Abstract
The development of analytical tools and proce-dures for process control is a prerequisite for the integra-tion of high permittivity and/or ferroelectric materials inCMOS devices. The thickness and composition of pe-rovskite oxide films were determined by wavelength dis-persive X-ray fluorescence analysis (XRF) with specialemphasis on the ratio of the group-II elements to the Ticontent, and a precision of 0.5% was achieved for a typi-cal film thickness of 20–30nm. Secondary ion mass spec-trometry (SIMS) and sputtered neutrals mass spectrome-try (SNMS) was used for depth profiling to determinefilm homogeneity and elemental interdiffusion at hetero-
interfaces. Examples are given for Ba
x
Sr
1–x
TiO
3
andSr
TiO
x
thin films which were grown in a prototypeMOCVD production tool. No interdiffusion was observedfor films grown at 600°C on Pt electrodes in contrast tofilms grown directly on Si.
Keywords
XRF · SIMS · SNMS · MOCVD · BST ·DRAM
Introduction
Electroceramic materials can be integrated into novel de-vices with unique functionality: multi-Gbit memory mod-
ules, nano-sized transistors, high-performance sensors and
nano-actuators are examples of applications incorporatingceramic materials which are likely to come to the marketin the near future. Perovskite oxides are prime candidatesfor high-k [1] as well as for ferroelectric applications [2]and BST, PZT and SBT were analysed in detail. As an ex-ample we concentrate here on the high-k material bar-ium–strontium–titanate, BST, which is considered to be apromising candidate to enter the DRAM manufacturingprocess as a replacement for the conventional oxide/ni-tride/oxide (ONO) dielectric layers. Produced in thinfilms, BST has a high permittivity of 100–400, comparedto 3.9 for pure SiO
2
, thus allowing the design of the cell ina simple stack structure even for the future Gbit DRAMsSpecial emphasis is given to the exact determination of the group-II/Ti ratio. Bulk ceramics of these perovskitesare exactly stoichiometric and a possible surplus of metal-lic elements precipitate at grain boundaries and triplepoints. For thin films grown at lower temperatures, suchprecipitates are not identified up to rather large deviationsfrom the stoichiometric composition. The surplus metalsare incorporated in the films and affect the electrical prop-erties [2]. Hence, a perfect control of the group-II/Ti ratiois necessary, and we applied XRF as a nondestructive toolto determine the average composition of the films. Theseinvestigations are supplemented by studies of the homo-geneity of the film and especially the interfacial reactionson different substrates by SIMS/SNMS.
MOCVD thin films
MOCVD was used for thin film deposition which allowsthe fast deposition on large area wafers as required for amass production technique. Thin films were deposited oncommercial p-type Si(100) substrates and on substrateswith sputter-deposited Pt films as electrodes. These pla-tinized films generally include additional adhesion layers(i.e. the film stacks used are Pt/TiO
2
/SiO
2
/Si or Pt/ZrO
2
/ SiO
2
/Si). The precursors for the MOCVD were suppliedby a liquid delivery system which mixes solutions fromthree sources: 0.35M solutions of Ba(thd)
2
and Sr(thd)
2
and a 0.4M solution of Ti(O-
i
-Pr)
2
(thd)
2
dissolved in butyl
acetate.The AIXTRON Planetary Reactor of the 2600G3 se-ries can handle five 6-inch wafers simultaneously. Thewafers are placed on a coated graphite susceptor that ro-tates typically at 8rpm and carries five smaller plates
U. Breuer · W. Krumpen · F. Fitsilis
XRF and SIMS/SNMS analyses of Ba
x
Sr
1–x
TiO
3
dielectrics
Anal Bioanal Chem (2003) 375:906–911DOI 10.1007/s00216-003-1806-4Received: 9 October 2002 / Revised: 8 January 2003 / Accepted: 16 January 2003 / Published online: 27 February 2003
SPECIAL ISSUE PAPER
U. Breuer (
✉
) · W. KrumpenZCH, Research Centre Jülich, 52425 Jülich, Germanye-mail: uwe.breuer@fz-juelich.deF. FitsilisIFF, Research Centre Jülich, 52425 Jülich, Germany©Springer-Verlag 2003
(satellites) which rotate at 40rpm by gas foil rotation. Thegas inlet nozzle is placed centrally above the reactor pro-viding a pure horizontal gas flow direction which makesthis reactor a radial flow system. The oxidizer gases (O
2
/ N
2
O) enter the reactor separately from the precursors justbelow the nozzle in order to avoid premature reactions.The reactor operates under low pressure at approximately2mbar to increase the gas diffusivity and prevent pre-re-actions. The deposition temperatures were varied 500– 700°C. The process conditions are summarized in Table1[3, 4].
