Clip-on lens for scanning tunneling luminescence microscopy.

We demonstrate and verify the in-situ addition of a collecting lens for electroluminescence experiments to an existing scanning tunneling microscope. We fabricate a simple clip-on lens that we reversibly attach at the sample plate via regular sample transfer tools to collimate the light emitted from a plasmonic tunneling junction to the viewport ordinarily used for optical access. The proximity of the lens to the tunneling junction allows us achieve good collection efficiencies, demonstrating the quick turnaround of converting an existing setup with optical access into a practical scanning luminescence microscope. We verify the function of the clip-on lens by measuring the bias dependent plasmon of Au, Ag, and spatial luminescence maps.•Reversible clip-on lens.•In-situ transfer.•Luminescence.

Advanced Vibrational Spectroscopy and Bacteriophages Team Up: Dynamic Synergy for Medical and Environmental Applications.

Bacteriophages are emerging as a promising alternative in combating antibiotic-resistant bacteria amidst the escalating global antimicrobial resistance crisis. Recently, there has been a notable resurgence of interest in phages, prompting extensive research into their therapeutic potential. Beyond conventional microbiology and virology techniques, such as genomics and proteomics, novel phenotypic and chemical characterization methods are being explored. Among these, there is a growing interest in vibrational spectroscopy, especially in advanced modalities such as surface-enhanced Raman spectroscopy (SERS), tip-enhanced Raman spectroscopy (TERS), and atomic force microscopy-infrared spectroscopy (AFM-IR), which offer improved sensitivity and spatial resolution. This review explores the spectrum of uses of vibrational spectroscopy for bacteriophages, including its role in diagnostics, biosensing, phage detection, assistance in phage-based therapy, and advancing basic research.

Resonant Tip-Enhanced Raman Spectroscopy of a Single-Molecule Kondo System.

Tip-enhanced Raman spectroscopy (TERS) under ultrahigh vacuum and cryogenic conditions enables exploration of the relations between the adsorption geometry, electronic state, and vibrational fingerprints of individual molecules. TERS capability of reflecting spin states in open-shell molecular configurations is yet unexplored. Here, we use the tip of a scanning probe microscope to lift a perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecule from a metal surface to bring it into an open-shell spin one-half anionic state. We reveal a correlation between the appearance of a Kondo resonance in differential conductance spectroscopy and concurrent characteristic changes captured by the TERS measurements. Through a detailed investigation of various adsorbed and tip-contacted PTCDA scenarios, we infer that the Raman scattering on suspended PTCDA is resonant with a higher excited state. Theoretical simulation of the vibrational spectra enables a precise assignment of the individual TERS peaks to high-symmetry Ag modes, including the fingerprints of the observed spin state. These findings highlight the potential of TERS in capturing complex interactions between charge, spin, and photophysical properties in nanoscale molecular systems and suggest a pathway for designing single-molecule spin-optical devices.

Fabrication of plasmonic probes for reproducible nanospectroscopic investigation of lipid monolayers - The electrochemical etching with DC-pulsed voltage.

Tip-enhanced Raman spectroscopy (TERS) is a label-free analytical technique that characterizes molecular systems, potentially even with a nanometric resolution. In principle, the metallic plasmonic probe is illuminated with a laser beam generating the localized surface plasmons, which induce a strong local electric field enhancement in close proximity to the probe. Such field enhancement improves the Raman scattering cross-section from the sample volume localized near the probe apex. TERS provides a high spatial resolution and a great sensitivity, however, it is rather rarely used due to technical limitations causing unstable enhancement and the relative lack of data reproducibility. Despite many scientific efforts for the fabrication of effective TER probes providing robust TER enhancement still requires further investigations. In this work, we explore new possibilities based on preparation of scanning tunnelling microscopy (STM) plasmonic probes, since by nature of the tunnelling effect, they potentially could offer a very high spatial resolution in STM guided TERS experiments. Here we compare two methods of STM-TERS probe preparation for effective spectra acquisition. Our results strongly indicate that an application of square pulse voltage upon the etching procedure significantly improves the quality of the TER data over those obtained with a constant voltage one. To demonstrate the efficiency of our probes we present the results of hyperspectral TER mapping of the 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE) monolayer deposited on an ultra-pure and atomically flat gold substrate.

