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X-RAY SPECTROMETRY

X-Ray Spectrom. 28, 433–439 (1999)

ACCOUNT

Surface-Sensitive X-Ray Fluorescence and
Diffraction Analysis with Grazing-Exit Geometry
T. Noma,1 * K. Takada1 and A. Iida2
1
2

Canon Research Center, Morinosato-Wakamiya, Atsugi, Kanagawa 243-0193, Japan
Photon Factory, Institute of Materials Structure Science, 1-1 Oho, Tsukuba, Ibaraki 305-0801, Japan

Surface-sensitive x-ray analysis techniques are explained. Using grazing-exit geometry, structural information
about a sample surface could be obtained by measuring the angular distribution of x-ray fluorescence or
x-ray diffraction intensity. A model based on the reciprocity theorem was used and its correctness was
confirmed by achieving good agreement with experimental results. The interference of fluorescent x-rays in
layered thin films was observed. The refraction effect in x-ray diffraction was detected. These phenomena
can be utilized in thin-film characterization. Use of a synchrotron x-ray microbeam in combination with
the grazing-exit condition permitted surface analysis with lateral spatial resolution. Layered thin films were
characterized. The principle of this method and results obtained are presented. Copyright  1999 John
Wiley & Sons, Ltd.

INTRODUCTION
Many electronic and optical devices have been developed
as a result of progress in materials technology. In many
cases, their functions depend mainly on the property of the
surface thin layers of materials. Therefore, near-surface
compositions and structures are important. Although
x-ray analysis techniques, including both x-ray diffraction
(XRD) and x-ray fluorescence (XRF) analysis, have a
high accuracy and a non-destructive nature, sensitivity
to the surface is low compared with techniques that use
electrons and ions. The grazing-incidence (GI) condition
has enabled the x-ray characterization technique to be used
to characterize the surface of materials. It has been used
in various x-ray research fields; GI XRD,1 total reflection
x-ray absorption fine structure,2 GI x-ray reflectometry3
and GI XRF4,5 have been successfully applied to the
characterization of surfaces. These techniques avail
themselves of the fact that the x-ray penetration depth
depends on the angle of incidence, and is extremely
shallow under the grazing-incidence condition.
Surface analysis of a practical sample sometimes requires lateral spatial resolution. Recently, various types of
synchrotron x-ray microprobes have been developed.6 – 18
Using the grazing-incidence condition, however, x-ray
microprobes are not effective because the incident x-rays
spread out over the sample surface.
Becker et al.19 have pointed out that the grazing-exit
(GE) XRF experiment also provides the same information as the GI XRF experiment, according to the
optical reciprocity theorem,20 which was confirmed by
* Correspondence to: T. Noma, Canon Research Center, MorinosatoWakamiya, Atsugi, Kanagawa 243-0193, Japan.
E-mail address: noma@crc.canon.co.jp

CCC 0049–8246/99/060433–07 $17.50
Copyright  1999 John Wiley & Sons, Ltd.

measuring the exit and incidence angular dependence of
the XRF intensity of a germanium crystal. Various types
of GE XRF experiments have been performed.21 – 31 Noma
et al.22 observed the interference phenomenon of fluorescent x-rays in layered thin films using synchrotron radiation. De Bokx and co-workers23 – 26 developed a laboratory
GE XRF spectrometer with wavelength-dispersive detection and applied it to the determination of light element
contaminants on Si wafers. In GE XRF experiments, the
angle of incidence can be adopted at any value. Tsuji and
co-workers27 – 30 developed the technique of GE XRF in
conjunction with grazing incidence and achieved higher
surface sensitivity.
Since normal-incidence geometry can be realized, the
GE XRF in combination with a synchrotron x-ray microprobe permits surface-sensitive analysis with lateral spatial
resolution.31
For polycrystalline thin films, GI XRD has been used to
conduct crystal structure analysis.32 The authors proposed
use of the GE XRD technique instead, since it allows thinfilm characterization with a high spatial resolution.33,34
This paper summarizes our recent work on x-ray analysis using the grazing-exit condition, and shows some
applications of GE XRF and GE XRD to practical
samples. In the first section, we present a model for
grazing-exit conditions and the role of the reciprocity theorem in the data analysis process. The reciprocity theorem
is useful in explaining the experimental results, and therefore simplifies the calculations. The second section of the
paper presents the principles and phenomena observed in
GE XRF experiments; the interference effect of fluorescent x-rays in layered materials is demonstrated. In the
third section, we describe the principles and applications
of GE XRD; thin-film characterization by synchrotron
x-ray micro-diffraction is introduced. Finally, we summarize the possibilities of grazing-exit techniques.
Received 10 May 1999
Accepted 25 July 1999

