61 XRF X-Ray Fluorescence TING C. HUANG ictive, rapid,Basic Principles ‘The fundamental principles of XRF can be found in the literature.!-? Briefly, X rays are electromagnetic radiation of very high energy (or short wavelength). The unit of measurement for X rays is the angstrom (A), which is equal to 10“ cm. When an X- ray photon strikes an atom and knocks out an inner shell electron, if the incident photon has energy greater than the binding energy of the inner shell electron, a readjustment occurs in the atom by filling the inner shell vacancy with one of the outer electrons and simultaneously emitting an X-ray photon, The emitred photon ation) has the characteristic energy of the difference between the (or fluorescent ra binding energies of the inner and the outer shells. The penetration depth of a high- m- energy photon into a material is normally in che wm range. (Another method cor monly used ro produce X rays is electron-beam excitation; the penetration depth of beam js about an order of magnitude smaller than that of X rays. See Xray line spectra of a number of elements jn 1913. He found that the square root of exhibited a linear relationship with the the lines. This fundamental “Moseley law” istic X-ray spectrum and that the wave- ‘one element to another. The wavelengths ents increase. In addition to the spectra ectrum of brass, which showed strong Cu XRF analysis. The use of XRF for routine not carried out, however, until the intro- late 1940s. XRF measurements normally comprises 5 the crystal spectrometer, and the is shown in Figure 1. Fluorescent high-energy (or short-wavelength) fluorescent X rays from the speci- primary collimator. The analyz- planes of known d-spacing, (@) in accordance with Bragg’s giving the order of reflection. lar speed of the detector, the Teflected one by one as the ana- . The intensity of at each lure is known also as the 339a i Secondary oe collimator X-ray tube gth-dispersive method is used exten- volume.) fo, Ag, ot Cr target is commonly used as specimen. A secondary target mate- gmetimes to excite fluorescence. This ent energy close to the absorption (or not exciting) interfering ele- Xray sources, including syn- (which emits Mn KX rays) tube in some applications, 0), which have 2 spacings te (002), spacing 6.715 A: and synthetic multilayers =160 A. The lowest-Z cle- on the d-spacing of the » and each reflection is the crystal used be of angular spread of the QUES = Chapter 6Figure2 XRF spectrum of MnFe/NiFe thin film. selecting a crystal with a smaller 4 Atillation counters having thin Be window ths (above 3 A or 4 keV), and gas-flow propo: ibsorbing windows and Ar/CHy gas for long A single-channel pulse amplitude analyzer is ithin a selected wavelength range to imp liminate unwanted high-order reflections. Reasurement range between 2 few seconds gon specimen characteristics and the desir. Fe thin film is plotted in Figure 2. The the film are identified, and the remaini 1e X-ray tube. The experimental conditions dat 45 kV, a LiF (200) analyzing crystal, nel pulse amplitude analyzer. The 9 keV was 24 cV, compared to 145 eV (sce EDS article). The high spectral made possible the measurements of it peaks, ‘on the angle of incidence. It region to several wm at large 341nates from lc, the grazing incidence angles (a few tens of degrees). The XRF beam, which variable depths, can be used for elemental depth analysis. Por exar incidence XRF method has been used for studies of concentration profiles of a dix solved polymer near the air/liquid interface,‘ Langmuir-Blodgett multilayers and multipletayer films on substrates.® This type of analysis requires a parallel-incs dence beam geometry, which currently is not possible with a trometer Chemica! State Analysis The XRF wavelengths and relative intensities of a given element are constant to first approximation, Small changes may occur when the distribution of the out valence) electron changes. A major area of research in XRF invol Xeray emission (or long-wavelength XRF) spectra for chemical state analysis Structure, which is a direct indication of the elec jund the emitting atom. Thus the shift in tion, or appearance of additional peaks factors, including the oxidation st ly bound ligands, etc. The equip tical to that required for conventional lastudy of transitions involving the outer fe X-ray analysis employs 2 long-wave- Ke) or Cu (13.36 A for Cu La). Spe- ing wavelengths in the range 10-100 A ent pelements present, XRF can be used to fand layer thicknesses of thin films. must be corrected for various fac- the incident X rays, fluorescent Two general methods used for method and the fundamen- thematical approximation are predetermined from the ind thicknesses of chi predetermination of the is possible, Because of standards with either the the empirical parameters imited. film HNIQUES = Chapter 6i ived directly from The fundamental parameters method uses XRF equations ae first principles. Primary and secondary excitations are 8 Be ah excitations are caused directly by the incident X rays from the X-ray sours, WY * the secondary excitations are caused by other elements in the same film, whose pri mary fluorescent X-ray radiation has sufficient energy to excite the characteristic radiation of the analyzed element. Higher order excitations are generally considered insignificant because of their much lower intensities. XRF equations relate inten- sity, composition, and thickness through physical constants (fundamental parame- ters) like fluorescent yields, atomic transition probabilities, absorption coefficients, etc, For example, the XRF equations for single-layer films were reported by Laguit- ton