Tip-enhanced Raman scattering (TERS) microscopy is a unique analytical tool to provide complementary chemical and topographic information of surfaces with nanometric resolution. However, difficulties in reliably producing the necessary metallized scanning probe tips has limited its widespread utilisation, particularly in the case of cantilever-based atomic force microscopy. Attempts to alleviate tip related issues using colloidal or bottom-up engineered tips have so far not reported consistent probes for both Raman and topographic imaging. Here we demonstrate the reproducible fabrication of cantilever-based high-performance TERS probes for both topographic and Raman measurements, based on an approach that utilises noble metal nanowires as the active TERS probe. The tips show 10 times higher TERS contrasts than the most typically used electrochemically-etched tips, and show a reproducibility for TERS greater than 90%, far greater than found with standard methods. We show that TERS can be performed in tapping as well as contact AFM mode, with optical resolutions around or below 15 nm, and with a maximum resolution achieved in tapping-mode of 6 nm. Our work illustrates that superior TERS probes can be produced in a fast and cost-effective manner using simple wet-chemistry methods, leading to reliable and reproducible high-resolution and high-sensitivity TERS, and thus renders the technique applicable for a broad community.
Lanthanides, holmium(iii), dysprosium(iii), and terbium(iii), were coordinated to an amphiphilic DOTA bis-coumarin derivative and then further assembled with an amphiphilic europium(iii) DTPA bis-coumarin derivative into mono-disperse micelles. The self-assembled micelles were characterized and assessed for their potential as bimodal contrast agents for high field magnetic resonance and optical imaging applications. All micelles showed a high transverse relaxation (r) of 46, 34, and 30 s mM at 500 MHz and 37 °C for Dy(iii), Ho(iii) and Tb(iii), respectively, which is a result of the high magnetic moment of these lanthanides and the long rotational correlation time of the micelles. The quantum yield in aqueous solution ranged from 1.8% for Tb/Eu to 1.4% for Dy/Eu and 1.0% for the Ho/Eu micelles. Multi-photon excited emission spectroscopy has shown that due to the two-photon absorption of the coumarin chromophore the characteristic Eu(iii) emission could be observed upon excitation at 800 nm, demonstrating the usefulness of the system for in vivo fluorescence imaging applications. To the best of our knowledge, this is the first example reporting the potential of a holmium(iii) chelate as a negative MRI contrast agent.
TERS is a powerful tool for nanoscale optical characterization of surfaces. However, even after 20 years of development, the parameters for optimal TERS tips are still up for debate. As a result, routine measurements on bulk or dielectric substrates remain exceptionally challenging. Herein we help to alleviate this by using electrical cutting to strategically modify silver nanowire TERS probes. Following cutting, the tips present a large, spherical apex and are often nanostructured with numerous nanoparticles, which we argue improve light collection and optical coupling. This doubles TERS signals on a highly enhancing, gap-mode substrate compared to our standard nanowire tips while maintaining a high reproducibility and resolution. More interestingly, on a dielectric substrate (graphene on SiO 2 ) the tips give ∼7× higher signals than our standard tips. Further investigations point to the nonlocal nature of the enhancement using standard, smooth TERS probes without gap-mode, making such nanostructuring highly beneficial in these cases.
Tip-enhanced Raman scattering (TERS) microscopy is an advanced technique for investigation at the nanoscale because of its excellent properties, such as label-free functionality, non-invasiveness, and the ability to simultaneously provide...
The potential of nonlinear optical microscopy for the label-free visualization of heterogeneities and defects in metal–organic frameworks is demonstrated.
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