X-RAY FLUORESCENCE METHOD FOR DETERMINING THE THICKNESS OF AN ALUMINUM COATING ON STEEL N. I. Mashin, a* A. A. Leonteva, a A. N. Tumanova, a and A. A.

Ershov b UDC 543.422.8 We have used an EDX-720 energy-dispersive x-ray fluorescence spectrometer to develop a technique for determining the thickness of an aluminum coating deposited on steel 47 NKhR. We have calculated the mass absorption coefficients for absorption of the fluorescent emission of nickel by the aluminum coating, where nickel is a major component of the substrate material. We have established and present the metrological characteristics. Keywords: energy-dispersive x-ray fluorescence method, coating thickness, interelement interference effects. Introduction. The nondestructive x-ray fluorescence method is widely used to determine the composition and thickness of deposited layers in microelectronics, the metal refining industry, data acquisition devices, and also corrosion-resistant coatings in metallurgy and the automobile industry. This method makes it possible to rapidly and highly accurately determine the thickness and composition of several stacked layers in the thickness range from nanometers to micrometers. In [1, 2], the authors demonstrate theoretically and experimentally the possibility of measuring the thickness of different single-component films and also a layer of silver electrolytically deposited on brass, as well as chromium, cobalt, nickel, and zinc foil. The authors of [1], as in [3], note that in order to measure the thickness of

films (to 5 m), it is necessary to use the dependence of the intensity of fluorescent x-radiation on its surface density. In determining the thickness of coatings made from copper, chromium, and nickel in the range 50 m, the authors of [4] used the dependence of the fluorescence intensity of the above-indicated elements on the coating thickness without taking into account the background, which ultimately affected the accuracy of the analysis. The experimental data showed that x-ray fluorescence analysis (XFA) has an uncertainty (~10%) practically comparable with the uncertainty in x-ray spectral microanalysis. In [5], local sections of the surface were analyzed for samples of area 0.011.00 cm 2 . The range of determined thicknesses of gold coatings on a nickel substrate was 0.2513.40 m, and the uncertainty in the determination was 1220%. The authors of [6] used XFA to determine the thicknesses of thin coatings (with surface density ms < 500 g/cm 2 ), which then were used as single-component reference samples in xray spectral microanalysis. Earlier, techniques were proposed for determination of the thickness of thin monolayer multicomponent [7, 8] and bilayer films, both single-component [9, 10] and composites in which one layer was multicomponent [11, 12]. This work was devoted to developing a technique for a nondestructive method for determining the thickness (dAl 100 m) of an aluminum coating deposited on a steel 47 NKhR substrate (cNi = 46.25%, cFe = 47.35%, cMn = 0.40%, cCr = 5.25%). We investigated the possibilities for two methods for determining the thickness of aluminum coatings on steel

substrates, using an EDX-720 energy-dispersive x-ray fluorescence spectrometer (Shimadzu, Japan). The optimal conditions for excitation of the analytical lines for the analyte elements are given in Table 1. The area of the sample irradiated by the x-ray tube was 0.8 cm 2 . The first method (I) is based on the rise in the relative intensity of the characteristic emission I rel AlK as the thickness of the deposited coating dAl increases. The method essentially involves plotting the calibration curve for the fluorescence intensity vs. surface density using films of known surface density. a Nizhny Novgorod N. I. Lobachevskii State University, 23 prosp. Gagarina, Bldg. 5, Nizhny Novgorod 603600, Russia; e-mail: mashin@chem.unn.ru; b Nizhny Novgorod Scientific Research Institute of Radioengineering, Russia; e-mail nnirt@nnirt.ru.Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 78, No. 3, pp. 454459, May June, 2011. Original article submitted December 27, 2010. To whom correspondence should be addressed. 0021-9037/11/7803-0427 2011 Springer Science+Business Media, Inc. 427 Journal of Applied Spectroscopy, Vol. 78, No. 3, July, 2011 (Russian Original Vol. 78, No. 3, MayJune, 2011)The second method (II) is based on the decrease in the relative intensity of fluorescence for elements of the substrate as the thickness of the aluminum coating increases, since when x-rays are incident on the object under study, characteristic emission is excited for both the coating and the substrate. Experimental Section. Method I. Determination of the thickness of an aluminum coating from the rise in

the relative intensity of the AlK characteristic emission as the thickness of the coating increases. Determination of the thickness of thin layers (dAl 400 nm) of an aluminum coating. We know that for very thin films, the dependence of the relative intensity on surface density is linear [14]. Accordingly, when establishing the surface density of an aluminum coating h < 104.1 g/cm 2 , it is valid to use the ratio applicable in analysis of single-component thin films: I rel AlK I AlK 0 I AlK = AlK Al m Al , (1) where

