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Buffer-gas assisted high irradiance nanosecond and femtosecond laser ionization orthogonal time-of-flight mass spectrometry(ns/fs-LI-O-TOFMS)have been applied for the depth profile analysis of multilayer samples(Conductive sample: Rh 160 nm/Au <20 nm/Pd 1100 nm/Cu; nonconductive sample: Cr 1500 nm/Ni 200nm/Cu 7000 nm/ABS).