Mussel-Inspired Strategy for Stabilizing Ultrathin Polymer Films and Its Application to Spin-On Doping of Semiconductors,Chemistry of Materials

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Mussel-Inspired Strategy for Stabilizing Ultrathin Polymer Films and Its Application to Spin-On Doping of Semiconductors
Chemistry of Materials ( IF 7.2 ) Pub Date : 2018-07-19 00:00:00 , DOI: 10.1021/acs.chemmater.8b02027
Reika Katsumata ₁ , Ratchana Limary ₂ , Yuanyi Zhang ₃ , Bhooshan C. Popere _{1,

3} , Andrew T. Heitsch ₄ , Mingqi Li ₅ , Peter Trefonas ₅ , Rachel A. Segalman _{1,

3,

6}

Affiliation

Stabilizing ultrathin films, in particular avoiding dewetting, is critical to the application of polymer thin films from biology to electronics. To address this issue, a wide range of approaches have been developed, including self-assembled monolayers to modify surface energy, and covalent attachment methods, such as surface-initiated polymerization and grafting of end-functionalized polymers. However, most of these approaches either require postprocessing of the substrates or are applicable only to the specific combination of polymers and substrates. Herein, we introduce a mussel-inspired universal adhesive moiety, dopamine, as an end group for any polymer to promote film stability, and demonstrate its application to spin-on doping on silicon, in particular. Leveraging the versatility of reversible addition–fragmentation chain transfer (RAFT) polymerization, the dopamine moiety is incorporated as an end group. Dopamine functionalized 15 nm thick films are more thermally stable at 230 °C on a variety of semiconductor-relevant surfaces (Si–OH, SiO_x, TiN, and Si₃N₄), while control polymer films with a carboxyl end group severely dewet. The dopamine end group also ensures successful sub-10 nm thick conformal coatings on three-dimensional surfaces, confirmed by cross-sectional scanning transmission electron microscopy with electron energy loss spectroscopy (STEM-EELS). Furthermore, as a polymeric spin-on doping material, dosage of dopant with the dopamine-functionalized polymer is comparable or higher than that with the control end group, demonstrating one of the promising applications of such conformal coatings.

中文翻译：

贻贝启发的稳定超薄聚合物膜的策略及其在半导体旋涂中的应用

稳定超薄膜，特别是避免去湿，对于从生物学到电子学领域的聚合物薄膜的应用至关重要。为了解决这个问题，已经开发了各种各样的方法，包括用于修饰表面能的自组装单分子膜，以及共价连接方法，例如表面引发的聚合和末端官能化聚合物的接枝。但是，这些方法中的大多数要么需要对基材进行后处理，要么仅适用于聚合物和基材的特定组合。本文中，我们介绍了一种受到贻贝启发的通用粘合剂部分，即多巴胺，作为任何聚合物的端基，以提高薄膜的稳定性，并特别展示了其在旋涂式硅上的应用。利用可逆加成-断裂链转移（RAFT）聚合的多功能性，将多巴胺部分作为端基并入。多巴胺官能化的15 nm厚膜在各种半导体相关表面（Si-OH，SiO_x，TiN和Si₃ N₄），而带有羧基端基的对照聚合物薄膜则严重润湿。多巴胺端基还可以确保在三维表面上成功实现亚10纳米厚的保形涂层，这一点已通过具有电子能量损失谱（STEM-EELS）的截面扫描透射电子显微镜进行了证实。此外，作为聚合物旋涂掺杂材料，与多巴胺官能化的聚合物相比，掺杂剂的剂量与对照组端基的相当或更高，这证明了这种保形涂料的一种有前途的应用。

更新日期：2018-07-19

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