Estimation of Uncertainty in Plate Thickness Measurement By X-ray Fluorescence Spectrometry

Glenn E. Staudt AMP Incorporated

ABSTRACT
A foundation is developed for assessment of the uncertainty of coating layer thickness analysis using commercial x-ray fluorescence instrumentation. Proper evaluation of the measurement uncertainty is requisite for effectual application to plating process control and product disposition, but traditional methods of assessment (by repetitive measurement) are inadequate due to exclusion of major sources of experimental variability. The major sources of measurement uncertainty are identified and their contributions to the overall uncertainty of the analytical results are estimated. The effect of calibration uncertainty due to variation in calibration standards is found to be dominant under many practical circumstances. Failure to account for these important sources of variation properly will yield substantial underestimates of the overall measurement uncertainty that will seriously compromise efforts to improve plating process control and plated product quality.

tainty such as substrate and saturation uncertainties and calibration standard thicknesses. These sources of measurement uncertainty can be estimated by other means.

OBJECTIVE
The objective of this work is to provide a basis for accurate evaluation of the measurement uncertainty associated with the determination of coating thickness using commercial x-ray fluorescence apparatus. This will be accomplished through the identification of the major sources of measurement uncertainty and the development of reasonable estimates of the magnitude of their contributions to the overall uncertainty of the analytical results. In this context, the term uncertainty is used to denote the overall extent to which the measurement result remains indeterminate (i.e., the amount to which the measured value may be in error with respect to the actual value of the measured quantity). This term is used in preference to the statistical terms accuracy and precision since it is the overall effect relative to the true value (i.e., the magnitude of possible error) that is of interest regardless of the nature of its source. Such an approach is appropriate for the determination of the results of measurement (if deviation from an actual value rather than reproducibility of a specific experiment is desired) since an observed quantity can be equally uncertain whether its lack of exactitude derives from random or systematic sources. Adoption of this perspective avoids the potentially contentious consideration of whether individual sources of uncertainty are attributable to random or systematic factors. This perspective reflects a randomatic 3 interpretation of a traditionally systematic effect (e.g., calibration bias) wherein the bias is considered as a random, precursory sampling of a parent population, which is assumed to be

INTRODUCTION
The thickness of metallic coatings is routinely determined by x-ray fluorescence spectrometry.l This provides a basis for assessing the quality of coated materials and therefore influences decisions regarding disposition (acceptability) of coated product as well as control of coating processes. Knowledge of the variability associated with these measurements of coating thickness is necessary for proper interpretation of test results. This variability is often estimated from repetitive measurements either on the same sample (yielding a good estimate of the inherent precision of the measurement technique) or on similar samples (in which case variation between samples is included in the uncertainty estimate). However, such an evaluation yields severe underestimation of the measurement uncertainty due to exclusion of major sources of measurement uncer-

Copyright 2004 by Tyco Electronics Corporation. All rights reserved.

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unbiased overall.4 The adoption of this randomized concept of traditionally systematic errors is justifiable on the basis of the evident existence of underlying sampling distributions (such as from the population of all calibration standards), which are expected to be accurate (or very nearly so) on the average. This representation provides a consistent methodology for the treatment of uncertainties regardless of origin (e.g., random or systematic in a traditional viewpoint).5,6 Consequently, the uncertainty of each quantity is expressed as an estimated standard deviation, and the uncertainty components are combined accordingly. 7

system, which induces variation in the x-ray intensity observed within an established window (region of interest) of detector output voltage. The magnitude of variation produced by such phenomena is highly dependent upon the specific application (such as material combinations and chosen region of interest) and is difficult to assess. Since these effects are expected to be modest in well-designed instruments operated under sound experimental protocols, they will be excluded from further consideration. Since the analysis is comparative, the accuracy of the calibration standards will also exert a profound influence over the accuracy of resulting thickness determinations. This constitutes another major contribution to the uncertainty of thickness measurement by x-ray fluorescence instrumentation. Figure 1 exhibits a block diagram of the analytical process comprising thickness determination by the technique of x-ray fluorescence using commercial x-ray systems indicating the previously discussed sources of uncertainty.