The wave amplitude E. We describe some examples below. which dictates that the radiation propagation process has a source that is symmetrical with the point of observation. the oscillation structure of the fluorescent x-rays as a function of the glancing angle is observed as a result of the interference between incident and reflected x-rays. Figure 2 shows the calculated curves for Cr K˛ from Cr–Au layered structures. According to the reciprocity theorem. which is induced by incident radiation having the same wavelength under grazing-incidence geometry.35 The observed x-ray intensity I. The film thickness strongly affects the oscillation structure. Figure 3. z/j2 dz . 1(a). 28. the oscillation structure is also expected in the exit angle dependence as a result of the interference of the fluorescent x-rays themselves.˛. Experimental arrangement of GE XRF. IIDA We performed experiments using synchrotron radiation at the Photon Factory on beamline 4A.1/ I. I.˛/ oscillates as a function of ˛. TAKADA AND A.z/ is the x-ray source density at depth z. (b) X-ray wave intensity estimation under the grazing incidence geometry. 433–439 (1999) . NOMA. GRAZING-EXIT X-RAY FLUORESCENCE When a layered thin film is measured under the grazingincidence condition.˛/ at exit angle ˛ is given by Z T C. x-ray emission induced by charged particles and x-ray diffraction/scattering. which is induced by the incident radiation with glancing angle ˛. Calculation of film thickness effect on exit angle dependence of Cr K˛. and interface roughness.434 T. z/ at depth z in the layered structure.˛/ D K 0 where C. (a) Conceptual drawing of the x-ray propagation process in layered materials. Let us assume that the x-ray radiation from Po is detected at a point outside the material under the grazing-exit condition. x-ray fluorescence. Ltd. T is the thickness of the layer and K is a proportional coefficient. Po is an x-ray source inside the material.37 On the other hand.z/jE. Figure 2. as illustrated in Fig. 1(b). can be calculated by applying Fresnel’s recursion equation.20 We used the stratified layered structure to explain the basic principle of the calculation. The exit angle dependence provides information about the structure of layered materials. The basic idea behind this treatment is similar to that of Kossel lines by Laue. the intensity contribution from individual sources is the same as the wave intensity at the position of each source.21 Figure 1(a) is a conceptual drawing of the x-ray propagation and exit process from the stratified layered material. Figure 1. in which fluorescent radiation from the source within a crystal is diffracted by its crystal lattice. as illustrated in Fig. The intensity distribution of the radiation is the sum of the contribution from sources within the x-ray emitting region. Copyright  1999 John Wiley & Sons. under the grazing-exit condition.36 The present approach is available for use in the analysis of any type of x-ray emission phenomena. In the case of layered structures. K. THEORY X-ray intensity emitted from a sample surface at a grazingexit angle was estimated by the model by applying the reciprocity theorem.˛. X-Ray Spectrom. including information on thickness and density variation.