Strained Silicon Technology: Non-Destructive High-Lateral-Resolution Characterization Through Tip-Enhanced Raman Spectroscopy.

The semiconductor industry is undergoing a transformative phase, marked by the relentless drive for miniaturization and a constant demand for higher performance and energy efficiency. However, the reduction of metal-oxide-semiconductor field-effect transistor sizes for advanced technology nodes below 10 nm presents several challenges. In response, strained silicon technology has emerged as a key player, exploiting strain induction in the silicon crystal lattice to improve device performance. At the same time, there has been a growing need for characterization techniques that allow in-line monitoring of sample conditions during semiconductor manufacturing, as an alternative to traditional methods such as transmission electron microscopy or high-resolution X-ray diffraction, which have several limitations in terms of measurement time and sample destructiveness. This paper explores the application of advanced spectroscopic characterization techniques, in particular µ-Raman spectroscopy and tip-enhanced Raman spectroscopy (TERS), to meet the evolving needs of the semiconductor industry for quality control and failure analysis, increasingly requiring faster and non-destructive characterization techniques. µ-Raman provides insight into strain values and distributions of strained layers with different thicknesses and germanium concentrations, but its lateral resolution is constrained by the Abbe diffraction limit. TERS, on the other hand, emerges as a powerful non-destructive technique capable of overcoming diffraction limits by exploiting the combination of an atomic force microscope with a Raman spectrometer. This breakthrough makes it possible to estimate the chemical composition and induced strain in the lattice by evaluating the Raman peak position shifts in strained and unstrained silicon layers, providing crucial insights for nanoscale strain control. In particular, this paper focuses on the TERS characterization of Si0.7Ge0.3 epitaxial layers grown on a silicon-on-insulator device, demonstrating the effectiveness of this technique and the high lateral resolution that can be achieved.

A Full Quantum Mechanical Approach Assessing the Chemical and Electromagnetic Effect in TERS.

Tip-enhanced Raman spectroscopy (TERS) is a valuable method for surface analysis with nanometer to angstrom-scale resolution; however, the accurate simulation of particular TERS signals remains a computational challenge. We approach this challenge by combining the two main contributors to plasmon-enhanced Raman spectroscopy and to the high resolution in TERS, in particular, the electromagnetic and the chemical effect, into one quantum mechanical simulation. The electromagnetic effect describes the sample's interaction with the strong, highly localized, and inhomogeneous electric fields associated with the plasmonic tip and is typically the thematic focus for most mechanistic studies. On the other hand, the chemical effect covers the different responses to the extremely close-range and highly position-sensitive chemical interaction between the apex tip atom(s) and the sample, and, as we could show in previous works, plays an often underestimated role. Starting from a (time-dependent) density functional theory description of the chemical model system, comprised of a tin(II) phthalocyanine sample molecule and a single silver atom as the tip, we introduce the electromagnetic effect through a series of static point charges that recreate the electric field in the vicinity of the plasmonic Ag nanoparticle. By scanning the tip over the molecule along a 3D grid, we can investigate the system's Raman response on each position for nonresonant and resonant illumination. Simulating both effects on their own already hints at the achievable signal enhancement and resolution, but the combination of both creates even stronger evidence that TERS is capable of resolving submolecular features.

Spatially Coherent Tip-Enhanced Raman Spectroscopy Measurements of Electron-Phonon Interaction in a Graphene Device.

Coherence length (Lc) of the Raman scattering process in graphene as a function of Fermi energy is obtained with spatially coherent tip-enhanced Raman spectroscopy. Lc decreases when the Fermi energy is moved into the neutrality point, consistent with the concept of the Kohn anomaly within a ballistic transport regime. Since the Raman scattering involves electrons and phonons, the observed results can be rationalized either as due to unusually large variation of the longitudinal optical phonon group velocity vg, reaching twice the value for the longitudinal acoustic phonon, or due to changes in the electron energy uncertainty, both properties being important for optical and transport phenomena that might not be observable by any other technique.

Apex-Confined Plasmonic Tip for High Resolution Tip-Enhanced Raman Spectroscopic Imaging of Carbon Nanotubes.