Wavelength dispersive XRF
Tool descriptionThe XRF tool is a RIGAKU ZSX-100e with a 3-kW Rh-tube which was generally operated at its maximum tubepower of 50kV–60mA. The wavelength dispersive ele-ment characterization is based on Bragg’s law:
n
λ
=
2
d
sin
θ
(1)where
n
is the order,
λ
the wavelength,
d
is the lattice pa-rameter of the analyser crystal and
θ
is the position of thediffraction maximum. The analysing crystal and the de-tector are rotated in the
θ
/
2
θ
mode.For the analysis of thin films which contain the ele-ments Ba, Sr, Ti, Pb and Ta the standard analysing crystalLiF200 was used with a lattice parameter 2
d
=4.0276Å.For Bi, which was overlapped by the Pt L
β
lines, the M
line and a Ge crystal with a lattice parameter of 2
d
=6.532Å
was chosen. The beam diameter was set to 25mm, thesample size was 1
×
1-inch square, and a stainless steelsample holder mask restricted the sample area to a definedsize of
A
=4.91cm
2
.Additionally, the samples were rotatedduring the measurement in order to average any inhomo-geneity in the composition and thickness. Analysis wasperformed at a base pressure of 3mbar in order to avoidabsorption of the fluorescent X-rays as well as air scatter-ing.In addition to the fluorescent radiation, a disturbingdiffraction background may pass the analysing crystal of the spectrometer. As we use
single crystalline
Si sub-
strates, such effects may not be very reproducible even with
a rotating sample holder. These diffraction effects becomemore serious with decreasing wavelength and can in prin-
ciple be avoided by taking a fluorescent wavelength which
is longer than the diffraction limit of the sample. In thecase of BST, diffraction effects become significant for thehigh energy Sr-
K
α
line. A second important backgroundcontribution appearing at high energies, corresponding tolow theta angles comes from the Compton tail of the char-acteristic
K
α
-
line of the Rh tube. In the case of our thinfilms the penetration of the X-rays can be several mi-crometers (
µ
m) and is consequently much deeper than thefilm thickness (<10nm and 150nm). That means that notonly the elements in the desired film but also sublayersmust be taken into account. In order to achieve a reliablebackground subtraction the background must be investi-gated for every film substrate combination.XRF calibration strategyWe will concentrate on the cation composition by XRFand especially the group-II/Ti ratio. Figure1 depicts thescan profile of a BST standard near the interesting lines.The lines are characteristic for the concentration of the
907
Table 1
Typical deposition conditions for BST filmsSubstrate temperature (°C) 500–750Reactor pressure (mbar) 1–3O
2
/N
2
O flow rate (sccm) 50–500Liquid source feeding rate (mLs
–1
) 0.08Vaporization temperature (°C) 225–245Film thickness (nm) 10–120
Fig.1a,b
Line spectrum of fluorescence analysis with back-ground fitting and peak deconvolution
a
Sr-Ka,
b
Ti-Ka and Ba-Laline
specific elements in the sample, while the background in-tensity level depends on the substrate (e.g. platinizedwafers, typically Pt/adhesion-layer/SiO
2
/Si, have a higher background than SiO
2
/Si wafers).For the quantitative evaluation of the integral intensitythe peak form can be considered as a pure Gaussian dis-
tribution. The intensity calculation starts by fitting the back
-ground using a linear, multi-point or polynomial fit. Incase of overlapping lines, peak deconvolution is neces-sary and Gaussian distributions are fitted in the line pro-file, as shown in Fig.1. Background calculation is differ-ent for the high energetic peaks (Sr) than for the low en-ergetic ones (Ba, Ti) at the other end of the spectrum,where the background remains almost constant. In thefirst case, a 4-point fitting is used to find a mean value for background extraction in the high-noise region (±50cps),in contrast to the 2-point linear fit for the Ti and Ba peaks.The fluorescence intensity is directly proportional tothe mass of an element in an unknown sample; however,in order to obtain absolute values this mass must be deter-mined from a comparison to the standards:
m
E
A
=
c
Est
I
E N
(2)where
m
E
is the mass of the element in the irradiated sur-face
A
,
I
E N
is the net intensity of the examined peak in theXRF spectrum, and
c
=(
m
E
/
A
)/
I
E
and is the calibration fac-tor derived from the calibrated standards.Such standards with known stoichiometry and thick-
ness were prepared by chemical solution deposition (CSD).
