Black-CuO: surface-enhanced Raman scattering and infrared properties

Balčytis, Armandas; Ryu, Meguya; Seniutinas, Gediminas; Juodkazytė, Jurga; Cowie, Bruce C. C.; Stoddart, Paul R.; Zamengo, Massimiliano; Morikawa, Junko; Juodkazis, Saulius

doi:10.1039/c5nr04783h

Cited by 37 publications

(18 citation statements)

References 43 publications

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“…1(d)). Noteworthy, the density of the spikes is similar to those for b-Si, while the SERS yield is also comparable, as shown in previous studies [32,34,35]. Meanwhile, the density of the surface textures both substrate ensure that several (≈10-20) randomly arranged spiky nano-features will be always within the laser irradiated spot (see Methods for details).…”

Section: Resultssupporting

confidence: 80%

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

et al. 2018

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All-dielectric resonant micro- and nano-structures made of high-index dielectrics have recently emerged 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, 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 the 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 the applicability of the metal-free b-Si for ultra-sensitive non-invasive SERS detection at a concentration level as low as 10-6 M. We performed 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. A proposed SERS substrate can be fabricated using the easy-to-implement scalable technology of plasma etching amenable on substrate areas over 10 × 10 cm2 making such inexpensive all-dielectric substrates promising for routine SERS applications, where the non-invasiveness is of high importance.

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Section: Resultssupporting

confidence: 80%

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

et al. 2018

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“…Mechanisms controlling crystallisation of protein coils via ordered hydrogen bonding and their unzip-decomposition at different annealing temperatures, laser and electron beam exposure conditions are of interest for applications in material science and bio-medical fields [11,12,13]. Silk can be used as a bio-compatible scaffold [14] with water solubility dependent on its crystallinity [15].…”

Section: Introductionmentioning

confidence: 99%

Silk: Optical Properties over 12.6 Octaves THz-IR-Visible-UV Range

et al. 2017

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Domestic (Bombyx mori) and wild (Antheraea pernyi) silk fibers were characterised over a wide spectral range from THz 8 cm−1 (λ= 1.25 mm, f= 0.24 THz) to deep-UV 50×103 cm−1 (λ= 200 nm, f= 1500 THz) wavelengths or over a 12.6 octave frequency range. Spectral features at β-sheet, α-coil and amorphous fibroin were analysed at different spectral ranges. Single fiber cross sections at mid-IR were used to determine spatial distribution of different silk constituents and revealed an α-coil rich core and more broadly spread β-sheets in natural silk fibers obtained from wild Antheraea pernyi moths. Low energy T-ray bands at 243 and 229 cm−1 were observed in crystalline fibers of domestic and wild silk fibers, respectively, and showed no spectral shift down to 78 K temperature. A distinct 20±4 cm−1 band was observed in the crystalline Antheraea pernyi silk fibers. Systematic analysis and assignment of the observed spectral bands is presented. Water solubility and biodegradability of silk, required for bio-medical and sensor applications, are directly inferred from specific spectral bands.

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“…It is evident from the comparison of Figures 4 and 5 that the intensity of spectra in the case of the Pd coated black-CuO electrode was about 10 times less. This, most likely, should be attributed to blocking of the black-CuO surface by Pd, rather than a decrease in electrode surface area, because the evaporated ∼200 nm thick Pd layer could not significantly reduce the true surface area of the electrode, as we found in earlier SERS studies [21]. The same electrode was used in both experiments.…”

Section: Spectroelectrochemical Measurementsmentioning

confidence: 81%

“…A flat circular copper electrode of ca. 5 mm in diameter, press-fitted into a Teflon rod, was oxidized chemically as described in our previous paper [21] to produce a SERS active nanostructured Cu(II) oxide layer, further in the text referred to as black-CuO because of its black appearance due to its anti-reflective surface texture. Using synchrotron X-ray surface analysis, we confirmed that only CuO was present on the surface of black-CuO [21] prepared by the method used in this study.…”

Section: Samples For Spectroelectrochemical Measurementsmentioning

confidence: 99%

Hydrogen Evolution on Nano-StructuredCuO/Pd Electrode: Raman Scattering Study

et al. 2019

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In this study, the processes taking place on the surfaces of nanostructured Cu/CuO and Cu/CuO/Pd electrodes at different potential, E, values in the solutions of 0.1 M KOH in H 2 O and D 2 O (heavy water) were probed by surface enhanced Raman spectroscopy (SERS), and the analysis of electrochemical reactions occurring under experimental conditions is presented. The bands of the SERS spectra of the Cu/CuO/Pd electrode observed in the range of E values from +0.3 V to 0 V (standard hydrogen electrode (SHE)) at 1328–1569 cm − 1 are consistent with the existence of species that are adsorbed or weakly bound to the surface with the energy of interaction close to 15–21 kJ mol − 1 . These bands can be attributed to the ad(ab)sorbed (H 3 O + ) ad , (H 2 + ) ab , and (H 2 + ) ad ions as intermediates in reversible hydrogen evolution and oxidation reactions (HER/HOR) taking place on the Cu/CuO/Pd electrode. There was no isotopic effect observed; this is consistent with the dipole nature of the electron-ion pair formation of adsorbed (H 3 O + ) ad and (H 2 + ) ad or (D 3 O + ) ad and (D 2 + ) ad . In accordance with the literature data, SERS bands at 125–146 cm − 1 and ∼520–565 cm − 1 were assigned to Cu(I) and Cu(II) oxygen species. These findings corroborate the quantitative stepwise mechanism of water reduction.

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Black-CuO: surface-enhanced Raman scattering and infrared properties

Cited by 37 publications

References 43 publications

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

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

Silk: Optical Properties over 12.6 Octaves THz-IR-Visible-UV Range

Hydrogen Evolution on Nano-StructuredCuO/Pd Electrode: Raman Scattering Study

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