DESCRIPTION OF MEASUREMENT PROCESS

X-ray fluorescence does not provide a direct measure of coating layer thickness. Rather, the technique operates by comparison of the level of fluorescent x-radiation detected from an unknown sample with other levels associated with known thicknesses. Therefore, the initial activity in the analytical scheme is calibration of the x-ray fluorescence apparatus with coating layer thickness standards.8 The basic instrument response that is measured is the x-ray intensity or counting rate, which is the number of individual x-rays (photons) collected per unit time. Since the absolute detected counting rate is highly dependent upon many factors, the thickness is traditionally related to the normalized intensity, which expresses the observed intensity as a fraction of the range of the counting rate between that from the substrate and that from a sample of saturation thickness.9 Consequently, remeasurement of the substrate and saturation intensities provides a means for correcting the results for instrumental drift. However, to facilitate compensation of total intensity variations, commercial x-ray thickness measurement units generally furnish the ability to correct many independent calibrations by measurement of a single reference standard. This signal correction procedure operates by scaling the actual measured counting rates in accordance with the observed ratio of reference intensities at the times of calibration and measurement. This presumes that all measured counting rates are affected equally and change proportionally, which are reasonable assumptions. Since the production of x-radiation is a random process, every observation of an x-ray intensity contributes uncertainty to the resulting thickness even for a perfect measurement instrument. Contribution from the analysis of the thickness of an unknown sample includes measurement of both the unknown and the signal correction sample (assuming the use of signal correction rather than remeasurement of substrate and saturation samples). The calibration procedure also contributes imprecision due to the measurement of (1) the calibration standards, (2) the substrate, (3) the saturation sample, and (4) the signal correction sample. Effects other than random intensity variation also influence the uncertainty of the resulting thickness. An example is fluctuation of the energy calibration of the detection

Figure 1. Shown is a process diagram for a commercial x-ray fluorescence thickness measurement instrument illustrating the sources of uncertainty and the sequence of their interaction.

X-ray fluorescence does not respond to layer thickness but rather to mass per unit area of the element of interest. 10 Therefore, the thickness must be derived on the basis of the material density. However, accurate knowledge of the density of thin coating layers is elusive. Also, material costs (and perhaps product function) are related to the mass of coated material rather than to its thickness. Therefore, it is conventional to specify an assumed density to which the thickness measurement is applicable. Consequently, the

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(assumed) density of the coating does not contribute uncertainty to the measured thickness.

THEORETICAL MODEL OF UNCERTAINTY PROPAGATION

The quantitative effect of each source of uncertainty on the overall uncertainty in the measured thickness can be assessed theoretically from the relationship between the instrumental responses (measured fluorescent x-ray intensities) and the derived thickness. Under the usual assumptions of constant background (independent of thickness) and of the effective wavelength approximation (that is, treating the x-ray source as monochromatic), the ideal relationship between layer thickness and instrument response is obtained as shown in Equation 1. 11

normalized intensity), which are dominated by the random counting statistics governing the production of fluorescent x-radiation. Consequently, the covariance between these effects is considered to be zero. Under this assumption, the experimental uncertainty (standard deviation) in the measured thickness is approximated by the first order sensitivities to variation in the measured quantities, as shown in Equations 4 and 5.12,13

where standard deviation of coating layer thickness = standard deviation of calibration constant xn = standard deviation of normalized intensity
t=

where t = thickness of coating layer = calibration constant Xn = normalized intensity The normalized intensity is defined in terms of the measured counting rates (absolute intensities) by equation (2). where = standard deviation of intensity at thickness t xo = standard deviation of substrate intensity xs = standard deviation of saturation intensity xsc = standard deviation of signal correction intensity xref = standard deviation of reference intensity
x

where

X = Intensity at Thickness t Xo = Substrate Intensity ( t = 0 ) Xs = Saturation Intensity ( t )

With substrate and saturation intensities measured at the time of calibration, the expression for the normalized intensity is modified to account for signal correction by measurement of a reference standard according to Equation 3.

Application of the calculus to Equations 1 and 3 yields the partial derivatives shown in Equations 6 through 12:

where Xsc = measured intensity on signal correction sample (at the time of the sample measurement) Xref = reference intensity on signal correction sample (at the time of calibration) The uncertainty in the calibration constant results primarily from uncertainty in the assigned values of the calibration standards. Since this originates from the procedure employed in characterization of the thickness standards, it is expected to be independent of the uncertainty in the measured counting rates (and hence in the

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ESTIMATION METHODS
The contributions to uncertainty from the various sources can be estimated from readily available information. The sources of uncertainty and associated estimation methods are represented diagrammatically in Figure 2.

