IntroductionNowadays, especially in semiconductor industries, large amounts of ultrapurified chemicals, such as water, hydrogen peroxide, acids, and bases, are required for manufacturing highquality semiconductors in microelectronic industries. 1 The use of ultrapurified chemicals can help to fulfill two main objectives, namely the production of high-quality products and the minimization of rejects.2 Consequently, there has been a growing demand for the sensitive and accurate determination of trace and ultratrace amounts of impurities, such as boron, phosphorus and silicon, in ultrapurified chemicals. In general, such nonmetallic elements/compounds are less sensitive to conventional atomic spectroscopic methods, such as AAS, ICP-AES and ICP-MS. For example, the limits of detection (LOD) of silicate and phosphate in ICP-MS, which is known to be one of the most sensitive instruments and is often used in semiconductor analysis, are about 1 ppb or larger. Therefore, its sensitivity is not sufficient for the determination of a sub-ppb or ppt level of such non-metallic substances.The determination of trace and ultratrace amounts of phosphorus has become more and more important in such fields as semiconductor industry, ultrapurified chemicals (UPC) and ultrapurified water (UPW) manufactures etc. 3 The phosphomolybdenum blue method, either with or without solidphase enrichment, has often been used for phosphorus and silicate determination, 4-8 though the procedures are sometimes troublesome and time-consuming, for improving the sensitivity they need filtration/collection procedures with membrane filters. Sensitive spectrophotometric and fluorometric methods based on ion-associate formation deserve much attention. Molybdophosphate forms ion-association complexes with bulky cationic or basic dyes, which are the basis of sensitive detection methods for determining phosphorus spectrophotometrically. Malachite Green has found the widest application.9-15 Motomizu et al. [16][17][18] have reported a highly sensitive spectrophotometric method for determining phosphorus at sub-ppb and ppt levels using relatively small volumes of the sample solutions, an organic solvent (methyl cellosolve: MC), and a tiny membrane filter for collecting the ion associate of molybdophosphate with Malachite Green. The absorbance of the collected ion associate dissolved in MC was measured by an off-line flow injection-spectrophotometric detection method, which is relatively simple and shows excellent sensitivity. However, the collection/concentration procedure with a tiny membrane filter and dissolution of the ion associate in MC is troublesome and time-consuming.Highly sensitive fluorescence quenching methods for the determination of phosphate coupled with a flow-injection technique were also reported. These methods are based on the formation of an ion associate of molybdophosphate with Rhodamine 6G. 19,20 They are very sensitive with a detection limit of 0.1 ppb, 19 though the prepared reagent solution was not stable. Later, a method with Rhodamine...
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