the technique that uses grazing-incidence x-rays and asymmetric Bragg diffraction is useful. Dots are the measured data and solid lines are fitting curves. The structure was estimated to be Cr2 O3 (4 nm)–Cr (46 nm) based on a parameter-fitting calculation. 28. X-ray microbeams were formed by using the Kirkpatric–Baez system consisting of a pair of elliptical mirrors. Synchrotron x-rays were monochromated with an Si(111) double-crystal monochromator.32 Using the grazing-incidence condition.5 and 12. The exit angle dependence of the Cr K˛ intensity is shown in Fig. The measured data were normalized by the primary x-ray intensity. The highest value of Au L˛ intensity measured was 3015 counts per 200 s. which is the critical angle of total external reflection for Cr K˛ radiation. This geometry attained an angular resolution of less than 0. Figure 4. Therefore.SURFACE-SENSITIVE XRF AND DIFFRACTION WITH GRAZING-EXIT GEOMETRY 435 Figure 5. A receiving slit 80 µm wide was placed before the Si(Li) detector at a distance of 360 mm from the sample.3 mrad. The exit angular dependences of the Cr K˛ and Au L˛ intensity of the sample are shown in Fig. the presence of a thin surface oxide layer was taken into consideration.22 Figure 3 shows the experimental arrangement. because incident x-rays irradiate a X-Ray Spectrom. Since it is expected that the chromium oxide layer was formed at the chromium surface. The two curves are different in oscillation amplitude and phase. The synchrotron x-ray microbeam system using Kirkpatrick–Baez optics. The x-ray irradiated area was about 1 ð 1 mm2 at the sample surface. Primary x-rays impinged on the sample surface at nearly normal incidence. respectively. GRAZING-EXIT X-RAY DIFFRACTION To conduct structural analysis of polycrystalline thin films. The exit angle dependences of (a) Cr K˛ and (b) Au L˛ intensity from the layered thin film sample. The vacuum path was not used. The intensity of fluorescent x-rays was measured as a function of the exit angle ˛. Fluorescent x-rays were detected by an Si(Li) detector. the Cr K˛ intensity increases steeply at 9 mrad. information about internal interfaces can be obtained by the grazing exit x-rays. The GE XRF in combination with a synchrotron x-ray microbeam allows small-area surface analysis. The mirrors were made of platinum-coated fused quartz. A receiving slit 100 µm wide was placed before the Si(Li) detector at a distance of 100 mm from the sample. 4 depicts the sample configuration. The Au L˛ intensity curve does not exhibit strong oscillations. It is necessary to optimize the angular resolution to promote detection efficiency. 433–439 (1999) .31 The synchrotron x-ray microbeam system is illustrated in Fig. The beam size was about 7 ð 6 µm2 at the sample position. A W–Si multilayer monochromator was used instead of a double-crystal monochromator to increase the photon flux density. 6. 4(a) and (b) respectively. The Au layer is thick enough to mask the radiation from lower layers under the grazing-exit condition. 3. The highest value of Cr K˛ intensity measured was 1123 counts per 50 s. The theoretical curves (solid Copyright  1999 John Wiley & Sons. x-rays reflected at the Cr(top)–Au interface are the main contributors. which depend on reflectivity at the interfaces of the Cr layer and the layer underneath. The interference oscillation structure is observed in the Cr K˛ intensity curve. 6.17 The sample was mounted on XZ translation stages that were mounted on a rotation stage with a vertical rotation axis. since the higher angular resolution results in a poor signal output. We demonstrated grazing exit micro-XRF using a Cr thin film deposited on patterned Ni thin films. This geometry attained an angular resolution of around 1 mrad. We observed the interference of fluorescent x-rays in Cr–Au layered thin films. A more detailed description of the focusing system has been presented elsewhere. 5. As the exit angle increases. The structural parameters obtained from the fitting calculations are also shown in Fig. The samples used were Cr(top)–Au–Cr layered thin films deposited on synthetic quartz substrates.5 keV were used for Cr and Au excitation. X-rays tuned at 9. The inset in Fig. These curves agree with the experimental data very well. 4 were obtained using the model mentioned above. The material beneath the Cr layer affects the Cr K˛ intensity distribution curves. and increases just as in the case of bulk materials. The angular dependence of the fluorescent x-ray intensity was measured by using the method illustrated in Fig. it is difficult to conduct a small-area analysis. lines) in Fig. Ltd.