in the intensity measurement. However, it is usually assessed by direct experimental observation of the variability in the thickness determination from an uninterrupted sequence of repetitive measurements in the absence of operator intervention. In practice, the positioning of the sample for measurement may also contribute to the apparent measurement uncertainty this will transpire when the actual plate thickness varies with position on the sample over distances on the order of the positioning capability of the measuring instrument (typically about 0.05 mm) or when the sample geometry is critical. This is not truly part of the measurement uncertainty since it represents actual changes in the thickness of the plate. Nevertheless, it contributes to the effective uncertainty of the measurement result. This effect can be explicitly included in the precision estimate by completely repositioning the sample between repetitive measurements. The contributions to uncertainty in the thickness due to the counting statistics of measurements other than that of the sample (i.e., substrate, saturation, and signal correction intensities) are also determined by propagation from the precision of the corresponding measured intensities. Although these uncertainties in counting rates are also directly accessible empirically, they are usually estimated from the Poisson distribution, as shown in Equations 14 through 17:

Figure 2. This modification of the x-ray fluorescence thickness measurement diagram depicts the methods of estimation of uncertainty components and the propagation of the resulting uncertainty estimates. where Fluorescent emission of x-radiation is a discrete random process and consequently is Poisson distributed in time.14 This allows estimation of the contributions to measurement uncertainty introduced by random intensity variations since the standard deviation associated with an observed number of Poisson distributed entities (in this case x-ray photons) is the square root of the number observed. This variation constitutes the limit of inherent precision for x-ray fluorescence analysis. Since more x-rays are detected in longer time intervals, this inherent precision limit can be controlled directly by manipulation of the measurement time. The inherent precision of the counting rate can be estimated from the Poisson distribution of the x-radiation as indicated in Equation 13: To = measurement time for substrate

where Ts = measurement time for saturation sample

where Tsc = measurement time for signal correction

where Tm = measurement time for sample. The inherent variability in the thickness measurement can consequently be estimated by propagation of the precision

where Tref = measurement time for reference measurement The reference and signal correction intensities are ascertained by identical measurements (one at the time of

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calibration and the other at the time of sample analysis). Consequently, the measurement times are the same for these two determinations (i.e., Tsc = Tref ). Sufficient measurement time is allocated to signal correction to restrict its contribution to the overall uncertainty in the thickness result to a low level. In addition, the signal correction intensity should not be (and generally does not) allowed to differ substantially from the reference intensity. That is, signal correction is only permitted to correct instrumental drifts of small magnitude; larger changes in intensity require full recalibration. Consequently, the signal correction intensity can be equated to the reference intensity in the calculation of the uncertainty component estimates yielding the approximation shown in Equation 18.

INDIVIDUAL CONTRIBUTIONS TO UNCERTAINTY

The expression for the total uncertainty in the measured thickness, Equation 4, can be interpreted as the combination (in a root mean square sense) of variation in the thickness from two sources: calibration and measured normalized intensity. The latter can be further expanded into contributions from four sources (sample, substrate, saturation, and reference intensities) by Equation 19. This yields a description of the total uncertainty in the measured thickness (not normalized intensity) as a combination (again in a root mean square sense) of individual component uncertainties as shown in Equation 20; each of these components represents a thickness uncertainty that includes both the variation in the source (e.g., a measured intensity) and the sensitivity of the measured thickness to that factor.

This results in simplification of the expression relating the uncertainty in the normalized intensity to variation in measured intensities, as indicated in Equation 19.

where = standard deviation of measured thickness due to variation in calibration = standard deviation of measured thickness due to tx sample intensity variation xo = standard deviation of measured thickness due to substrate intensity variation = standard deviation of measured thickness due to tx s saturation intensity variation standard deviation of measured thickness due to tx ref = reference intensity variation
t

Although the substrate and saturation intensities also vary slightly with time, the impact on the overall uncertainty is similarly negligible. Consequently, the substrate and saturation intensities need not be adjusted from the correspending calibration values. This enables estimation of the uncertainty from direct thickness measurement results and parameters of the calibration (without additional experimental work at the time of measurement). Since the uncertainty in the calibration constant is contingent upon the accuracy of the calibration standards, direct observation of this uncertainty requires repetitive calibration with sets of standards selected randomly from a vast collection of independent standards. This is impractical (if not impossible) due to the paucity of sources of accurate standards, the large expense of such standards, and the relatively long duration of the calibration procedure. Consequently, the uncertainty in the calibration is taken to be the uncertainty within which the standards are certified. Certification of optimal commercial standards is typically specified as 5 percent of the assigned coating thickness. This is considered to be indicative of a 95-percent confidence interval for a normal distribution (1.96 standard deviations), although the exact statistical interpretation of the certified tolerance is frequently unstated. It should be noted that this assumption of a confidence level yields a smaller estimate of the associated standard deviation than would be derived from the assumption of a uniform distribution across the stated interval.

