Handbook of ICP-QQQ Applications using the Agilent 8800 and 8900

Significance of Topic

Advances in inductively coupled plasma triple quadrupole mass spectrometry (ICP-QQQ) have transformed ultratrace elemental analysis in high-purity chemicals used for semiconductor processing. By combining double mass filtering (MS/MS), versatile reaction/collision cell chemistry, and optional cool or hot plasma modes, ICP-QQQ addresses challenging spectral overlaps and delivers detection limits in the low ppt to sub-ppt (fg/L) range. Reliable measurement of elements such as P, S, Si, Cl, Ca, K, V, Cr, Ge, As and more ensures contamination control at the wafer surface, underpinning device performance and yield.

Goals and Overview of Studies

Eleven application examples showcase the capabilities of Agilent’s 8800 and 8900 ICP-QQQ instruments for semiconductor-grade analytes:

• Ultrapure water (UPW) and process chemical analysis under cool and hot plasma conditions
• Automated Method of Standard Additions (MSA) calibration using prepFAST S
• Sub-ppt determination of K, Ca, Fe, Li, Na, Mg, Al and trace metals in UPW
• High-purity H2O2 and HCl evaluation without sample pretreatment
• Ultratrace quantification of P, S, Si, Cl using oxygen and hydrogen cell gases
• Direct analysis of undiluted HNO3 and HCl with minimized sample handling

Methodology and Instrumentation

All studies employed Agilent 8800 or 8900 ICP-QQQ instruments fitted with PFA nebulizers, quartz or PFA spray chambers and Pt-tipped cones. Tuning steps combined hot or cool plasma conditions with no-gas, He, H2, NH3 and O2 cell gas modes. MS/MS operation (Q1 → cell → Q2) allowed strict precursor/product ion selection. Cool plasma (RF ~600 W, CeO/Ce < 2 %) minimized argide and EIE backgrounds in low-matrix samples. Hot plasma with optional m-lens and skimmer cones enhanced sensitivity for higher matrix digests. Automated MSA via the ESI prepFAST S minimized contamination and improved throughput.

Main Results and Discussion

– UPW analysis under hot plasma (m-lens) and MS/MS achieved BECs < 0.5 ppt and DLs < 0.3 ppt for 25 SEMI elements; B and Li were also measured at sub-ppt levels.
– High-purity 35 % H2O2 was quantified undiluted by MS/MS, meeting SEMI Grade 5 limits (10 ppt) for 26 target elements with RSD < 8 % over 3.7 h.
– Automated MSA of DI water and H2O2 via prepFAST S delivered sub-ppt DLs for Na, K, Ca, As, Zn, and mass-shift quantification of P and S in < 30 min total run time.
– ICP-QQQ in cool plasma/NH3 mode achieved ppq-level BECs for K (30 ppq), Ca, Cr, Mn, Fe, Ni and Cu in UPW.
– O2 MS/MS mass-shift enabled ppt-level P and S analysis; H2 on-mass resolved Si; H2 MS/MS mass-shift quantified ClH2+. BECs and DLs for P, S, Si and Cl in UPW were < 85 ppt (BEC) and < 15 ppt (DL).
– Direct analysis of high-purity HNO3 (68 %) and HCl (20 %) without pretreatment yielded sub-ppt BECs for Li, Mg, Ca, Sc, V, Cr, Mn, Co, Ni, Cu, Zn and single-digit ppt detection of B, Na, Al, Ti, As and Mo, easily exceeding SEMI C35 and C27 requirements.

Benefits and Practical Applications

• Comprehensive ultratrace control of metallic and non-metallic contaminants in semiconductor reagents
• Reduction of sample preparation steps, eliminating dilution and matrix removal procedures
• Flexibility to switch between plasma and cell gas modes in a single run
• Automated calibration and acidification to improve data quality and throughput
• Reliable, interference-free quantification for QA/QC, process monitoring and research labs

Future Trends and Possibilities

• Integration with laser ablation and single particle ICP-QQQ for nanoparticle and microanalysis
• Expansion of speciation workflows combining HPLC/GC with MS/MS for organometallics and hydrides
• Continued refinement of cell gas chemistries to target emerging interferences and novel isotopes
• Wider adoption of automated sample introduction for high-throughput semiconductor and environmental testing

Conclusion

Agilent’s 8800 and 8900 triple quadrupole ICP-MS instruments redefine ultratrace elemental analysis in high-purity semiconductor process chemicals. Through MS/MS operation, multi-gas reaction modes and automated calibration, they deliver reliable detection limits at the ppt to ppq level across a broad range of challenging analytes. These capabilities support contamination control, process optimization and quality assurance in advanced semiconductor manufacturing.

Reference

[1] SEMI C27-0708 and C35-0708 specifications for HCl and HNO3; [2] K. Sakata & K. Kawabata, Spectrochim. Acta B, 1994; [3] J. Takahashi et al., Asia Pacific Winter Plasma Conference, 2008; [4] Agilent application notes on ICP-QQQ.