This paper reports a handy technical scheme to decorate atomic force microscopy (AFM) tips toward tip-enhanced Raman spectroscopy (TERS) applications. The major attraction of these homemade tips lies in that silver decoration can be confined at the apex of commercial tips by the means of an AFM-controlled electrochemical reaction. The reduction of Ag+ occurs in a highly sealed environment to secure the metal coating efficiency. Key factors include silver nitrate solution to provide Ag+, ambient relative humidity and temperature in a humidity cell, electric potential bias, and tip-surface distance. Subsequently, these silver-coated tips are evaluated for TERS measurement of carbon nanotubes (CNTs) so that both morphological and chemical characteristics of CNTs are concurrently obtained. The Raman spectra reveal that our plasmonic tip competently possesses an ∼30-fold local field signal increase and the corresponding TERS image laterally resolves at the single-pixel level.

Ecological risk assessment of pesticides on soil biota: An integrated field-modelling approach.

Pesticide residues in soils can cause negative impacts on soil health as well as soil biota. However, research related to the toxicity and exposure risks of pesticides to soil biota are scarce, especially in the North China Plain (NCP) where pesticides are intensively applied. In this study, the occurrence and distribution of 15 commonly used pesticides in 41 fields in Quzhou county in the NCP were determined during the growing season in 2020. The ecological risks of pesticides to the soil biota, including earthworms, enchytraeids, springtails, mites and nitrogen mineralization microorganisms, were assessed using toxicity exposure ratios (TERs) and risk quotient (RQ) methods. Based on pesticide detection rates and RQs, pesticide hazards were ranked using the Hasse diagram. The results showed that pesticides were concentrated in the 0-2 cm soil depth. Chlorantraniliprole was the most frequently detected pesticide with a detection rate of 37%, while the highest concentration of 1.85 mg kg-1 was found for carbendazim in apple orchards. Chlorpyrifos, carbendazim and imidacloprid posed a chronic exposure risk to E. fetida, F. candida and E. crypticus with the TERs exceeding the trigger value. Pesticide mixtures posed ecological risks to soil biota in 70% of the investigated sites. 47.5% of samples were ranked as high-risk, with the maximum RQ exceeding 490. According to the Hasse diagram, abamectin, tebuconazole, chlorantraniliprole and chlorpyrifos were ranked as the most hazardous pesticides for soil biota in the study region, indicating that alternative methods of pest management need to be considered. Therefore, practical risk mitigation solutions are recommended, in which the use of hazardous pesticides would be replaced with low-risk pesticides with similar functions from the Hasse diagram, or with biopesticides.

Inside Block Copolymer Micelles-Tracing Interfacial Influences on Crosslinking Efficiency in Nanoscale Confined Spaces.

Recently, several studies have demonstrated the excellent capabilities of tip-enhanced Raman spectroscopyfor in-depth investigations of structural properties of matter with unprecedented resolution and chemical specificity. These capabilities are utilized here to study the internal structure of core-crosslinked micelles, which are formed by self-assembly of the diblock terpolymer poly(ethylene oxide)-block-poly(furfuryl glycidylether-co-tert-butylglycidyl ether). Supplementing force-volume atomic force microscopy experiments address additionally the nanomechanical properties. Particularly, TERS enables investigating the underlying principles influencing the homogeneity and efficiency of the Diels-Alder core-crosslinking process in the confined hydrophobic core. While the central core region is homogenously crosslinked, a breakdown of the crosslinking reaction is observed in the core-corona interfacial region. The results corroborate that a strong crosslinking efficiency is directly correlated to the formation of a mixed zone of the glycidyl ether and PEO corona blocks reaching ≈5 nm into the core region. Concomitantly a strong exclusion of the encapsulated bismaleimide crosslinker from the interfacial region is observed. It is conceivable that a changed structure, chemical composition and altered nanomechanical properties of this interfacial region may also influence the crosslinking efficiency across the entire core region by a modification of the solubility of the crosslinker in the interfacial core-corona region.

Homogeneous Pt nanostructures surface functionalized with phenylboronic acid phosphonic acid derivatives as potential biochemical nanosensors and drugs: SERS and TERS studies.