The theoretical estimates of these uncertainty components are given in Equations 21 through 25; since the sample counting rate is generally not reported, these estimates are expressed only in terms of the measured thickness and calibration parameters (the calibration constant and substrate, saturation, and reference counting rates).

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EXPERIMENTAL WORK
Empirical estimates of inherent measurement precision were obtained by repetitive analysis at a single location on each of four gold plate thickness standards using a commercial x-ray fluorescence thickness measurement instrument (FISCHERSCOPE X-RAY 1510Z from Fischer Technology, Inc., 750 Marshall Phelps Rd., Windsor, Connecticut 06095) with a 0.015 by 0.3 mm rectangular collimator. The distribution of the fundamental instrument response (measured intensity) was verified by repeated measurement of the counting rate on the four gold thickness standards as well as on a bare nickel substrate and a saturation (effectively infinite thickness) gold sample. The effect of the intensity variation on the measured thickness was assessed by repetitive thickness measurements on the four plating thickness standards. Both of these sets of experiments were performed at each of two measurement times to demonstrate the effect of measurement time on precision. Direct empirical assessment of the effects of variation in substrate, saturation, and reference intensities is not experimentally accessible because measurements cannot be made in the absence of variation in the counting rate of the measured sample. Therefore, the following procedure was employed as illustrated for the case of variation in the substrate. The substrate intensity was determined (by partial application of the function called Normalization on the Fischer x-ray unit ) using a short measurement time (1 second). The thickness of each of the four plating thickness standards was then measured with a long measurement time (100 seconds) using the newly measured substrate intensity. This series of two measurements was repeated positioning to the same points on both the substrate and the plating thickness standards in each iteration. A long acquisition time for the thickness measurement but a short time for the determination of the substrate counting rate were employed in an attempt to obtain relatively good precision in the former; this approach produced poor precision in the latter, thereby causing the substrate effect to dominate the observed variation. Since the variability of the obtained measurements derives from two sources (sample and substrate intensities), the corresponding theoretical estimate is obtained by combining the individual contributions (in a root mean square sense). The effect of the saturation intensity is assessed in a manner exactly analogous to the assessment of the effect of the substrate. For the effect of variation in the reference intensity, the methodology was also analogous but with several slight differences. The reference intensity is only assignable by performing the instruments signal correction procedure. Therefore, the Fischer x-ray Reference measurement function was invoked between each set of repetitive thickness measurements. Since this function also accomplishes energy calibration of the detection system, the resulting uncertainty estimate may by contaminated by the effect of variation in energy calibration (which is being excluded from consideration). The measurement time for the intensity portion of the signal correction is fixed at 100

seconds. Accordingly, the thickness measurement time is lengthened (to 300 seconds) in an attempt to retain dominance of the effect of interest in the observed variation. Since the reference measurement is a composite of several functions (energy calibration of the detection system and intensity correction), the measurement time associated with the intensity portion of the signal correction procedure is not directly observable. Consequently, the effective measurement time for determination of the reference intensity (Xref) is estimated empirically from repetitive signal corrections. Calibration of the Fischer x-ray instrument for thickness measurement was performed by fitting the ideal calibration relationship to intensity data from 30 measurements on each of 39 gold plate thickness standards on three different substrates (nickel, copper, and nickel-plated brass) from three different sources including the National Institute of Standards and Technology (NIST), formerly the-National Bureau of Standards (NBS). The fitting procedure employed was a weighted linear least squares regression with only one adjustable parameter (a), in accordance with the simplified model of Equation 1. As is usual, the weighings were taken to be the reciprocals of the estimated variances in the thicknesses.15 Since the assigned thicknesses of calibration standards are certified to a relative tolerance (5 percent), the variances were taken to be proportional to the squares of the thicknesses. This assumption of a constant coefficient of variation is also appropriate to the inherent precision of coating thicknesses measured by x-ray fluorescence in the middle of the measurable range. 16 Correspondingly, the uncertainties in the thickness measurement are also expressed in relative terms as the coefficient of variation (CV), which is also known as the relative standard deviation (standard deviation divided by the mean). The effective calibration precision and the uncertainty of calibration imposed by the calibration standards were assessed using the previously cited calibration data for gold plate thickness measurement from the Fischer x-ray system. Analogous calibration data from 17 gold flash (gold plate less than approximately 0.25 m) thickness standards (encompassing both foils and electrodeposits on nickel from four different sources, including the NIST) were also considered as an additional example. The assigned thicknesses for all gold standards assume wrought gold density (19.3 g/cm3).

