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首页> 外文期刊>The journal of physical chemistry, C. Nanomaterials and interfaces >Kinetic to Transport-Limited Anhydrous HF Etching of Silicon Oxynitride Films in Supercritical CO2
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Kinetic to Transport-Limited Anhydrous HF Etching of Silicon Oxynitride Films in Supercritical CO2

机译：超临界CO2中氧氮化硅薄膜的运动至无迁移限制的无水HF刻蚀

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摘要

A silicon oxynitride film (SiO0.8N0.2) was etched with anhydrous HF/pyridine mixtures dissolved in supercritical carbon dioxide at 50-75 °C and 160 ± 10 bar to achieve concentrations of 2.8-22.4 mM, spanning the range from kinetically limited to transport-limited etching. The SiF4 and NH3 etching products reacted further, forming an insoluble salt layer chemically identified as (NH4)2SiF6 using FTIR and quantitative XPS and imaged using SEM and AFM. The etching reaction was first-order below 11 mM because the surface was open to the fluid phase between salt crystals, and etching rates were approximately 1 nm/min. In this regime, salt crystals did not hinder etching and formed primarily by the addition of fluorosilicates to the bottom interface with the silicon oxynitride film. The reaction order was less than one above 11 mM HF because lateral growth of salt crystals became significant and hindered transport of the fluid to the film. Between 50 and 70 °C, the salt formed cubic crystals, whereas at 75 °C a powder-like product formed. Partial removal of the (NH4)2SiF6 salt was accomplished by sublimation under ultrahigh vacuum conditions at room temperature.
机译：在50-75°C和160±10 bar下，用溶于超临界二氧化碳的无水HF /吡啶混合物蚀刻氮氧化硅膜（SiO0.8N0.2），以达到2.8-22.4 mM的浓度，其范围从动力学极限进行有限的蚀刻。 SiF4和NH3蚀刻产物进一步反应，形成不溶性盐层，使用FTIR和定量XPS在化学上鉴定为（NH4）2SiF6，并使用SEM和AFM进行成像。蚀刻反应在低于11 mM时是一级反应，因为表面对盐晶体之间的液相开放，并且蚀刻速率约为1 nm / min。在这种情况下，盐晶体不妨碍蚀刻，并且主要是通过在与氧氮化硅膜的底部界面添加氟硅酸盐而形成的。在11 mM HF以上，反应顺序小于1。这是因为盐晶体的侧向生长变得显着，并阻碍了流体向膜的传输。在50到70°C之间，盐形成了立方晶体，而在75°C下，形成了粉末状的产物。 （NH 4）2 SiF 6盐的部分除去是通过在室温下在超高真空条件下升华来完成的。

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