Leveraging the Assembly of a Rylene Dye to Tune the Semiconducting Properties of Functionalized n-Type, Hybrid Si Interfaces
Leveraging the Assembly of a Rylene Dye to Tune the Semiconducting Properties of Functionalized n-Type, Hybrid Si Interfaces
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利用萘嵌苯染料的组装来调节功能化 n 型混合硅界面的半导体特性
DOI：
10.1021/acsami.0c18222
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发表时间：
2021
影响因子：
9.5
通讯作者：
Olivier, Jean-Hubert
中科院分区：
文献类型：
--
作者：
Mukhopadhyay, Arindam;Paulino, Victor;Liu, Kaixuan;Donley, Carrie L.;Bernard, Brianna;Shomar, Alfred;Liu, Chuan;Olivier, Jean-Hubert
π共轭发色团的硅电极功能化为设计与信息存储和处理相关的混合半导体接口开辟了新的途径。值得注意的是，分子溶解π共轭单元，如二茂铁衍生物，传统上被用作构建定义良好的界面的基石，这些界面建立了电化学可寻址的平台，用于研究电子转移特性和电荷存储能力。相反，平面π共轭结构块，如萘二亚胺（NDI）核，可以形成溶剂化聚集体，具有母体分子溶解结构块所没有的紧急电子结构。为了探究π共轭发色团的聚集态在多大程度上可以调节功能化电极的n型半导体特性，我们设计了一种两亲乙烯核（NDI），它在水介质中表现出不可忽略的聚集程度。利用电化学、还原滴定实验和光谱电化学相结合的方法对NDI衍生聚集体的电子结构进行表征，揭示了π-阴离子堆的存在，其形成取决于NDI构建块的初始浓度。我们发现，通过“点击”反应将n掺杂的NDI聚集体接枝到具有高密度锚定基团的硅电极前驱体上，可以形成hybridsi -NDI电极（Si-NDI-15@1），与由分子溶解的NDI单元构建的Si界面相比，它可以促进超过400 mV的电子注入。此外，以低密度锚定基团为特征的Si前驱体表面的工程设计提供了额外的证据，以强调从NDI单元记录的电位特性forSi-NDI-15@1originate，证明了不可忽略的聚集程度。目前的工作提供了工具来操纵的电位学性质的功能化电极利用的电子结构聚集，π共轭前驱体。
The functionalization of silicon electrodes with π-conjugated chromophores opens new avenues to engineer hybrid semiconducting interfaces relevant to information storage and processing. Notably, molecularly dissolved π-conjugated units, such as ferrocene derivatives, are traditionally exploited as building blocks to construct well-defined interfaces that establish electrochemically addressable platforms with which to investigate electron transfer properties and charge storage capabilities. In contrast, planar π-conjugated building blocks such as naphthalene diimide (NDI) cores enable the formation of solvated aggregates equipped with emergent electronic structures not manifested by the parent, molecularly dissolved building blocks. To interrogate the extent to which the aggregated states of π-conjugated chromophores can be leveraged to regulate the n-type semiconducting properties of functionalized electrodes, we have devised an amphiphilic rylene core (NDI) that demonstrates a non-negligible degree of aggregation in an aqueous medium. Characterization of the electronic structures of the NDI-derived aggregates using a combination of electrochemistry, reductive titration experiments, and spectroelectrochemistry unveils the existence of π-anion stacks, the formation of which is contingent on the initial concentration of NDI building blocks. We show that grafting n-doped NDI aggregates on silicon electrode precursors equipped with a high density of anchoring groups by means of “click” reaction enables the formation of the hybridSi-NDIelectrode (Si-NDI-15@1) that facilitates electron injection by more than 400 mV when compared to Si interfaces constructed from molecularly dissolved NDI units. Furthermore, the engineering of a Si precursor surface characterized by a low density of anchoring groups provides additional proof to highlight that the potentiometric properties recorded forSi-NDI-15@1originate from NDI units, evidencing a non-negligible degree of aggregation. The present work delivers tools to manipulate the potentiometric properties of functionalized electrodes by leveraging on the electronic structures of aggregated, π-conjugated precursors.