Vishnevskiy Alexey S, Vorotyntsev Dmitry A, Seregin Dmitry S, Vorotilov Konstantin A, Sigov Alexander S
Research and Educational Center "Technological Center", MIREA-Russian Technological University (RTU MIREA), 78 Vernadsky Ave., Moscow 119454, Russia.
Polymers (Basel). 2025 Sep 8;17(17):2433. doi: 10.3390/polym17172433.
Organosilica films, composed of a silicon oxide network with terminal methyl groups, are widely utilized in various applications, including microelectronics. Many of these applications require high hydrophobicity and good mechanical properties, which pose a significant challenge because the Si-CH groups disrupt the Si-O-Si network. This issue becomes particularly pronounced in porous films. Here, we investigate whether material properties can be tuned by simply altering the spatial arrangement of methyl groups. To achieve this, we prepared copolymer films with one or two methyl groups bonded to a silicon atom, while maintaining a constant total amount of methyl groups. The films were deposited using a sol-gel technique combined with template self-assembly. The precursor content was varied to compare films with different proportions of Si-CH and Si(-CH). Film characterization included FTIR, ellipsometric porosimetry, AFM, and WCA measurements and dielectric constant evaluations. Our findings indicate that precursors containing dimethyl groups enhance the connectivity of the Si-O-Si network, resulting in a higher Young's modulus and smaller pore size compared to films with an equivalent amount of methyl groups. However, the lower thermal stability of dimethyl bonds limits the thermal budget of these films. Thus, the spatial arrangement of organic groups within the polymer structure can be employed to tune material properties. These results expand the understanding of organic-inorganic hybrid materials and offer novel approaches for their applications.
由带有末端甲基的氧化硅网络组成的有机硅薄膜被广泛应用于包括微电子学在内的各种领域。这些应用中的许多都需要高疏水性和良好的机械性能，这构成了一项重大挑战，因为硅-碳氢键会破坏硅-氧-硅网络。这个问题在多孔薄膜中尤为突出。在这里，我们研究是否可以通过简单改变甲基的空间排列来调整材料性能。为了实现这一点，我们制备了硅原子上键合有一个或两个甲基的共聚物薄膜，同时保持甲基的总量恒定。使用溶胶-凝胶技术结合模板自组装来沉积薄膜。改变前驱体含量以比较具有不同比例硅-碳氢键和硅（-碳氢键）的薄膜。薄膜表征包括傅里叶变换红外光谱（FTIR）、椭偏测孔法、原子力显微镜（AFM）、水接触角（WCA）测量以及介电常数评估。我们的研究结果表明，含有二甲基的前驱体增强了硅-氧-硅网络的连通性，与具有等量甲基的薄膜相比，导致更高的杨氏模量和更小的孔径。然而，二甲基键较低的热稳定性限制了这些薄膜的热预算。因此，聚合物结构内有机基团的空间排列可用于调整材料性能。这些结果扩展了对有机-无机杂化材料的理解，并为其应用提供了新方法。
