Room-Temperature Optical Picocavities below 1 nm3 Accessing Single-Atom Geometries
Room-Temperature Optical Picocavities below 1 nm3 Accessing Single-Atom Geometries
复制标题
DOI：
10.1021/acs.jpclett.8b03466
复制
发表时间：
2018-12-20
影响因子：
5.7
通讯作者：
Baumberg, Jeremy J.
中科院分区：
文献类型：
--
作者：
Carnegie, Cloudy;Griffiths, Jack;Baumberg, Jeremy J.
光在纳米尺度上的可再现限制对于在单分子水平上观察和控制化学反应的能力至关重要。在这里，我们可靠地形成了数百万个相同的纳米腔，并表明通过创建picocavities，具有埃级分辨率的单吸附原子突起，可以将光进一步聚焦到亚纳米级。我们首次在室温下通过高速表面增强拉曼光谱对特定分子组分进行稳定和分析，收集和分析了200多万个光谱。在这些picocavities上获得的数据使我们能够推断出纳米尺度上的结构信息，表明硫醇与金的结合使金属表面对光辐射不稳定。发现腈部分使皮腔稳定10倍以防止其消失，通常存活>1秒。这样的构建体证明了在环境条件下单分子化学的可及性。
Reproducible confinement of light on the nanoscale is essential for the ability to observe and control chemical reactions at the single-molecule level. Here we reliably form millions of identical nanocavities and show that the light can be further focused down to the subnanometer scale via the creation of picocavities, single-adatom protrusions with angstrom-level resolution. For the first time, we stabilize and analyze these cavities at room temperatures through high-speed surface-enhanced Raman spectroscopy on specifically selected molecular components, collecting and analyzing more than 2 million spectra. Data obtained on these picocavities allows us to deduce structural information on the nanoscale, showing that thiol binding to gold destabilizes the metal surface to optical irradiation. Nitrile moieties are found to stabilize picocavities by 10-fold against their disappearance, typically surviving for >1 s. Such constructs demonstrate the accessibility of single-molecule chemistry under ambient conditions.