HF、HNO3 和 H2SiF6 二元和三元混合物中硅酸性湿化学蚀刻的动力学研究,Physical Chemistry Chemical Physics

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HF、HNO3 和 H2SiF6 二元和三元混合物中硅酸性湿化学蚀刻的动力学研究
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2023-09-11 , DOI: 10.1039/d3cp03188h
Anja Rietig ₁ , Jörg Acker ₁

Affiliation

_{使用氢氟酸 (HF)、硝酸 (HNO 3} ) 和六氟硅酸 (H ₂ SiF ₆ )的混合物蚀刻硅是在由相互作用的副反应组成的复杂反应场景中进行的。几乎没有其他溶解反应如此严重地依赖于影响蚀刻速率和各个反应机制的反应条件。对二元和三元酸混合物中硅蚀刻反应速率的广泛研究已经允许将反应控制和扩散控制反应体系之间的转变点确定为蚀刻混合物的组成的函数。经验证，二元和三元混合物的反应机理没有差异，只是三元混合物中较低的水含量有利于副反应中反应性N( III )中间体HNO ₂的形成。基于对机理变化点的准确了解，在本体蚀刻范围内的准等温条件下确定反应速率，首次可以从动力学数据中推导出形式动力学项来描述两种腐蚀速率下的溶解速率。反应控制和扩散控制机制。形式动力学项的设计既针对硅体中溶解速率的动力学正确的准等温方法，又针对面向应用的方法，包括所考虑的溶解期间的诱导阶段和温度升高以及表面性质的影响。此外，通过使用蚀刻混合物的水含量作为代理变量，可以统一计算应用的整个成分范围内的HF/HNO ₃以及HF/HNO ₃ /H ₂ SiF ₆混合物中的蚀刻速率。被制定。

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Kinetic studies on acidic wet chemical etching of silicon in binary and ternary mixtures of HF, HNO3 and H2SiF6

The etching of silicon with mixtures of hydrofluoric acid (HF), nitric acid (HNO₃) and hexafluorosilicic acid (H₂SiF₆) proceeds in a complex reaction scenario consisting of interacting side reactions. Almost no other dissolution reaction is so massively dependent on the reaction conditions that influence the etching rate and the mechanism of the individual reactions. Extensive studies of the reaction rate of silicon etching in binary and ternary acid mixtures have allowed the transition point between the reaction-controlled and diffusion-controlled reaction regimes to be determined as a function of the composition of the etching mixture. It was verified that the reaction mechanism for binary and ternary mixtures does not differ and only the lower water content in ternary mixtures favours an enhanced formation of the reactive N(III) intermediate HNO₂ in side reactions. Based on the exact knowledge of the point of mechanism change, determination of the reaction rate under quasi-isothermal conditions in the bulk etching range allows, for the first time, deriving formal kinetic terms from the kinetic data to describe the dissolution rate in both the reaction-controlled and diffusion-controlled regimes. The formal kinetic terms were designed both for the kinetically correct quasi-isothermal approach to the dissolution rate in the Si bulk and for the application-oriented approach that includes induction phases and temperature increases in the considered dissolution period as well as influences of the surface properties. Moreover, by using the water content of the etching mixtures as a proxy variable, uniform calculation of the etching rates in HF/HNO₃ as well as in HF/HNO₃/H₂SiF₆ mixtures in the entire composition range of the application can be formulated.

更新日期：2023-09-11

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