ANALYTICAL

SCIENCES

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DETERMINATION

OF

TRACE

ELEMENTS

IN

PHOTORESISTS

USED IN

THE FABRICATION

OF SUBMICRON

VLSI

TSU-YEN Materials Chutung,

CHANG*, LIAN-SHERN CHEN, MEEI-YUN SHIUE AND YA-CHUN Research Laboratories, Industrial Technology Research Hsinchu, Taiwan R.O.C.

SUN, Institute,

Abstract have been

Chloride determined

ion and at their

several trace

metals levels.

in submicron VLSI grade Chloride ion was determined

photoresists by poten-

tiometric argentometric titration of standard silver nitrate solution in acetone. Good recovery was obtained for as low as 2,ug of total chloride, including those attributed to blank and sample, in the titration cell. In the determination of trace metals, we made comparison between two methods, namely, flame AAS preceded by dry ashing of the photoresist and the direct analysis using graphite furnace AAS without sample digestion. In the latter method, oxygen ashing was employed. Analytical results for iron and zinc by the two methods were comparable. Key words photoresist, metals, chloride ion, trace analysis.

INTRODUCTION Trace contaminants in the chemicals used in microelectronic industry are usually of high interest to both manufacturers and end users. The contaminants not only change the electrical properties of integrated circuits but also corrode their metallic parts and shorten their lifetime [1,2]. In this study, we investigated the determination of chloride ion and several metals in photoresists used in the fabrication of submicron VLSI. Because manufacturers generally desire less than 0.5ug/g each of elements in photoresists, highly sensitive techniques are necessary. Photoresists are dark-colored, highly viscous organic materials. Normal techniques for the determination of trace chloride ion [3-5] are not directly applicable to such materials. The dark color of photoresists forbids the proper detection of end point in mercuric nitrate titration and interferes strongly in spectrophotometric technique, while their viscous organic matrices forbid the use of ion chromatographic or ion selective electrode techniques. Potentiometric argentometric titration in organic solvents [6,7] on the other hand seems feasible, and thus are investigated in this study. For the determination of trace metals in organic materials, direct analysis of samples are highly desirable because of its high speed, low risk of contamination and low loss of interested metals [8-10]. We therefore used the direct analysis approach for the analysis of photoresists using graphite furnace atomic absorption spectrometry. Because of the lack of proper standard reference materials for the evaluation of accuracy, we compared the results with those of conventional dry-ashing pretreatment of samples followed by flame AAs. The results from calibration curve method and standard addition method were also compared. EXPERIMENTAL Apparatus For the determination of chloride ion in photoresists, a Kyoto AT-118 po entTometric automatic titrator was used, with a Metrohm 6.0404.100(OC) combined silver electrode. For the determination of metals, a Varian 875 flame atomic absorption spectrometer and a Perkin-Elmer 5100 atomic absorption spectrometer were used. The Perkin-Elmer 5100 instrument was equiped with a model HGA 600 graphite furnace and was capable of performing Zeeman background correction. Manual injection by micropipette was used for analyzing photoresist samples. Pyrolytically coated graphite tubes with L'vov platforms were used throughout the study. The preparation of all standard solutions and samples were performed in a clean room to minimize airborne contamination. All labwares were soaked in (1:4) nitric acid (v/v) overnight and rinsed by deionzed water, Reagents All the reagents used were OR grade chemicals. Silver nitrate stock solution of OTIN was prepared from E.Merck volumetric solution. Chloride and metal stock solutions of 1000 pug/ml were prepared from E.Merck Titrisol solutions. Chloride-free acetone was distilled from GR grade acetone with added silver nitrate crystallines. Deionized double distilled water and subboiled acids were used throughout the experiment for metal determination. Oxygen gas as matrix modifier was of a purity greater than 99.99% and argon gas was of the similar purity.