During CSD deposition there is no loss of material and thefinal composition of the film is therefore identical to theoriginal solution, which was additionally controlled byICP–AES. Hence, a comparison of the intensity ratiosyields directly the cation stoichiometry of the films withhigh precision. For the determination of the areal massdensity and the film thickness, the thickness of the cali-bration standards was determined by profilometry using a
VEECO DEKTAK system, and the mass density was de-duced assuming the ideal density of the corresponding pe-rovskite. Hence the stoichiometry (e.g. the group-II/Ti ra-tio) can be determined with a precision of the order of 0.5%, whereas the thickness includes the additional uncer-tainties of the profilometer and possible deviations fromthe ideal density. In order not to rely on one calibrationsample only, the average over a thickness series was used.
Figure2 shows an intensity versus mass (
µ
g)/illumi-nated area plot prepared from the data of the calibration
standards. We observe a linear increase of the intensity with
the mass for all elements. The proportionality factor for each element is derived from the slope of the curves. Theparameters of the linear regression model,
X
=
C
×
I+
D
, for the BST system are as shown in Table2. Intercept
D
wasset to zero. The precision of the calibration is depicted inthe quality of the fits, as the correlation factor
R
2
is alwaysnear unity. The reproducibility of the measurements is ex-cellent and is below 0.35% for the Sr, Ba, and Ti elements(average of 10measurements).As the intensities for the single elements in the sampleincreases, within the given uncertainties, proportionally tothe areal mass density, influences of matrix effects and in-ter-element effects can be neglected for these film thick-nesses.The layer thickness,
t
, can be derived from Eq.(3) if the density of the film is known additionally; we generallyuse the theoretical density of the crystalline bulk, 5.758gcm
–3
for Ba
0.7
Sr
0.3
TiO
3
as an approximation.
t
=
m
E
A
ρ
f ilm
(3)ApplicationFor the measurement of the unknown BST samples weuse the same measurement parameters as used for calibra-tion samples, and especially the same sample size. Analy-sis of films grown on Si or oxidized wafers are straight-forward; however, layer stacks need special consideration.
Our standard platinized wafers have a TiO
x
, TiN
x
or TiAlN
adhesion layer, which corroborate the Ti stoichiometry.Therefore separate depositions on wafers without adhe-sion layer or replacement of the Ti by Zr in the adhesionlayer was necessary.
Under these conditions films of typical thickness 30nm
could be analysed within 5min (average of 3measure-ments) with a precision of 0.5%. Homogeneity tests over
6-inch wafers could be performed after cutting into
1’’
×
1’’
908
Fig.2
Mass versus fluorescence intensity plot for CSD depositedcalibration samples. Both stoichiometric (
filled symbols
) and off-stoichiometric (
open symbols
) samples are included
Table 2
Extracted parameter from the linear fits in Fig.2Element
C R
2
Reproducibility(%)Sr 4.84027 0.99973 0.34Ti 13.0588 0.99966 0.21Ba 44.7132 0.99973 0.28
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XRF and SIMS/SNMS analysis of Bax Sr1-x TiO3 dielectrics
U. Breuer, W. Krumpen, F. Fitsilis, “XRF and SIMS/SNMS analysis of Bax Sr1-x TiO3 dielectrics”, Analytical and Bioanalytical Chemistry Vol. 375, No. 7, p. 906-911 (2003)
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