EXPERIMENTAL RESULTS
The gold plate thickness calibration data are presented in Table 1 and displayed graphically in Figure 3. The resulting calibration parameters are shown in Table 2. The calibration data for gold flash are presented in Table 3. Since portions of the experimental procedure encompassed large numbers of long measurements, the total time period spanned by a single set of measurements was quite extensive in some cases. Consequently, the overall variation

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Table 1. Gold plate thickness calibration data.

ments did not produce reported thickness values due to measured counting rates approaching or exceeding the saturation intensity (whereupon the measured thickness becomes unfoundedly large). This is a natural consequence of high variability imposed by the short measurement time.

Table 2. Gold plate thickness calibration parameters.

Table 3. Gold flash thickness calibration data.

observed in these measurements may include effects of instrumental drift (which could be compensated by more frequent application of the signal correction procedure). To eliminate this potential corruption of the experimental data, the standard deviation was computed between successive pairs of data, and these values were pooled (by calculating the root mean square) to obtain the final empirical estimate of the variability. Although 1000 measurements were taken in each series, only 997 results were obtained for the saturation sample with the short measurement time. Three of the measure-

COMPARISON BETWEEN EMPIRICAL AND THEORETICAL ESTIMATES

The theoretical estimates of uncertainty corresponding to the measured variations in counting rate and thickness are obtained from Equation 13 and Equations 22 through 25 using the calibration parameters indicated in Table 2. These theoretical and empirical values are compared in Tables 4 through 6. The statistical significance of the disparities between these two estimates is assessed by means of the ratio (experimental to theoretical) of the variances (uncertainty values squared), which is expected to follow a 2 /df distribution. Accordingly, the pertinent variance

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ratios are plotted against thickness in Figures 4 through 6, along with the critical values of 2/df at the 95-percent confidence level.

Table 5. Empirical and theoretical thickness precision estimates ( 2/ d f0.025 (500) = 0.879, ( 2/ d f0.975 (500) = 1.127).

Table 6. Empirical and theoretical uncertainty estimates for substrate, saturation, and reference components ( 2/ d f0.025 (50) = 0.638, 2/ d f 0.975 (50) = 1.418). Figure 3. X-ray fluorescence calibration data is displayed in this plot of the measured x-ray intensity as a function of the assigned thickness of gold calibration standards. The line representing the best fit of this data to the ideal calibration relationship is also shown.

Table 4. Empirical and theoretical intensity precision estimates ( 2/df 0.025 (500) = 0.879, 2/df 0.975 (500) = 1.127).

producing superior precision on one given sample is enigmatic. Consequently, the origin of the observed discrepancies is deemed to be statistical rather than systematic. For the sample intensity component of the thickness measurement uncertainty, the 95-percent confidence limits are exceeded in none of the eight cases. Two out of the twelve experimental determinations of the inherent precision of the measured counting rates are lower than the theoretical estimates by an amount that is statistically significant. Since the production of x-radiation is known to be Poisson distributed in time, the theoretical results constitute limits to observed precision upon which improvement is implausible. Further, both of the inconsistencies occur when measuring the lowest gold plate thickness standard (0.035 m); the nature of a mechanism Of the twelve cases representing the substrate, saturation, and reference intensity components of the thickness measurement uncertainty, the upper 95-percent confidence limit is exceeded in one instance (of the reference intensity component) indicating an experimental observation significantly higher than the theoretical estimate. This may result from variation due to energy calibration of the detection system, which is included in the signal correction procedure (reference measurement) but is not considered in the theoretical estimate.

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Figure 4. The ratios of the observed variances from repetitive intensity measurements to theoretical estimates are plotted versus thickness to verify the applicability of Poisson counting statistics. The 95% confidence limits of the 2/df distribution with 500 degrees of freedom are shown for comparison.

Figure 6. The ratios of the observed thickness variances to theoretical estimates are shown as a function of thickness. The observed values were obtained from series of thickness measurements with intervening redetermination of the substrate, saturation, or reference counting rates. This provides an assessment of the validity of the estimation methods for the contributions to thickness measurement uncertainty from the substrate, saturation, and reference intensities. The 95-percent confidence limits of the 2/df distribution with 50 degrees of freedom are shown for comparison.