1266 Procedure for chloride ion determination Weigh 1 to 10 grams of photoresist sample into lop m beaker. Add 40 m acetone an ml (1:1) nitric acid (v/v). Mix well and then potentiometrically titrated with 0.01 to 0.5 mN standard silver nitrate solution. The choice of the concentration of silver nitrate solution lies in the chloride content of sample and the weight of sample used. Usually, the titrant volume exhausted was kept to less than 1 ml i n order to eliminate the error caused by the dissolution of silver chloride. Procedure for metal determination using flame AAS preceded by dry ashing/acid
dissolution len grams of photoresist sample was weignea into a piatinum cruciDle. The sample was then dried completely on a hot plate and under an infrared lamp in clean room for 10-15 hours, followed by dry ashing in muffle furnace at 500C. The ash was dissolved in 2 ml (1:1) subboiled hydrochloric acid and diluted to 10 ml with deionized double distilled water. The metal content was then determined by flame AAS. Procedure for metal determination using graphite furnace AAS Both of standard addition me o an ca ira Ton method were emp aye or the de termination of the metals. Photoresist samples were diluted with GR grade acetone to proper ratio by weight. For standard addition method, a 25aul aliquot of sample was carefully injected into the graphite tube followed by a 5 ul aliquot of the standard solution of varying concentration. The sample was then dried, ashed and atomized with a temperature program shown in TABLE 1.

TABLE 1.

Instrument

parameters

for graphite

furnace

AAS.

RESULTS AND DISCUSSION Chloride ion determination Chloride is highly prone to contamination, therefore, samples must be handled with special care. All the containers must be cleaned thoroughly as decribed in the experimental section. Electrodes used to potentiometrically detect the end point of argentometric titration must be carefully selected so that there is no leakage of chloride to the sample solution. Regular Ag/AgCI reference electrodes filled with KC1 solution, thus, are not appropriate. A combined silver electrode filled with KNO3 solution was employed in this study and proved its excellent applicability. Acetone was chosen as the titration medium because it suppressed the solubility of silver chloride and offered high solubility for photoresists. Chloride concentrations as low as 0.04&ug/ml was determined with good accuracy. Recovery study of chloride ion added to chloride-free acetone showed 92 to 103% recovery for 2,ug to 20,ug added chloride. For the case of spiked chloride less than 2Mg, recovery dropped dramatically and thus this method was not applicable. The accuracy of this method for photoresist analysis was proved by the recovery study of chloride ion spiked to photoresists and GR grade acetone(Fig.1). We found that chloride content in GR grade acetone (blank value) varied widely from 0.002 to 0.12 pug/ml. Therefore, blank value must be determined before samples are analyzed. Standard chloride should be added to make up the total amount of chloride in acetone to greater than 2ug in the case of low blank value. The detection limit of this method is dependent upon the precision of the measurements and is estimated as 0.02~ug/ml (3 SD). The ratio of acetone to photoresist sample was adjusted according to the viscosity and the chloride content of the photoresist. For photoresists of low viscosity and low chloride content, lower ratio was a better choice. As shown in Fig. 2, accurate results were obtainable at the ratio as low as 0.4 for typical photoresist samples.

ANALYTICAL

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Fl g.1

Recovery study of chloride ion spiked to photoresists and GR grade acetone.

Fi g.2 The effect of the anaunt of photoresists (PR) to the analytical results. Voltme of acetone:2D ml.

The that ion

analytical samples contents.

of

results of different

several lot

commercial numbers

photoresists showed

were quite

shown large

in

TABLE

2.

We found on chloride

sometimes

deviation

TABLE 2. Analytical

results

of chloride

content i n conmercial photoresists

Metal element determination Commercial photoresists used in the fabrication of submicron VLSI were mixtures o p o osensitizer, binder, solvent, and additives if necessary. The binder used are mostly Novolac. The solvent can be xylene, ethoxyethyl acetate (EEA), propylene glycol methyl ether acetate (PGMEA) etc, or mixture of these. The diluted sample contained a lower b.p. solvent (acetone, b.p. =53C) and a higher b.p solvent (xylene, EEA.., b.p. in the range of 100-150C). For drying process, a stepwise temperature program was carefully designed in accordance to the b.p. of solvents to ensure no spattering occurred. Fig. 3 shows that Novolac resists to thermal decomposition in inert atmosphere while it decomposes easily in air at 600C. Therefore, oxygen were used as matrix modifier in the ashing step to eliminate carbonaceous build-up on platform and in graphite tube. For some elements, such as zinc and sodium, background absorbance was largely reduced (Fig.4).

