Nanoscaled or porous silicon (p-Si) with and without surface passivation exhibits unusually tunable properties that its parent bulk does never show. Such property tunability amplifies the applicability of Si in the concurrent and upcoming technologies. However, consistent understanding of the fundamental nature of nanoscaled Si remains a high challenge. This article aims to address the recent progress in this regard with focus on reconciling the tunable dielectric, electronic, phononic, and photonic properties of p-Si in terms of skin dominance. We show that the skin-depth bond contraction, local quantum entrapment, and electron localization is responsible for the size-induced property tunability. The shorter and stronger bonds between undercoordinated skin atoms result in the local densification and quantum entrapment of the binding energy and the bonding electrons, which in turn polarizes the dangling bond electrons. Such local entrapment modifies the Hamiltonian and associated properties such as the band gap, core level shift, Stokes shift (electron–phonon interaction), phonon and dielectric relaxation. Therefore, given the known trend of one property change, one is expected to be able to predict the variation of the rest based on the notations of the bond order–length–strength correlation and local bond average approach (BOLS-LBA). Furthermore, skin bond reformation due to Al, Cu, and Ti metallization and O and F passivation adds another freedom to enhance or attenuate the size effect. The developed formulations, spectral analytical methods, and importantly, the established database and knowledge could be of use in engineering p-Si and beyond for desired functions.

具有和不具有表面钝化的纳米级或多孔硅（p-Si）都具有异常的可调谐特性，而其母体从未显示出这种特性。这种特性可调性增强了Si在并行技术和即将到来的技术中的适用性。然而，对纳米级硅基本性质的一致理解仍然是一个很高的挑战。本文旨在解决这方面的最新进展，重点是调和p-Si的可调介电，电子，声子和光子特性就皮肤优势而言。我们表明，趋肤深度的键收缩，局部量子截留和电子局部化是引起尺寸诱导的性质可调性的原因。配位不足的皮肤原子之间较短且较强的键导致键合能和键合电子的局部致密化和量子俘获，进而使悬空的键合电子极化。这种局部夹带改变了哈密顿量和相关性质，例如带隙，核能级位移，斯托克斯位移（电子-声子相互作用），声子和介电弛豫。因此，给定一种性质变化的已知趋势，可以预期一种能够基于键序-长度-强度相关性和局部键平均法（BOLS-LBA）的符号来预测其余性质的变化。此外，由于Al，Cu和Ti金属化以及O和F钝化导致的表皮结合再形成增加了增强或减弱尺寸效应的另一自由度。开发的配方，光谱分析方法，以及重要的是，已建立的数据库和知识可以在工程中使用p-Si及更高功能。