we characterized palladium thin films in the process of oxidization and reduction. the diffraction peaks were fitted with Gaussian functions. 28. X-ray microbeams were formed by using the Kirkpatrick–Baez system mentioned above. however. Ltd.03° in 2 angle. The incidence angle ω was fixed at 30° . First. The films turned brown. 9(b)]. We found that the palladium oxide films were reduced inhomogeneously through the hydrogen reduction process. These films were then exposed to diluted hydrogen gas (H2 2%. Copyright  1999 John Wiley & Sons. These results also demonstrate the lateral resolution and surface sensitivity of this measurement. The sample was mounted on XZ translation stages that were mounted on an ω-rotation stage with a vertical rotation axis. observation through an optical microscope revealed that many dark spots had appeared and had become enlarged in the brown-colored films. Figure 11 shows diffraction peak height and peak position as a function of ˛ (exit angle). 7. they are deformed by absorption and refraction effects due to the grazing-exit condition. In order to obtain the diffraction angle and peak intensity. The theoretical diffraction intensity is derived using Eqn (1). where ω is the incident angle of the primary x-ray beam to the sample surface and ˛ is the exit angle of the diffracted x-rays. The x-ray energy used was 8 keV. The highest value of Cr K˛ (a) intensity measured was 592 counts per 100 s. the diffraction profile as a function of 2 at a given ˛. Figure 7. i.33 The principle is illustrated in Fig. large area of the sample surface. NOMA. Therefore. 10 µm per step for the Zscan [Fig. The angular resolution of the present system was determined by the energy bandwidth of the multilayer monochromator. Each curve is a combination of the 2-dependent diffraction curve and ˛-dependent x-ray transmission curve. Synchrotron radiation from a bending magnet was monochromated using a W–Si multilayer monochromator. The samples were prepared as follows. K.34 Palladium thin films can be oxidized by annealing in air and palladium oxide thin films can be reduced by exposing them to hydrogen gas at room temperature. by analogy with x-ray fluorescence intensity. A series of x-ray diffraction patterns across the boundary were obtained. Figure 9 shows the micro-diffraction results for the film after hydrogen reduction. Figure 8 shows the experimental arrangement. The angular distribution measurement was taken at a point in the dark spots (reduced area). The resolution of PSPC is about 0.8° at an angle (2) of 40° . N2 98%) for a few minutes. As an application of this technique. Experimental arrangement of micro-GE XRD. Figure 10(b) shows the Pd(111) converted diffraction profiles for various exit angles ˛. The measured data were normalized by the primary x-ray intensity. TAKADA AND A. Many dark spots over a bright area can be observed via an optical microscope [Fig. The density values 89% and 91% indicate the density relative to the bulk value. A position-sensitive proportional counter (PSPC) was placed 200 mm from the sample to detect x-rays scattered from the sample. the x-ray diffraction angle (2) measured by the PSPC is ω C ˛. It is useful to separate the two parameters.436 T. Figure 10(a) shows a series of x-ray diffraction patterns measured at various incidence angles ω (36–42° ). Experimental results of micro-GE XRF. The monochromated x-ray beams impinge on the sample surface at a large glancing angle and diffracted x-rays are detected with a small (grazing) exit angle. The solid line is the X-Ray Spectrom. 9(a)]. These patterns contain crystallographic information. The divergence of the primary x-ray beam is about 0. Dots are the measured data and solid lines are the fitting curves. we deposited about 45 nm of palladium on fused quartz substrates and annealed them in air at 400 ° C for 10 hs. 433–439 (1999) . IIDA Figure 6. and is about 0. Only the Pd(111) peak can be observed in the dark area and the PdO peak appeared in the bright area. The inhomogeneous films obtained through the above process were analyzed.e. In the present experiment. Conceptual drawing of grazing exit x-ray diffraction from a polycrystalline thin film. In this geometry. During this process. Figure 8. These data show that the dark area was reduced completely and oxide still remained in the bright area. The XZ translation stages were used for sample positioning. An optical microscope was used to align the ω-rotation stage and the sample with the focal point.2° in the diffraction plane. the grazingexit condition is required to characterize polycrystalline thin films with a lateral spatial resolution. the beam size was about 6 ð 6 µm2 at the sample position (focusing point).

(b) X-ray diffraction profiles as a function of the exit angle (˛).38. Experimental results of micro-GE XRD with a high spatial resolution. 28. The density of the sample was obtained through the refractive index derived from the diffraction peak shift curves. The XRD patterns were measured by a PSPC.SURFACE-SENSITIVE XRF AND DIFFRACTION WITH GRAZING-EXIT GEOMETRY 437 Figure 9. . the density and the thickness were obtained. 433–439 (1999) .˛2 2 C . is given by 2 D ˛ 1 p f[. (b) Series of x-ray diffraction patterns across the boundary. The shift angle 2. 10 µm per step for the Z-scan.˛2 2υ/2 C 4ˇ2 ]1/2 2υ/g1/2 Copyright  1999 John Wiley & Sons. The circles indicate the points of measurement. at exit angle ˛. A sufficient number of crystallites are required to estimate the exit angle distribution of the x-ray diffraction X-Ray Spectrom. Ltd.39 The diffraction peak shift by refraction is also expected in the grazing-exit condition. as shown in Fig. 11 is the curve calculated using Eqn (2). It has been pointed out that x-ray diffraction peak positions are shifted by the effect of refraction in a grazing-incidence condition. We should comment on three points regarding the sample texture in GE XRD analysis: 1. (a) X-ray diffraction patterns as a function of the incidence angle (ω). The dashed line in Fig. (a) Optical micrograph of the sample. Figure 10. 11. From the fitting parameters. Figure 12 shows the calculated curves that exhibit the film density effect of the palladium thin films. Dots are the measured data and solid lines are fitting curves.2/ where υ and ˇ are the factors in the refractive index (r D 1 υ iˇ) of the sample. Information obtained from the exit angle dependence on the Pd thin film after hydrogen reduction. The incidence angle ω was fixed at 30° . fitting curve for the peak height calculated using a stratified thin-film model. The experimental data agreed with the calculation very well.

