specific elements in the sample, while the background in-tensity level depends on the substrate (e.g. platinizedwafers, typically Pt/adhesion-layer/SiO
/Si, have a higher background than SiO
/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:
is the mass of the element in the irradiated sur-face
is the net intensity of the examined peak in theXRF spectrum, and
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 (
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,
, for the BST system are as shown in Table2. Intercept
wasset to zero. The precision of the calibration is depicted inthe quality of the fits, as the correlation factor
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,
, 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
as an approximation.
(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
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
Mass versus fluorescence intensity plot for CSD depositedcalibration samples. Both stoichiometric (
) and off-stoichiometric (
) samples are included
Extracted parameter from the linear fits in Fig.2Element
Reproducibility(%)Sr 4.84027 0.99973 0.34Ti 13.0588 0.99966 0.21Ba 44.7132 0.99973 0.28