and Parrish,® and for multiple-layer films by Mantler.? The equations for thin films are yery complex, and the values of composition and thickness cannot be determined directly from the observed intensities. They are obtained by computer using cither linear or hyperbolic approximation algorithm. The funda- is suitable for the analysis of thin films because it or mixed element and bulk or thin-film stan- -film analysis is in the simultaneous determi- The technique has been used for the routine 1977 and multiple-layer films! since 1986. the fields are the annual volumes of Advances lew York, and the Journal of X-Ray Spectrome- ical examples on the analysis of single-layer it illustrate the capabilities of the technique. of compositions were selected because of tof Fe KX rays in the films, XRF quartz substrates are listed in Table 1 ‘Atomic Absorption Spectroscopy (AAS) ). Since the strong X-ray absorption XRF and EPMA but not present in the two non-XRF techniques pro- in Table 1, there is good agreement and the average deviation is 0.9% and EPMA. It is worth noting FeNi films obtained by XRF, AAS, atended compositions (see values 1). The discrepancy shows the 343,Film XRF AAS EPMA FeGNios) 4205 Fe (10)-Ni (90) 92 90 62 Fe (20)-Ni (80) 19.4 19,2 19.4 Fe (34)-Ni(66) 47.30 48.4 44.5 Fe(50)-Ni(50) 591 61.7 59-1 Fe (66)-Ni (34) 78.9 79.8 78.4 i (20) 89.6 89.2 (% wt.) for Felvi films. he important of determining composition stechniques. ofa film appear together as a single param- af pz the areal density (not the thickness) is the areal density, the film thickness can be iS known experimentally or theoretically. the film composition and the published esses of 12 Fey9Nigg films were calcu- re compared to those obtained by a nitor). As shown in Table 2, good es are obtained with average and ly (see the last column of ple, the volume densities of 8 50-10,000 A were calculated hat the volume density of the fith the film’s thickness. It is of the presence of XRF ts in the same layer lculation of XRF inten- 13 Proper correc- QUES Chapter 6Nooxret —-A/XRF (3) Film XRF 2 —st«ia 8 2 858 848 12 a 1117 1142 22 4 3180 2967 67 5 3215 3011 63 6 3558 3473 24 ‘ is 05 15 5.6 1.0 37 essential for a successful XRF analysis compositions and thicknesses for those for single-layer films. analyze two triple-layer films of Cr, 2 14 The two films, Ti and T2, have different order. In T1, the FeNi the Cr layer at the bottom; in T2, , with Cr on top and FeNi ar the iddle, Because of this reversal of t effects are grossly different in the observed intensities 1 and T2 were ~17%, +2%, and Ni Ket observed intensi- the results obtained by two DF270 from Japan’ are in composition and 1% in 345Parameter ‘Triple layer 11 12 (FeNi/Cu/Cd) — (C/Co/FeNI) Fe(owe) 10.25 10.25 NiQwe) 89.75 89.75 tor (A) 1652 1698 1674 — tReni(A) 2121 2048 - 2115 sont teal) 2470 2457 = aAi6 Tables XRF results for films of Cr, FoNi, and Cu. ¢ listed in Table 3. In Fe and Ni, the com- are essentially the thickness. The results obtained by the LAMA-III program 2x rge diff iin the observed intensities of Cr, yrs determined by XRF : In an XRF analysis was also done on three sin- '§2, and S3) prepared under identical deposi- films. As shown in Table 3, good agreement triple-layer films. This indicates that the rption effects observed in Tl and T2 were that the deviations between the results of in the accuracy reported for the single-layer ossible thar some of the clements may be layers. XRF analysis of this type of film can lely from their observed intensities. Addi- tions or thickness of some of the layers is XRF information required depends on the tthe analysis of a FeMn/NiFe double-layer led can be the composition or thickness of 1€ composition or thickness of one of the {deposited under idenccal conditions, , Which are described elsewhere in and each of these three tech- ISSION TECHNIQUES — Chapter 6EPMA Both XRF and EPMA are used for elemental analysis of chin films. XRF uses a non- focusing X-ray source, while EPMA uses a focusing clectron beam to generate fluo- rescent X rays, XRF gives information over a large area, up to cm in diameter, while EPMA samples small spots, jum in size. An important use of EPMA is in point-to- point analysis of elemental distribution, Microanalysis on a sub-um scale can be done with electron microscopes. The penetration depth for an X-ray beam is nor- mally in the 10-um range, while it is around 1 wm for an electron beam. There is, therefore, also a difference in the depth of material analyzed by XRF and EPMA. eps EDS is another widely used elemen tal analysis technique and employs a solid state desector with a multichannel analyzer to detect and resolve fluorescent X rays Scoring to their energies. EDS uses either X rays or an electron beam as a source il » which uses the wavelength-dispersive method One, EDS collects all the fluorescent X rays from tation of EDS is its energy resolution, which is an thar of the wavelength-dispersive method. For fon elements overlap the KB peaks of the next lytical difficulties. The poorer resolution also aground ratios in EDS data, eribed in this article, is normally used for ele- Hons of 0.1% or higher. Total Reflection X-Ray ieidence angles of a few tenths of a degree is ectable limits down to 10° atoms/cm? are now fay source, Examples of the use of this tech- ithe article on TXRF in this volume, achnique for the elemental-composition film materials. The technique is nonde- entially very accurate. XRF character- » development, and manufacture g; superconducting, and other types ent is expected in the area of micro- idence XRF analysis of surfaces chemical state analysis, and syn- 347