Pollard Benjamin, Muller Eric A, Hinrichs Karsten, Raschke Markus B
1] Department of Physics, Department of Chemistry, and JILA, University of Colorado, Boulder, Colorado 80309, USA [2].
Department Berlin, Leibniz-Institut für Analytische, Wissenschaften - ISAS - e.V., Albert-Einstein-Strasse 9, Berlin 12489, Germany.
Nat Commun. 2014 Apr 11;5:3587. doi: 10.1038/ncomms4587.
Molecular self-assembly, the function of biomembranes and the performance of organic solar cells rely on nanoscale molecular interactions. Understanding and control of such materials have been impeded by difficulties in imaging their properties with the desired nanometre spatial resolution, attomolar sensitivity and intermolecular spectroscopic specificity. Here we implement vibrational scattering-scanning near-field optical microscopy with high spectral precision to investigate the structure-function relationship in nano-phase separated block copolymers. A vibrational resonance is used as a sensitive reporter of the local chemical environment and we image, with few nanometre spatial resolution and 0.2 cm(-1) spectral precision, solvatochromic Stark shifts and line broadening correlated with molecular-scale morphologies. We discriminate local variations in electric fields between nano-domains with quantitative agreement with dielectric continuum models. This ability to directly resolve nanoscale morphology and associated intermolecular interactions can form a basis for the systematic control of functionality in multicomponent soft matter systems.
分子自组装、生物膜的功能以及有机太阳能电池的性能都依赖于纳米级的分子相互作用。由于难以以所需的纳米空间分辨率、阿托摩尔灵敏度和分子间光谱特异性对这些材料的性质进行成像，对这类材料的理解和控制受到了阻碍。在这里，我们采用具有高光谱精度的振动散射扫描近场光学显微镜来研究纳米相分离嵌段共聚物中的结构-功能关系。振动共振被用作局部化学环境的灵敏报告器，我们以几纳米的空间分辨率和0.2厘米-1的光谱精度对与分子尺度形态相关的溶剂化显色斯塔克位移和谱线展宽进行成像。我们区分了纳米域之间电场的局部变化，与介电连续介质模型定量吻合。这种直接解析纳米级形态和相关分子间相互作用的能力可为多组分软物质系统中功能的系统控制奠定基础。