AlK Al = 1 Al sin + AlK Al sin ; (2) IAlK 0 and IAlK are the fluorescence intensities of the K line of aluminum from the reference sample and a bulk aluminum sample (after subtracting the background intensity); AlK Al is a coefficient whose value is determined from films with known surface density, mAl = Al dAl ; 1 Al

and AlK Al are the mass absorption coefficients for absorption of the primary radiation and the AlK line in Al; = 60 o and = 45 o are the angles of incidence and exit for the x-rays. As the bulk sample, we used reference samples with aluminum coating thickness equal to 100 m. In order to reduce the uncertainty level in determining the coefficient AlK Al , we conducted studies on selection of the specific characteristics of the reference sample enabling increased accuracy of the XFA. Using the data obtained, we plotted and studied the calibration curves (Fig. 1a) for the relative intensities of the AlK lines vs. the surface densities of the reference samples for the two cases. In the first case, we studied a kit of eight reference samples of aluminum films, the surface density of which varied within the interval 15.1104.1 g/cm 2 ; in the second case, all eight reference samples had a surface density of 104.1 g/cm 2 . According to (1), the coefficient AlK Al is equal to the slope of the calibration curve. In calculating this coefficient, we used the least-squares method, which allowed us to find both the value of AlK Al and its uncertainty AlK

Al . The major contribution to AlK Al comes from thin films with low surface density, having high relative standard deviations sr *8+, so in calculating AlK Al AlK Al we should use thin films having the maximum allowable surface density. The values of AlK Al for the curves shown in Fig. 1a for the two cases indicated above are equal to 1002 12 and 1006 4 cm 2 /g. As we see, the uncertainty in determining the coefficient AlK Al (n = 8, P = 0.95) is less in the second case, and accordingly this coefficient was used in calculating the thickness of the aluminum according to formula (1). The surface density of the thin film of aluminum serving as the reference sample was found by weighing the steel substrate before and after sputter deposition of the film, on a VRL-20g balance within 5 g. In order to eliminate error connected with the weight difference between the substrate and the sputtered film, we used the "compensation" method [7]. The thickness dAl was determined on an MII-11 multibeam microinterferometer within 2 nm. From TABLE 1. Optimal Operating Conditions for the EDX-720 Spectrometer Analyte element Energy, keV [13] Operating mode

Exposure time, Ks B 1 Kq U, kV I, A Al 1.49 1.56 1.56 15 350 100 Cr 5.41 5.95 5.99 50 17 Mn 5.89 6.49 6.54 Fe 6.39 7.06 7.11 Ni 7.46 8.26 8.33 428the measured mAl and dAl , we obtained the experimental density Al exp = 2.54 0.04 g/cm 3 of the aluminum in the thin film, which we used when going from the surface density of the thin film to its thickness. Determination of the thickness of layers of the aluminum coating for dAl 100 m. In order to plot the calibration curve I rel AlK = f(dAl ), we need to have a set of reference samples of different thicknesses. As we know, obtaining thinfilm reference samples, especially of intermediate thickness, is associated with considerable technological

difficulties. Therefore we propose a rather simple method for solving this problem: successive stacking of several layers of aluminum foil of thickness 10 m and 13 m on the steel substrate. When the sample under study is exposed to the primary x-ray beam, fluorescent x-ray emission of the AlK line appears, the intensity of which can be calculated using the equation: I rel AlK I AlK 0 I AlK = 1 exp ( AlK Al Al d Al ) , (3) where Al = 2.698 g/cm

3 [15] is the density of aluminum. Figure 1b shows the calibration curve I rel AlK = f(dAl ) plotted using data averaged over ten measurements of the relative fluorescence intensity of the AlK lines for films of different thicknesses. As the bulk sample, we used a reference sample with thickness of the aluminum coating equal to 100 m. The graph obtained can be divided into three linear sections: d = 1020 m, d = 2030 m, d > 30 m, and d 1020 m = 270.27I rel AlK 243.51 , (4) d 2030 m = 416.67I rel AlK 386.25 , (5) for dAl > 30 m the relative intensity I rel

AlK = 1 and does not depend on the thickness of the aluminum coating. The dependence illustrated in Fig. 1b, after taking the logarithms, rather clearly is represented by a straight line in the aluminum foil thickness range 1026 m (Fig. 2) and is described by the equation: d Al = 11.188 ln (1 I rel AlK ) 21.084 . (6) With the goal of establishing the accuracy of the proposed method, we measured the relative fluorescence intensities of the K lines of aluminum I rel AlK for two samples with known thickness of the aluminum coating (d1 = 13 m and d2 = 26 m), and from formulas (4)(6) we calculated the values of the parameter under study and the Fig. 1. Relative fluorescence intensity of the AlK line (I rel AlK = IAlK 0 /IAlK vs.