Here, surface-enhanced Raman scattering (SERS) and tip-enhanced Raman scattering (TERS) were used to characterize the selective adsorption of N-substituted 4-[(NH-R)(phosphono)-S-methyl]phenylboronic acids on the surface of platinum nanoparticles (PtNPs) from an aqueous solution and from air. The nature of the interaction of the studied compounds with the PtNPs/H2 O and PtNPs/air interfaces was discussed and compared. For this purpose, 4-[(N-anilino)(phosphono)-S-methyl]phenylboronic acid (1-PBA-PA) and its two analogs (2-PBA-PA and bis{1-PBA-PA}) as well as the PtNPs were synthesized in surfactant/ion-free solution via a synthetic route that allows control of the size and morphology of the NPs. The positively charged PtNPs with a size of ~12 nm were characterized by ultraviolet-visible spectroscopy (UV-Vis), dynamic light scattering (DLS), scanning electron microscopy (SEM), and X-ray powder diffraction (XRD).

Design of multi-axis micromotion system in TERS and its nonlinearity and crosstalk correction method.

Tip-Enhanced Raman Spectroscopy (TERS) is an advanced analytical measurement technology combining Raman spectroscopy with Scanning Probe Microscopy, which can detect the molecular structure and chemical composition in micro-nano-scale. As an indispensable part, the micromotion system directly determines TERS spatial resolution. The existing multi-axis system is often composed of several single-axis nonlinear systems, which solves whole problems with a superposition idea of single-axis part. But the multi-axis crosstalk under an overall idea is not fully considered and will cause system uncooperative and even oscillational. Therefore, a multi-axis micromotion system in TERS and its correction method are proposed. The improved Duhem model, simple calculation without inversion, accurate matching and fast response, has been built for nonlinearity. And the feedforward decoupling method is designed for crosstalk, having a favorable multi-axis coordination, good error tracking and simplified controllers. Experimental results show that it can greatly correct the nonlinearity and crosstalk of multi-axis system simultaneously.

Length-Controllable Gold-Coated Silver Nanowire Probes for High AFM-TERS Scattering Activity.

Tip-enhanced Raman scattering (TERS) microscopy is an advanced technique for investigation at the nanoscale that provides topographic and chemical information simultaneously. The TERS probe plays a crucial role in the microscopic performance. In the recent past, the development of silver nanowire (AgNW) based TERS probes solved the main tip fabrication issues, such as low mechanical strength and reproducibility. However, this fabrication method still suffers from low control of the protruded length of the AgNW. In this work, a simple water-air interface electrocutting method is proposed to achieve wide controllability of the length. This water cutting method was combined with a succedent Au coating on the AgNW surface, and the probe achieved an up to 100× higher enhancement factor (EF) and a 2× smaller spatial resolution compared to pristine AgNW. Thanks to this excellent EF, the water-cut Au-coated AgNW probes were found to possess high TERS activity even in the nongap mode, enabling broad applications.

Raman spectroscopy for profiling physical and chemical properties of atmospheric aerosol particles: A review.

Atmosphere aerosols have significant impact on human health and the environment. Aerosol particles have a number of characteristics that influence their health and environmental effects, including their size, shape, and chemical composition. A great deal of difficulty is associated with quantifying and identifying atmospheric aerosols because these parameters are highly variable on a spatial and temporal scale. An important component of understanding aerosol fate is Raman Spectroscopy (RS), which is capable of resolving chemical compositions of individual particles. This review presented strategic techniques, especially RS methods for characterizing atmospheric aerosols. The nature and properties of atmospheric aerosols and their influence on environment and human health were briefly described. Analytical methodologies that offer insight into the chemistry and multidimensional properties of aerosols were discussed. In addition, perspectives for practical applications of atmospheric aerosols using RS are featured.

Influence of TiO2 and ZnO Nanoparticles on α-Synuclein and ß-Amyloid Aggregation and Formation of Protein Fibrils.