COMPARISON OF MAGNITUDES OF UNCERTAINTY COMPONENTS

The relative importance of the uncertainty components can be assessed by comparison of the theoretical estimates under typical conditions. As before, the theoretical estimates are obtained from Equations 22 through 25 using the calibration parameters from Table 2. The measurement time for determination of the substrate and saturation counting rates was assumed to be ten times that of the measurement time for samples. As previously cited, the component of uncertainty due to calibration is estimated as 2.55 percent from the certified uncertainty of the calibration standards (5 percent at a 95-percent confidence level). These estimates are plotted in relative terms (coefficient of variation) as a function of thickness in Figure 7 for a measurement time of 10 seconds. Several features of interest emerge from this plot. The substrate component becomes important at very low thickness but is otherwise negligible. The saturation component is insignificant at low thickness but increases with thickness; it will become a dominant contribution at very high thickness although the plot does not extend to sufficiently high thickness to show this. As is desired, the reference component is inconsequential for all thicknesses. The component of uncertainty due to the sample intensity dominates at the thickness extremes. However, throughout the majority of the pertinent thickness range, the calibra-

Figure 5. The ratios of the observed variances from repetitive thickness measurements to theoretical estimates are shown as a function of thickness to validate the estimation method for the component of uncertainty in measured thickness due to variation in the sample intensity. The 95% confidence limits of the 2/df distribution with 500 degrees of freedom are shown for comparison.

In total, three inconsistencies are observed in 32 cases; this is only slightly in excess of expectation for the 95-percent confidence level. Consequently, the proposed theoretical model is determined to be suitable for estimation of the uncertainty of thickness measurement by x-ray fluorescence.

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tion component is predominant. Numerical values of these uncertainty components are presented in Table 7 for a typical application of a 0.7-m thick gold coating. These results show the dominance of the calibration uncertainty and the insignificance of the substrate, saturation, and reference components in a typical measurement situation.

Figure 8. The effect of measurement time on the overall uncertainty of gold plate thickness as measured by x-ray fluorescence is illustrated in this plot of theoretical uncertainty estimates versus thickness for several measurement times. Ten measurements of the substrate and saturation intensities and standards certified to 5% at the 95% confidence level are assumed.

Figure 7. The magnitudes of the various components of uncertainty in thickness as measured by x-ray fluorescence are compared by plotting the theoretical estimates against thickness. These are typical values for a measurement time of 10 seconds assuming ten measurements of the substrate and saturation intensities and standards certified to 5% at the 95% confidence level.

CALIBRATION UNCERTAINTY
Under most situations of interest, the total measurement uncertainty is dominated by the calibration uncertainty. Consequently, it would be most desirable to reduce this uncertainty component. Unfortunately, the contribution of calibration to measurement uncertainty is among the least amenable to control since it originates from the certified tolerance of the calibration standards. Plating thickness standards certified to better than 5 percent are generally not commercially available. Therefore, prospects are scant for substantial reduction in the calibration uncertainty by utilization of superior standards. Improvements in the uncertainty maybe attainable through the application of statistical estimation of the contribution due to calibration. Since the calibration relationship incorporates a single adjustable parameter ( ), this calibration constant is obtainable from a single thickness standard (presuming measurement of substrate and saturation samples). Therefore, if multiple calibration standards are available, the precision of the calibration constant can be estimated also. For calibration with multiple standards, the overall calibration constant corresponds conceptually to the average (properly weighted) of those from individual standards, and the precision estimate corresponds conceptually to the associated standard deviation among them. In practice, these values are obtained from a weighted linear least squares fit of the calibration relationship; the precision is taken to be the standard error of the regression parameter, which derives from the residuals from the line of best fit.17 It must be emphasized that a precision calculated in this manner is a reasonable estimate of the calibration uncertainty only if

Table 7. Typical components of uncertainty in measured thickness for 10 second measurement of 0.7 micrometer gold.

The effect of measurement time on the overall uncertainty is displayed in Figure 8. Due to the dominance of the calibration uncertainty (which is not a function of measurement time), extensive measurement times (beyond approximately 10 seconds for gold) do not yield substantial improvements in the overall measurement uncertainty despite an apparent improvement in the observed precision (from repetitive sample measurements).

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the complement of standards employed in the calibration comprises an unbiased set of independent standards. Such a statistical interpretation of the calibration constant obtained from multiple standards implies that the precision of calibration can be enhanced by inclusion of a large number of calibration standards. In general, the standard error of a mean value is expected to decrease as the square root of the number of individuals included in the random 18-20 sample in accordance with Equation 26.