Rev. Diffraction peak height and peak position as a function of exit angle (˛). P. J. K. since the average crystallite size of palladium thin films was about 20 nm. Phys. J. A. Suzuki and F. CONCLUSION Figure 12. Interference of fluorescent x-rays in layered thin films was observed. van Langeverde. 14. Prins (Eds). Gordon. 54. A. Sci. S. 9. A. However. Rondelez. J. Engstrom. Y. Instrum. Pounds. Appl. 127 (1992). G. Jones. Methods A 292. K. D. Becker. Nucl. Hanson. A. Acknowledgement The authors thank the Photon Factory staff for valuable support during the experiments. 719 (1990). 160 (1993). 12. Uchida and Y. Adv. Iida. Principles of Optics. La and J. 62. D. 5602 (1992). A means of averaging is required for samples with a coarser texture. Rev. X-Ray Anal. F. K. By using x-ray beams with a narrower energy bandwidth and a sufficient photon flux. Methods B 82. 1039 (1985). G. 2452 (1989). Suzuki. A. Y. Bloch. K. A. H. W. F. 50. X-Ray Anal. 7. 6. Underwood. Koningsberger and R. Uchida. T. TAKADA AND A. A. Noma. X-ray Absorption–Principles. M. Rindby. 433–439 (1999) . Wiley. C. Hirai. 7. Wu and R. Robinson. Sato. Iida and N. 11. K. Hayakawa. W. 13. Eisenberger. Application Techniques of EXAFS. In this work. Tros. Pincus. 2545 (1991). Hayakawa. K. M. 10. Lett. These phenomena can be utilized in thin-film characterization. Takahashi and Y. Phys. J. 8. Sci. J. 4. Yun. Hirano. W. intensity. Hayashi. de Boer. M. P. R. Adv. 15. 296 (1988). Lengeler. Rev. We used a model based on the reciprocity theorem and confirmed its correctness by obtaining satisfactory agreement with the experimental results. I. 20. M. H. North-Holland. B. We confirmed that the sample did not have a strong preferred orientation. the resolution of x-ray diffraction patterns was limited by the energy bandwidth of the primary x-ray beam. F. Jpn. 16. 18. edited by D. more detailed crystallographic information could be obtained. A. Gaul. Gohshi. M.6ð6 µm2 / was of the order of 105 . Brown. 32–2. G. Saitoh. J. in Handbook on Synchrotron Radiation. SEXAFS. Gohshi. 2. Lett. Rev. S. Hayakawa. 60. Calculation of refraction effects on the diffraction peak position. Phys. the solid line is a fitting curve for peak height and the dashed line is a fitting curve for peak position. Jpn. Kuiatek. R. D. Sci. Viccaro. Instrum. Nucl. T. A. Instrum. 63. J. Nucl. K. 19. A. Aoki and Y. Thompson. 59 (1988). Nucl. Amsterdam (1991). Thompson. X-Ray Spectrom. It is believed that only a few hundred or fewer crystallites contribute to a diffraction line accepted by the detector. Pergamon Press. Knochel and F. Sci. H. this peak shift is smaller than that caused by refraction in a small exit angle region. K. Chapt. R. Rev. Y. Aoki and K. Iida. 35. L. Thin-film structure parameters such as thickness. D. 17. 129 (1993). P. Underwood. Inagawa. Each curve indicates the Pd(111) peak shift as a function of exit angle (˛) for various film densities. L. and XANES. Bowen. The diffraction peak positions are shifted by the effect of residual stress as a function of ω. 153 (1983). D. 3. A. NOMA. Instrum. Vis. density and surface roughness were obtained from x-ray intensity as a function of the exit angle. M. J. Dots are the measured data. Rev. Rev. Higashi and K. Suppl. Instrum. p. Instrum. J. Sutton. The refraction effect in x-ray diffraction was detected. New York (1988). 28. R. Garbe. R. IIDA Figure 11. Gohshi. Moncton and G. Peiffer. Iida. Ltd. Buttkewitz. S. S. It was shown that grazing-exit x-rays provide useful information about the thin-film structure. Rivers. Both fluorescent x-rays and diffracted x-rays can be used as probes. S. F. M. C. S. Kim and P. Golovchenko and J. 221. Jpn. C. 31. S. S. 63. 63. J. Giauque. S. A. M. L1660 (1989). Chrzas. Methods A 302. J. Phys. Huizing and D. Phys. 795 (1992). Appl. B. Vol. Patel. 28. Kato. 27. the number of crystallites in the area . Giauque and Y. X-Ray Anal. Noma. B. Wolf. 3. A. 35. Larsson. The diffraction peak intensities are modified by the effect of the preferred orientation. Lechtenberg. A synchrotron x-ray microbeam in combination with the grazing-exit condition allowed surface-sensitive analysis with a spatial resolution of a few micrometers. and it can be applied to various types of polycrystalline materials. A. REFERENCES 1. Sansone. Y. W. Instrum. Wu. 2. Instrum. Iida and T. G. 582 (1992). B. GE XRD can be carried out with x-rays of various wavelengths. Appl. Instrum. Born and E. 5. S. 3. 547 (1991). 578 (1992). Copyright  1999 John Wiley & Sons. L2131 (1988). Sci. Iida. Adv. G. New York (1975). C. We can isolate these effects in the curves of angular dependence. Usami. In the above experiment. M.438 T. Kohra. Methods A 266. D.

