Materials Science Division, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL 60439, USA.
Rapid Commun Mass Spectrom. 2012 Oct 15;26(19):2224-30. doi: 10.1002/rcm.6344.
Although the fundamental physical limits for depth resolution of secondary ion mass spectrometry are well understood in theory, the experimental work to achieve and demonstrate them is still ongoing. We report results of high-resolution TOF SIMS (time-of-flight secondary ion mass spectrometry) depth profiling experiments on a nanolayered structure, a stack of 16 alternating MgO and ZnO ~5.5 nm layers grown on a Si substrate by atomic layer deposition.
The measurements were performed using a newly developed approach implementing a low-energy direct current normally incident Ar(+) ion beam for ion milling (250 eV and 500 eV energy), in combination with a pulsed 5 keV Ar(+) ion beam at 60° incidence for TOF SIMS analysis. By this optimized arrangement, a noticeably improved version of the dual-beam (DB) approach to TOF SIMS depth profiling is introduced, which can be dubbed gentleDB.
The mixing-roughness-information model was applied to detailed analysis of experimental results. It revealed that the gentleDB approach allows ultimate depth resolution by confining the ion beam mixing length to about two monolayers. This corresponds to the escape depth of secondary ions, the fundamental depth resolution limitation in SIMS. Other parameters deduced from the measured depth profiles indicated that a single layer thickness is equal to 6 nm so that the 'flat' layer thickness d is 3 nm and the interfacial roughness σ is 1.5 nm, thus yielding d + 2σ = 6 nm.
We have demonstrated that gentleDB TOF SIMS depth profiling with noble gas ion beams is capable of revealing the structural features of a stack of nanolayers, resolving its original surface and estimating the roughness of interlayer interfaces, information which is difficult to obtain by traditional approaches.
尽管在理论上已经很好地理解了二次离子质谱深度分辨率的基本物理限制,但仍在进行实现和证明这些限制的实验工作。我们报告了在纳米层结构上进行高分辨率飞行时间二次离子质谱(TOF SIMS)深度剖析实验的结果,该结构是通过原子层沉积在 Si 衬底上生长的 16 个交替的 MgO 和 ZnO~5.5nm 层的堆叠。
使用新开发的方法进行测量,该方法采用低能直流垂直入射 Ar(+)离子束进行离子铣削(250eV 和 500eV 能量),同时采用 60°入射的脉冲 5keVAr(+)离子束进行 TOF SIMS 分析。通过这种优化的布置,引入了一种明显改进的双束(DB)TOF SIMS 深度剖析方法,可称为 gentleDB。
混合粗糙度信息模型被应用于实验结果的详细分析。结果表明,gentleDB 方法通过将离子束混合长度限制在大约两个单层,可以实现最终的深度分辨率。这对应于二次离子的逸出深度,是 SIMS 中的基本深度分辨率限制。从测量的深度剖面中推断出的其他参数表明,单层厚度等于 6nm,因此“平坦”层厚度 d 为 3nm,界面粗糙度 σ 为 1.5nm,从而得到 d+2σ=6nm。
我们已经证明,使用惰性气体离子束的 gentleDB TOF SIMS 深度剖析能够揭示纳米层堆叠的结构特征,解析其原始表面并估计层间界面的粗糙度,这些信息很难通过传统方法获得。