surface density of aluminum thin films (a) and vs. thickness of the aluminum foil applied to the steel (b). 429uncertainties corresponding to them (Table 2). As we see, the uncertainty in its determination is unacceptably high: twice as high as the uncertainty in determination of the thickness with a micrometer. For dAl > 30 m, the relative fluorescence intensity I rel AlK does not depend on the thickness of the aluminum coating, and so we need to use another approach to determine it. Method II. Determination of the thickness of an aluminum coating from its absorption of fluorescent emission from elements in the substrate. Absorption of the characteristic emission of the K lines of the elements (Cr, Mn, Fe, and Ni) in the substrate occurs as the emission passes through the aluminum coating: I BK Al =I BK 0 exp ( BK Al Al

d Al ) , (7) where IBK 0 and IBK Al are the intensities of the characteristic emission from the elements in the substrate without the aluminum coating and with the aluminum coating. We conducted studies estimating the thickness of the aluminum layer by measuring the absorption by an aluminum coating of fluorescent emission from elements included in the composition of the 47NKhR steel substrate (cNi = 46.25%, cFe = 47.35%, cMn = 0.40%, cCr = 5.25%). In order to determine the thickness of the coating, using the second method we measured the fluorescence intensity of the K lines of nickel, manganese, iron, and chromium from a number of steel samples without a coating and from the same samples covered with aluminum foil of thickness 10100 m at 10 m intervals. We measured the intensities for the elements of the substrate by the fundamental parameter method (Table 1). Then from the measured fluorescence intensities, we calculated the absorption coefficients for fluorescent emissions of nickel, iron, manganese, and chromium in aluminum according to the formula: BK Al

= ln (I BK 0 I BK Al ) d Al Al , (8) Fig. 2. ln ( 1 I rel AlK ) vs. thickness of the aluminum foil applied to the steel. TABLE 2. Results of Measurement of the Thickness (m) of Aluminum Foil by Different Methods (n = 10, P = 0.95) Sample Micrometer method XFA method Method I Method II 1 13 0.5 13.7 0.8 12.95 0.06 2 26 0.5 25.2 1.2 25.96 0.07 430where BK Al

is the absorption coefficient for absorption of the fluorescent emission from the elements of the substrate in the aluminum coating; IBK 0 and IBK Al are the fluorescence intensities of the elements in the substrate detected from steel without a coating and steel covered with aluminum foil; dAl is the thickness of the aluminum foil. As we see from Fig. 3, the absorption coefficients for emission of the K lines of iron, manganese, and chromium decrease as the thickness of the aluminum foil increases. For nickel, the absorption coefficient NiK Al = 98.2 0.3 cm 2 /g remains constant over the entire range of variation in the thickness of the aluminum layer, which allows us to use this factor to determine the thickness. From Eq. (7), it follows that for calculation of the thickness of an aluminum coating from absorption of the NiK line, we need to measure its intensity before (INiK 0 ) and after (INiK Al ) passage through this layer: d Al =

ln (I NiK 0 I NiK Al ) NiK Al Al . (9) Using (9), we calculated the thicknesses and their corresponding uncertainties for two steel samples with known values of the parameter under study. In Table 2, we give a comparison of the thicknesses of the aluminum coating established using the dependence I rel AlK = f(dAl ) and calculated according to formula (9) for two samples of known thickness. As we see, better results are obtained by measuring the absorption by the aluminum of the characteristic emission from the nickel atoms (a major component of the substrate material).

Metrological treatment shows that determining the thickness of an aluminum layer in the 10100 m range is characterized by sr = 0.0040.001. The validity of determining the thickness of aluminum layers using the proposed method has been confirmed by comparing the values obtained with the certificate data: d20 m = 19.97 0.06 m; d50 m = 49.87 0.11 m; d90 m = 89.76 0.25 m. As we see, the agreement between the results and the uncertainty in determination of the thickness are quite satisfactory. Conclusions. We have developed rapid, nondestructive, highly accurate techniques for determining the thickness of aluminum coatings deposited on steel. We have shown that for a small coating thickness, we need to use a method based on the increase in the relative intensity of the characteristic emission I rel AlK with an increase in the thickness dAl of the coating. In the case when the linear relation between I rel AlK and dAl fails, we need to use a method taking into account absorption by the aluminum layer of the fluorescence from elements of the substrate. Fig. 3. Absorption coefficients for emission of the K lines of nickel, iron, manganese, and chromium vs. the thickness of the aluminum foil applied to the steel. 431REFERENCES 1. V. N. Karev, A. P. Klyucharev, and V. N. Medyanik, Zav. Lab., 28, No. 12, 14491451 (1962). 2. M. A. Blokhin and V. F. Volkov, Zav. Lab., 27, No. 9, 11101111 (1961). 3. B. A. Malyukov, Yu. M. Ukrainskii, and V. E. Korolev, Zav. Lab., 33, No. 8, 961965 (1967). 4. K. A. Gusev and V. I. Khomyakov, Pribory i Sistemy Upravleniya, No. 12, 2324 (1984).

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