Resonance Raman enhancement by the intralayer and interlayer electron–phonon processes in twisted bilayer graphene

Twisted bilayer graphene is a fascinating system due to the possibility of tuning the electronic and optical properties by controlling the twisting angle $$\theta$$ θ between the layers. The coupling between the Dirac cones of the two graphene layers gives rise to van Hove singularities (vHs) in the density of electronic states, whose energies vary with $$\theta$$ θ . Raman spectroscopy is a fundamental tool to study twisted bilayer graphene (TBG) systems since the Raman response is hugely enhanced when the photons are in resonance with transition between vHs and new peaks appear in the Raman spectra due to phonons within the interior of the Brillouin zone of graphene that are activated by the Moiré superlattice. It was recently shown that these new peaks can be activated by the intralayer and the interlayer electron–phonon processes. In this work we study how each one of these processes enhances the intensities of the peaks coming from the acoustic and optical phonon branches of graphene. Resonance Raman measurements, performed in many different TBG samples with $$\theta$$ θ between $$4^{\circ }$$ 4 ∘ and $$16^{\circ }$$ 16 ∘ and using several different laser excitation energies in the near-infrared (NIR) and visible ranges (1.39–2.71 eV), reveal the distinct enhancement of the different phonons of graphene by the intralayer and interlayer processes. Experimental results are nicely explained by theoretical calculations of the double-resonance Raman intensity in graphene by imposing the momentum conservation rules for the intralayer and the interlayer electron–phonon resonant conditions in TBGs. Our results show that the resonant enhancement of the Raman response in all cases is affected by the quantum interference effect and the symmetry requirements of the double resonance Raman process in graphene.

Development of Bio-Functionalized, Raman Responsive, and Potentially Excretable Gold Nanoclusters

Gold nanoparticles (AuNPs) are used experimentally for non-invasive in vivo Raman monitoring because they show a strong absorbance in the phototherapeutic window (650–850 nm), a feature that is accompanied by a particle size in excess of 100 nm. However, these AuNPs cannot be used clinically because they are likely to persist in mammalian systems and resist excretion. In this work, clustered ultrasmall (sub-5 nm) AuNP constructs for in vivo Raman diagnostic monitoring, which are also suitable for mammalian excretion, were synthesized and characterized. Sub-5 nm octadecyl amine (ODA)-coated AuNPs were clustered using a labile dithiol linker: ethylene glycol bis-mercaptoacetate (EGBMA). Upon clustering via a controlled reaction and finally coating with a polymeric amphiphile, a strong absorbance in the phototherapeutic window was demonstrated, thus showing the potential suitability of the construct for non-invasive in vivo detection and monitoring. The clusters, when labelled with a biphenyl-4-thiol (BPT) Raman tag, were shown to elicit a specific Raman response in plasma and to disaggregate back to sub-5 nm particles under physiological conditions (37 °C, 0.8 mM glutathione, pH 7.4). These data demonstrate the potential of these new AuNP clusters (Raman NanoTheranostics—RaNT) for in vivo applications while being in the excretable size window.

Thickness-Dependent Band Gap Modification in BaBiO3

The material BaBiO3 is known for its insulating character. However, for thin films, in the ultra-thin limit, metallicity is expected because the oxygen octahedra breathing mode will be suppressed as reported recently. Here, we confirm the influence of the oxygen breathing mode on the size of the band gap. The electronic properties of a BaBiO3 thickness series are studied using in-situ scanning tunneling microscopy. We observe a wide-gap (EG> 1.2 V) to small-gap (EG≈ 0.07 eV) semiconductor transition as a function of a decreasing BaBiO3 film thickness. However, even for an ultra-thin BaBiO3 film, no metallic state is present. The dependence of the band gap size is found to be coinciding with the intensity of the Raman response of the breathing phonon mode as a function of thickness.

Polarization-dependence of the Raman response of free-standing strained Ce0.8Gd0.2O2 membranes

Square-shaped Ce0.8Gd0.2O2 (GDC) membranes are prepared by microstructuring techniques from (111)-oriented, polycrystalline GDC thin films. The strain state of the membranes is investigated by micro-Raman mapping using polarized excitation light....