Fi g.3 Thermal decomposition of a photoresi st i n (a) air, and (b) nitrogen atmosphere

Fi g. 4 Absarbance profiles for Na and Zn of 20 U1 aliquot of a photoresist sair le Atomic absorbance profiles. Background absorbance profiles. (a) For Na, ashed in 0 , (b) For Na, ashed in A, ( c) For Zn, ashed i n 0 , (d) For Zn, ashed in A.

1268

The effect of the background reduction is even greater for zinc because the complete overlap of the background and atomic absorbance profiles. The complete expulsion of oxygen with argon gas under low temperature before atomization was necessary in order to avoid the excessive oxidation of graphite tubes. The optimum atomization temperature for sodium and iron were higher than those typically suggested in handbook as expected from the mechanisms proposed by Salmon, Davis and Holcombe [11,12]. The absorbance profiles for zinc and iron dropped back to baselines within 5 seconds while that of sodium showed a bad tailing. Huie and Curran [13] suggested that this was a result of strong interactions of sodium vapor with the furnace wall during the course of atom removal. Providing internal argon flow during atomization would reduce the tailling but at the same time lower the sensitivity. Nonlinear Curve of multiple standard additions for sodium was obtained and thus could not be used for the determination. The analytical results of iron and zinc in several commercial photoresists are shown in TABLE 3 and TABLE 4. Data obtained from standard addition by graphite furnace AAS and dry ashing/flame AAS for both elements showed reasonable agreement. Iron content in PR013 and zinc content in PR014 determined by flame AAS were suspected to be contaminated. It "s also shown in the tables that calibration curve method gave good results for iron but not for zinc. The averaged precision using graphite furnace AAS method was about 5 to 10% RSD while that using dry-aching/flame AAS method varied widely from 10 to 20% RSD.

TABLE 3.

Conpari son of anal yti cal results

of iron

i n photoresi

sts .

TABLE 4.

Con ari son of analytical

results

of zinc

i n photoresi

sts.

CONCLUSIONS Potentiometric argentometric titration using acetone as titration medium is proved to be an accurate method for the determination of trace chloride in photoresists. Zinc and iron can be directly determined without predigestion by graphite furnace AAS using oxygen as matrix modifier. The experimental conditions for sodium must be further investigated in order to attain accurate results.

REFERENCES 1. 2. 3. 4. 5. 6. 7 8. E. Sacher, IEEE Trans. Electr. Insul., El-18, 369 (1983). H,J.Neuhaus, D.R.Day and S.D.Senturia, J.. ohElectr. Materials, 14, 379 (1985). K. Tomlinson and K.Torrance, Analyst, 102, 1 (1977). ^' H.V.Malmstadt and J.D.Winefordener, Analyti a Chim. Acta, 20, 283 (1959). R.J.Bertolacini and J.E.Barney ll , Anal. Chem., 30,202 (1958). ASTMD512-81, "Standard Test Methods for Chloride Ion in Water', ASTM, 11.01, 1988. T.Y.Chang and D.Wang, MRLBull. Res. Dev., 4, 69 (1990). C.L.Chakarbarti, R.Karwowska, B.R. Hollebane and P.M.Johnson, Spectrochimic Acta, 42B, 1217 (1987). 9. 1T asaki, S.Hagi and H.Yamamoto, Sekiyu Gakkai Shi, 23, 210 (1980). 10.L.A.Way and B.J.Presley, Anal. Chim. Acta, 83, 385 (T75). 11.S.G.Salmon, R.H.Davis and J.Holcombe, J.AnaT: Chem. 53, 324 (1981). 12 . S . 0 . Salmon and J.Holcombe, Anal. Chem. 54, 630 (1982) 13.C,W.Huie and C.J.Curran Jr., Appl. SpecTT, 44, 1329 (1990).