Table 8. Effect of number of standards on calibration uncertainty by bootstrap estimation.

where = standard deviation of distribution of individuals n = standard deviation of the mean of n samples n = number of samples To investigate this concept, the calibration relationship was fit using a variable number of standards by bootstrap samplinglg19,20of the observed standards (see Tables 1 and 3). Two estimates of the precision for a fixed sample size can be obtained from the regression results: the standard deviation among the calibration constants and the root mean square of the standard errors of the calibration constants (for all cases except a single standard). The results of regression with the bootstrap samplings are listed in Table 8 and displayed graphically in Figure 9. The precision estimates are given in relative terms as the coefficient of variation among calibrations and the root mean square of the relative standard errors. As expected, the calibration precision estimates are very nearly proportional to the reciprocal of the square root of the number of standards (n). The only observable deviations occurs in the coefficient of variation among gold flash calibrations with a single standard; this is probably a result of one highly aberrant standard (0.071 m). Fitting these coefficients of variation to a relationship proportional to the reciprocal of the square root of the number of standards yields the results shown in Table 9. The coefficient of determination is very close to 1, indicating an excellent fit in accord with expectation. Interpretation of the certified tolerance of 5 percent as a 95 percent confidence interval yields an expected coefficient of variation between unbiased standards of 2.55 percent. Comparison of this value with the slopes (CV/[1/n 1/2]), which correspond to the projections of the calibration precision to a single standard, indicates that the thicknesses assigned to the gold standards are slightly less accurate than certified (6.4 percent at the 95-percent confidence level) whereas the gold flash standards are inferior (21 percent at the 95-percent confidence level). Consequently, reduction of calibration uncertainty through utilization of increased numbers of standards was observed with two sets of standards of vastly diverse quality. This simulation of the effect of the number of standards on calibration variability implies that implementation of calibration procedures exploiting multiple standards may be effective in alleviating the deleterious effects of calibration uncertainty. In practice, statistical determination of the uncertainty of calibration (from lack of fit in the calibration data) will encompass all sources of uncertainty associated with the calibration process including the counting statistics of measured quantities as well as the assigned thicknesses of calibration standards. However, this strategy is only applicable if an unbiased complement of independent standards is available. For a biased set of standards, a precision assessment based on comparison between standards (such as lack of fit) will

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thermore, the experimental burden associated with improvement of calibration precision by proliferation of standards is onerous because the uncertainty decreases only as the square root of the number of standards. Consequently, abatement of the calibration uncertainty will entail considerable expense and experimental effort and should only be attempted with great prudence. Nevertheless, if a large number of independent standards is available, the calibration uncertainty can be estimated directly from the standard error of the calibration constant as determined by regression.

CONCLUSIONS
Inclusion of all major sources of measurement uncertainty in empirical estimates minimally requires each measurement in the repetitive set to be made with a different calibration derived from an independent set of calibration standards. Since this is not practical, contributions to measurement uncertainty (other than the inherent precision due to the counting statistics) must be estimated by other means. Since these other sources of variability are substantial (relative to the inherent precision), their effects must be included in order to obtain meaningful overall estimates of the measurement uncertainty. In particular, the effect of calibration bias (due to limitations of certification of calibration standards) predominates in many situations. Failure to account properly for these sources of variation will yield substantial underestimates of the overall measurement uncertainty and may consequently engender erroneous decisions regarding the disposition of product.

Figure 9. The effect of the number of calibration standards on the statistically determined calibration uncertainty is depicted. Observed variations in the calibration constants are plotted as a function of the reciprocal of the square root of the number of standards (to which it is expected to be proportional). These results were derived from variously sized bootstrap samplings of the full set of calibration standards with three replicate runs often thousand trials at each sample size. For each of two calibrations (gold and gold flash), two estimates of calibration uncertainty are represented: 1) variation among calibrations with a fixed sample size as given by the coefficient of variation of the calibration constants (between Cal. CV); and 2) the root mean square (over all calibrations with a fixed sample size) of the relative standard error of the calibration constant as determined by regression (rms within Cal. CV).

ACKNOWLEDGMENT
The author is indebted to Marsha K. Lower for her assistance in the experimental work.

Table 9. Effect of number of standards on calibration precision by proportional fit of coefficient of variation to 1 /n1/2 .

