Highly Localized Strain in a MoS₂/Au Heterostructure Revealed by Tip-Enhanced Raman Spectroscopy

Tip-enhanced Raman spectroscopy (TERS) has been rapidly improved over the past decade and opened up opportunities to study phonon properties of materials at the nanometer scale. In this Letter, we report on TERS of an ultrathin MoS₂ flake on a nanostructured Au on silicon surface forming a two-dimensional (2D) crystal/plasmonic heterostructure. Au nanostructures (shaped in triangles) are prepared by nanosphere lithography, and then MoS₂ is mechanically exfoliated on top of them. The TERS spectra acquired under resonance conditions at 638 nm excitation wavelength evidence strain changes spatially localized to regions as small as 25 nm in TERS imaging. We observe the highest Raman intensity enhancement for MoS₂ on top of Au nanotriangles due to the strong electromagnetic confinement between the tip and a single triangle. Our results enable us to determine the local strain in MoS₂ induced during heterostructure formation. The maximum frequency shift of E_2g mode is determined to be (4.2 ± 0.8) cm^–1, corresponding to 1.4% of biaxial strain induced in the MoS₂ layer. We find that the regions of maximum local strain correspond to the regions of maximum topographic curvature as extracted from atomic force microscopy measurements. This tip-enhanced Raman spectroscopy study allows us to determine the built-in strain that arises when 2D materials interact with other nanostructures

Optical Absorption Imaging by Photothermal Expansion with 4 nm Resolution

For quite a long time, people thought of the diffraction limit of light as a fundamental unbreakable barrier that prevents seeing objects with sizes smaller than half the wavelength of light. Super-resolution optical methods and near-field optics enabled overcoming this limitation. Here we report an alternative approach based on tracking the photothermal expansion that a nano-object experiences upon visible light absorption, applied successfully in the characterization of samples with a spatial/lateral resolution down to 4 nm. Our device consists of an atomic force microscope coupled with a solid-state laser and a mechanical chopper synchronized with the natural oscillation mode of an in-house-made gold tip cantilever system. This configuration enhances the detection of nanostructures due to the intermittent light excitation and the consequent intermittent thermal expansion of the sample under investigation. The sensitivity and spatial resolution are further improved by the electric field enhancement due to the excitation of localized surface plasmons at the tip apex. Our concept is demonstrated by the analysis of a two-dimensional material (GaSe) on crystalline sp² carbon (graphite) and by an array of multiwalled carbon nanotubes lithographically designed in a SiO₂ matrix. The photothermal expansion originating from light absorption leads to an unprecedented spatial resolution for an optical absorption event imaged below 10 nm

Textile Electronics with Laser-Induced Graphene/Polymer Hybrid Fibers

The concept of wearables is rapidly evolving from flexible polymer-based devices to textile electronics. The reason for this shift is the ability of textiles to ensure close contact with the skin, resulting in comfortable, lightweight, and compact “always with you” sensors. We are contributing to this polymer-textile transition by introducing a novel and simple way of laser intermixing of graphene with synthetic fabrics to create wearable sensing platforms. Our hybrid materials exhibit high electrical conductivity (87.6 ± 36.2 Ω/sq) due to the laser reduction of graphene oxide and simultaneous laser-induced graphene formation on the surface of textiles. Furthermore, the composite created between graphene and nylon ensures the durability of our materials against sonication and washing with detergents. Both of these factors are essential for real-life applications, but what is especially useful is that our free-form composites could be used as-fabricated without encapsulation, which is typically required for conventional laser-scribed materials. We demonstrate the exceptional versatility of our new hybrid textiles by successfully recording muscle activity, heartbeat, and voice. We also show a gesture sensor and an electrothermal heater embedded within a single commercial glove. Additionally, the use of these textiles could be extended to personal protection equipment and smart clothes. We achieve this by implementing self-sterilization with light and laser-induced functionalization with silver nanoparticles, which results in multifunctional antibacterial textiles. Moreover, incorporating silver into such fabrics enables their use as surface-enhanced Raman spectroscopy sensors, allowing for the direct analysis of drugs and sweat components on the clothing itself. Our research offers valuable insights into simple and scalable processes of textile-based electronics, opening up new possibilities for paradigms like the Internet of Medical Things

Confirming the Dual Role of Etchants during the Enrichment of Semiconducting Single Wall Carbon Nanotubes by Chemical Vapor Deposition

The search for ways to synthesize single wall carbon nanotubes (SWCNT) of a given electronic type in a controlled manner persists despite great challenges because the potential rewards are huge, in particular as a material beyond silicon. In this work we take a systematic look at three primary aspects of semiconducting enriched SWCNT grown by chemical vapor deposition. The role of catalyst choice, substrate, and feedstock mixture are investigated. In terms of semiconducting yield enhancement, little influence is found from either the binary catalyst or substrate choice. However, a very clear enrichment is found as one adds nominal amounts of methanol to an ethanol feedstock. Yields of up to 97% semiconducting SWCNT are obtained. These changes are attributed to two known etchant processes. In the first, metal SWCNT are preferentially etched. In the second, we reveal etchants also preferentially etch small diameter tubes because they are more reactive. The etchants are confirmed to have a dual role, to preferentially etch metallic tubes and narrow diameter tubes (both metallic and semiconducting) which results in a narrowing of the SWCNT diameter distribution

Smart Graphene Textiles for Biopotential Monitoring: Laser-Tailored Electrochemical Property Enhancement

While most of the research in graphene-based materials seeks high electroactive surface area and ion intercalation, here, we show an alternative electrochemical behavior that leverages graphene’s potential in biosensing. We report a novel approach to fabricate graphene/polymer nanocomposites with near-record conductivity levels of 45 Ω sq–1 and enhanced biocompatibility. This is realized by laser processing of graphene oxide in a sandwich structure with a thin (100 μm) polyethylene terephthalate film on a textile substrate. Such hybrid materials exhibit high conductivity, low polarization, and stability. In addition, the nanocomposites are highly biocompatible, as evidenced by their low cytotoxicity and good skin adhesion. These results demonstrate the potential of graphene/polymer nanocomposites for smart clothing applications