Microchim. Acta 144, 9–15 (2004) DOI 10.1007/s00604-003-0093-2 Original Paper Multielement XRF Semimicroanalysis of Pb(Zr,Ti)O 3 Type Ferroelectric Ceramic Materials Doped with Pb(Nb,Mn)O 3 and Bi 2 O 3 by the Thin Layer Method Rafal Sitko 1; , Beata Zawisza 1 , Jerzy Jurczyk 1 , Dariusz Bochenek 2 , and Mal gorzata Pl on ´ska 2 1 Institute of Chemistry, Silesian University, 40-006 Katowice, Poland 2 Department of Material Science, Silesian University, 41-200 Sosnowiec, Poland Received August 26, 2003; accepted September 13, 2003; published online December 15, 2003 # Springer-Verlag 2003 Abstract. A method of wavelength-dispersive XRF analysis of Pb(Zr,Ti)O 3 type ferroelectric ceramics doped with Pb(Nb,Mn)O 3 and Bi 2 O 3 is presented. The major elements Pb, Zr, Ti and minor elements Nb, Mn, Bi were determined. Matrix effects were minimized by using the thin layer method. Standards of the same chemical composition but varied masses were prepared to simplify calibration. To minimize errors resulting from inhomogeneity of a mass per unit area, the internal standard was used. Preparation of the sample consisted in digesting 25 mg of the materials (with nickel as the internal standard) in sulfuric acid, evaporating to dryness and digesting in nitric acid and hydrogen peroxide, filling up to 25 mL, and dropping 0.5 mL of the solution onto a substrate. Standard sam- ples were prepared by dropping different amounts of the multielement solution onto the substrate. The re- sidual standard deviation for the reference sample of mass from 0.25 mg to 0.7 mg was within the range of 0.001–0.009 mg (correlation coefficient 0.998–0.999) for major elements and within the range of 0.00003– 0.0009 mg (correlation coefficient 0.989–0.993) for minor elements. The detection limits for 0.5 mg samples were within the range of 0.015%–0.35% for manganese and zirconium, respectively. Key words: XRF; thin layer analysis; ferroelectrics; PZT; lead titanate zirconate solid solution. Both bulk and thin film ferroelectric materials are often applied in practice e.g. in capacitor technology, electronic, electro-optic and electro-acoustic equip- ment [1, 2]. Chemical composition of practically applied ferroelectrics is different: BaTiO 3 , SrTiO 3 , (Ba,Sr)TiO 3 (termistors), LiTaO 3 (pyroelectric detec- tors), LiNbO 3 , NaNbO 3 , KNbO 3 , Pb(Zr,Ti)O 3 (piezo- electric transducers), (Pb,La)(Zr,Ti)O 3 (elements of memory), Bi 4 Ti 3 O 12 (photoelectric multipliers) and many more. A lot of detailed information about bulk and thin film ferroelectric materials is not published. The methods of preparing these materials require the use of high temperatures. Under such conditions ferroelectrics can lose oxygen (oxygen vacancies appear), and the lead compounds can lose lead. There- fore, it is necessary to analyze the chemical composi- tion of the obtained products and to determine minor elements, which modify physical properties of the product, as well as major elements. Trace elements, which are usually impurities, have to be determined, too. Pb(Zr,Ti)O 3 type materials (PZT) can be analyzed  Author for correspondence. E-mail: rsitko@us.edu.pl