on the same set of BST films are plotted in Figure 10, as a function of BST film
thickness. The relative agreement between laboratories for XRR is generally much better than for
XRF, with RSDs of about 1 % for BST films of 20 to 60 nm. However, the disagreement
becomes much larger for both thinner and thicker films. The large RSDs for films with thickness
less than 10 nm might be explained by the fewer number of Kiessig fringes for these films and/or
the difficulty in fitting the XRR spectra when
the BST films are present on an underlying
substrate such as Pt.
ACKNOWLEDGMENTS
The authors would like to acknowledge the
efforts of many technologists within their
respective companies who enabled the
performance of this work. Special thanks for
the individual contributions from Dennis
Werho, Peir Chu, Beth Baumert, Gary Mote
and Dan Sullivan of Motorola. Motivation
for this work came from the Materials
Technology Laboratories within Motorolas
Semiconductor Products Sector; many thanks
to the encouragement and support of Robert
E. Jones, Jr. and Peter Zurcher.
100.00%
E
G
4 & 10.00%
R
2
8 3 1 .OO%
0
$
C
0.10%
m
z
c4
0.01%
1 10 100
BST Thickness (nm)
FIGURE 10. Film thickness RSD from XRR
analyses plotted versus BST film thickness.
Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.43 517
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Copyright(c)JCPDS-International Centre for Diffraction Data 2000,Advances in X-ray Analysis,Vol.43 518