DEFINITION OF SYMBOLS
n = number of samples t = thickness of coating layer Tm = measurement time for sample To = measurement time for substrate Tref = measurement time for reference measurement Ts = measurement time for saturation sample Tsc = measurement time for signal correction X = intensity at thickness t Xn = normalized intensity Xo = substrate intensity (t = 0) Xref = reference intensity on signal correction sample Xs = saturation intensity (t ) Xsc = measured intensity on signal correction sample = calibration constant standard deviation of distribution of individuals standard deviation of the mean of n samples standard deviation of coating layer thickness standard deviation of measured thickness due to sample intensity variation standard deviation of measured thickness due to substrate intensity variation

underestimate the calibration uncertainty. Similarly, if the standards are not independent (for example, if there are systematic effects with thickness level), errors. in the uncertainty estimation (possibly varying with thickness) may ensue. Unfortunately, these stipulations are difficult to satisfy due to the dearth of availability of high-quality thickness standards. Generally, sets of standards obtained from a single source (which is common) maybe expected to be biased and are not anticipated to be independent. Fur-

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tXref

= standard deviation of measured thickness due to reference intensity variation tXs = standard deviation of measured thickness due to saturation intensity variation = standard deviation of measured thickness due to t variation in calibration X = standard deviation of intensity at thickness t Xn = standard deviation of normalized intensity Xo = standard deviation of substrate intensity Xref = standard deviation of reference intensity Xs = standard deviation of saturation intensity Xsc = standard deviation of signal correction intensity = standard deviation of calibration constant

11. E.P. Bertin, Introduction to X-ray Spectrometric Analysis (Plenum Press, New York, 1978), pp. 381-383. 12. Y. Ronen, Uncertainty Analysis (CRC Press, Boca Raton, FL 1988), p. 50. 13. S.K. Muthu, Probability and Errors for the Physical Sciences (Sangam Books Limited, London, 1982), p. 355. 14. R.D. Evans, The Atomic Nucleus (McGraw-Hill Book Co., New York, 1955), pp. 750-752. 15. G.E.P. Box, W.G. Hunter, and J.S. Hunter, Statistics for Experimenters (John Wiley & Sons, New York, 1978), p. 505. 16. B.J. Cross, D.C. Wherry, and T.H. Briggs, Plating and Surface Finishing 75 (2), 68 (1988). 17. N.R. Draper and H. Smith, Applied Regression Analysis (John Wiley & Sons, New York, 1966), pp. 77-80. 18. G.E.P. Box, W.G. Hunter, and J.S. Hunter, Statistics for Experimented (John Wiley & Sons, New York, 1978), pp. 66-68. 19. P.R. Bevington, Data Reduction and Error Analysis for the Physical Sciences (McGraw-Hill Book Co., New York, 1969), p. 117. 20. N.R. Draper and H. Smith, Applied Regression Analysis (John Wiley & Sons, New York, 1966), pp. 80-81. 21. B. Efron, Ann. Statist. 7, 1 (1979). 22. B. Efron and R. Tibshirani, Science 253, 390 (1991). Glenn E. Staudt is a Member of Technical Staff in the Technology Group at AMP Incorporated in Harrisburg, Pennsylvania. Mr. Staudt received a Bachelor of Science degree in chemistry from Bucknell University, Lewisburg, Pennsylvania in 1974 and a Master of Arts degree in chemistry from Princeton, New Jersey in 1976. From 1977 to 1981, he was employed as a chemist at Hamilton Technology, Inc. in Lancaster, Pennsylvania. Since joining the Technology Group of AMP Incorporated in 1981, his activities have included technological support and research in the areas of electrodeposition and electrodeposited materials. Current research interests focus on the characterization of metallic coating systems.

REFERENCES
1. ASTM Standard B568-90, Standard test method for measurement of coating thickness by x-ray spectrometry (American Society for Testing and Materials, Philadelphia, PA 1990). 2. A. Ott, Plating and Surface Finishing 63 (11), 28 (1976). 3. A.R. Colclough, Journal of Research of the National Bureau of Standards 92, 167 (1987). 4. W. Wger, in Quantum Metrology and Fundamental Physical Constants (proceedings of the NATO Advanced Studies Institute Conference, Erice, Sicily) Series B, Vol. 98, edited by P.H. Cutler and A.A. Lucas (Plenum Press, 1983), p. 613. 5. J.W. Mller, in Precision Measurement and Fundamental Constants II (Special Publication 617), edited by B. N. Taylor and W.D. Phillips (National Bureau of Standards, Gaithersburg, MD, 1984), p. 375. 6. E.R. Cohen, Proceedings of the 1986 Measurement Science Conference (Irvine, CA, 1986), p. 292. 7. S.S. Wagner, Phyikalisch-Technische Bundesanstalt Mitteilungen 89 (2), 83 (1979). 8. H. Brown, D. Lashmore, and F. Ogburn, Plating and Surface Finishing 70 (9),76 (1983). 9. H. Behncke, Plating and Surface Finishing 74 (5), 112 (1987). 10. F. Ogburn and J. Smit, Plating 60 (2), 149 (1973).

AMP Journal of Technology Vol. 3 November, 1993

G.E. Staudt

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