State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun 130012, People's Republic of China.
State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun 130012, People's Republic of China.
Spectrochim Acta A Mol Biomol Spectrosc. 2019 Dec 5;223:117336. doi: 10.1016/j.saa.2019.117336. Epub 2019 Jul 4.
Surface-enhanced Raman scattering (SERS) on organic-inorganic hybrid perovskites have been proved a promising SERS-active substrate. As its inorganic skeleton, lead iodide (PbI) also represents a novel semiconductor substrate material that serves as either a complement or an alternative to conventional metal-based SERS. Here, for the first time, enhanced Raman scattering (ERS) of 1,2-bis(4-pyridyl)ethylene (BPE) adsorbed on PbI film is observed. To our surprise, we obtained the same ERS spectra on the PbI as SERS spectra obtained on the perovskites, which demonstrates the enhancement of substrate comes from inorganic skeleton rather than organic-inorganic hybrid perovskites. Compared with the normal Raman spectrum of BPE molecules, we find the B mode of the BPE molecule was selectively enhanced. We demonstrate that it involves a charge transfer (CT) resonance mechanism and takes place between the HOMO of BPE and the conduction band edge of PbI. Moreover, the PbI substrate performs good reproducibility, uniformity and good Raman enhancement (EF ≥ 10). It is believed that this unusual discovery not only enables PbI to be an enhanced substrate, which also provides a new advance toward a better understanding of SERS chemical mechanism.
有机-无机杂化钙钛矿上的表面增强拉曼散射(SERS)已被证明是一种很有前途的 SERS 活性衬底。作为其无机骨架,碘化铅(PbI)也是一种新型半导体衬底材料,它可以作为传统基于金属的 SERS 的补充或替代物。在这里,首次观察到吸附在 PbI 薄膜上的 1,2-双(4-吡啶基)乙烯(BPE)的增强拉曼散射(ERS)。令我们惊讶的是,我们在 PbI 上获得了与在钙钛矿上获得的 SERS 光谱相同的 ERS 光谱,这表明衬底的增强来自于无机骨架,而不是有机-无机杂化钙钛矿。与 BPE 分子的正常拉曼光谱相比,我们发现 BPE 分子的 B 模式被选择性增强。我们证明它涉及电荷转移(CT)共振机制,发生在 BPE 的 HOMO 和 PbI 的导带边缘之间。此外,PbI 衬底具有良好的重现性、均匀性和良好的拉曼增强(EF≥10)。相信这一不寻常的发现不仅使 PbI 成为一种增强衬底,也为更好地理解 SERS 化学机制提供了新的进展。