Jpn. S. J. 34. 5. Yamada and T. 199 (1995). London (1982). Miyata and S. Rev. Sci. 837 (1994). James. Sato and K. J. 33. Phys. P. X-Ray Anal. 31. Adv. Rev. Huang. Urbach. C. 33. 24. Appl. L1277 (1994). J. Wagatsuma. Urbach. 32. B 53. Takada and A. 27. 23. A. 39. Tsuji. Instrum. K. Part B 52. Rev. Phys. Phys. Hirokawa. 66. B 39. 38. 30. 433–439 (1999) . in press. de Bokx and H. 95. G. Noma. Noma and A. 28. R. K. K. Parrat. P. S. K. Jpn. Bell. Anal. 25. K. Spectrochim. Matsumoto. A. Appl. Iida. Acta Part B 52. X-Ray Anal. X-Ray Anal. 109 (1990). Noma. Hirokawa. Rev. X-Ray Chem. T. 359 (1954). Wagatsuma. Appl. Chr. H. The Optical Principles of the Diffraction of X-Rays. Sakurai. T. 33. Ino. 438–456. B 48. T. Instrum. Sato and K. P. L1535 (1996). H. Phys. F. T. L900 (1992). 3752 (1996). Brennan. 26s. Adv. Noma and A. 35. 15 (1995). Instrum. Urbach and P. Rev. Phys. de Bokx. Iida and K. 65. 36. K. Jpn. X-Ray Anal. Urbach. Ltd. Bailleul. p. P. 23 (1991). Phys. Adv. Sci. 34. P. 4847 (1995). 66. Takayama and Y. L. K. Iida. T. 35. Synchrotron Radiat. K. Wiener and H. de Bokx and H. T. M. 17524 (1993). Adv. T. Hirokawa. Rev. 22. 902 (1998). Kok. de Bokx. Noma. Adv. K. 7963 (1989). A. Sci. K. Tsuji. 33. 91 (1990). Phys. Spectrochim. 829 (1997). Toney and S. Jpn. Acta. 37. G. W. Iida. P.SURFACE-SENSITIVE XRF AND DIFFRACTION WITH GRAZING-EXIT GEOMETRY 21. T. 31. 439 29. Tsuji and K. 28. Copyright  1999 John Wiley & Sons. Utaka. Iida. Rev. P. X-Ray Spectrom. 841 (1997). J. 26. Tsuji. K.