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Chemically non-perturbing SERS detection of catalytic reaction with black silicon

Abstract

All-dielectric resonant micro- and nano-structures made of the high-index dielectrics recently emerge as a promising surface-enhanced Raman scattering (SERS) platform which can complement or potentially replace the metal-based counterparts in routine sensing measurements. These unique structures combine the highly-tunable optical response and high field enhancement with the non-invasiveness, i.e., chemically non-perturbing the analyte, simple chemical modification and recyclability. Meanwhile, the commercially competitive fabrication technologies for mass production of such structures are still missing. Here, we attest a chemically inert black silicon (b-Si) substrate consisting of randomly-arranged spiky Mie resonators for a true non-invasive (chemically non-perturbing) SERS identification of the molecular fingerprints at low concentrations. Based on comparative in situ SERS tracking of the para-aminothiophenol (PATP)-to-4,4`-dimercaptoazobenzene (DMAB) catalytic conversion on the bare and metal-coated b-Si, we justify applicability of the metal-free b-Si for the ultra-sensitive non-invasive SERS detection at concentration level as low as 10^{-6} M. We perform supporting finite-difference time-domain (FDTD) calculations to reveal the electromagnetic enhancement provided by an isolated spiky Si resonator in the visible spectral range. Additional comparative SERS studies of the PATP-to-DMAB conversion performed with a chemically active bare black copper oxide (b-CuO) substrate as well as SERS detection of the slow daylight-driven PATP-to-DMAB catalytic conversion in the aqueous methanol solution loaded with colloidal silver nanoparticles (Ag NPs) confirm the non-invasive SERS performance of the all-dielectric crystalline b-Si substrate. Proposed SERS substrate can be fabricated using easy-to-implement scalable technology of plasma etching amenable on substrate areas over 10x10 cm^2 making such inexpensive all-dielectric substrates promising for routine SERS applications, where the non-invasiveness is of mandatory importance.

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Supplementary files

Publication details

The article was received on 14 Mar 2018, accepted on 13 Apr 2018 and first published on 17 Apr 2018


Article type: Paper
DOI: 10.1039/C8NR02123F
Citation: Nanoscale, 2018, Accepted Manuscript
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    Chemically non-perturbing SERS detection of catalytic reaction with black silicon

    E. Mitsai, A. Kuchmizhak, E. Pustovalov, A. A. Sergeev, A. Mironenko, S. Bratskaya, D. P. Linklater, A. Balcytis, E. P. Ivanova and S. Juodkazis, Nanoscale, 2018, Accepted Manuscript , DOI: 10.1039/C8NR02123F

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