The most common neurological disorders, i.e., Parkinson's disease (PD) and Alzheimer's disease (AD), are characterized by degeneration of cognitive functions due to the loss of neurons in the central nervous system. The aggregation of amyloid proteins is an important pathological feature of neurological disorders.The aggregation process involves a series of complex structural transitions from monomeric to the formation of fibrils. Despite its potential importance in understanding the pathobiology of PD and AD diseases, the details of the aggregation process are still unclear. Nanoparticles (NPs) absorbed by the human circulatory system can interact with amyloid proteins in the human brain and cause PD. In this work, we report the study of the interaction between TiO2 nanoparticles (TiO2-NPs) and ZnO nanoparticles (ZnO-NPs) on the aggregation kinetics of ß-amyloid fragment 1-40 (ßA) and α-synuclein protein using surface-enhanced Raman spectroscopy (SERS) and tip-enhanced Raman spectroscopy (TERS). The characterizations of ZnO-NPs and TiO2-NPs were evaluated by X-ray diffraction (XRD) spectrum, atomic force microscopy (AFM), and UV-Vis spectroscopy. The interaction of nanoparticles with amyloid proteins was investigated by SERS. Our study showed that exposure of amyloid protein molecules to TiO2-NPs and ZnO-NPs after incubation at 37 °C caused morphological changes and stimulated aggregation and fibrillation. In addition, significant differences in the intensity and location of active Raman frequencies in the amide I domain were found. The principal component analysis (PCA) results show that the effect of NPs after incubation at 4 °C does not cause changes in ßA structure.

Viral Small Terminase: A Divergent Structural Framework for a Conserved Biological Function.

The genome packaging motor of bacteriophages and herpesviruses is built by two terminase subunits, known as large (TerL) and small (TerS), both essential for viral genome packaging. TerL structure, composition, and assembly to an empty capsid, as well as the mechanisms of ATP-dependent DNA packaging, have been studied in depth, shedding light on the chemo-mechanical coupling between ATP hydrolysis and DNA translocation. Instead, significantly less is known about the small terminase subunit, TerS, which is dispensable or even inhibitory in vitro, but essential in vivo. By taking advantage of the recent revolution in cryo-electron microscopy (cryo-EM) and building upon a wealth of crystallographic structures of phage TerSs, in this review, we take an inventory of known TerSs studied to date. Our analysis suggests that TerS evolved and diversified into a flexible molecular framework that can conserve biological function with minimal sequence and quaternary structure conservation to fit different packaging strategies and environmental conditions.

Spatially-Localized Functionalization on Nanostructured Surfaces for Enhanced Plasmonic Sensing Efficacy.

This work demonstrates the enhancement in plasmonic sensing efficacy resulting from spatially-localized functionalization on nanostructured surfaces, whereby probe molecules are concentrated in areas of high field concentration. Comparison between SERS measurements on nanostructured surfaces (arrays of nanodisks 110 and 220 nm in diameter) with homogeneous and spatially-localized functionalization with thiophenol demonstrates that the Raman signal originates mainly from areas with high field concentration. TERS measurements with 10 nm spatial resolution confirm the field distribution profiles predicted by the numerical modeling. Though this enhancement in plasmonic sensing efficacy is demonstrated with SERS, results apply equally well to any type of optical/plasmonic sensing on functionalized surfaces with nanostructuring.

Can Light Alter the Yield of Plasmon-Driven Reactions on Gold and Gold-Palladium Nanoplates?

Noble-metal nanostructures, as well as their bimetallic analogues, catalyze a broad spectrum of plasmon-driven reactions. Catalytic properties of such nanostructures arise from light-generated surface plasmon resonances that decay forming transient hot electrons and holes. Hot carriers with "slower" dissipation rates accumulate on nanostructures generating an electrostatic potential. In this study, we examine whether light intensity can alter the electrostatic potential of mono- and bimetallic nanostructures changing yields of plasmon-driven reactions. Using tip-enhanced Raman spectroscopy (TERS), we quantified the yield of plasmon-driven transformations of 4-nitrobenzenethiol (4-NBT) and 3-mercaptobenzoic acid (3-MBA) on gold and gold-palladium nanoplates (AuNPs and Au@PdNPs, respectively). We found that on AuNPs 3-MBA decarboxylated forming thiophenol (TP), whereas 4-NBT was reduced to DMAB. The yield of both TP and DMAB gradually increased with increasing light intensity. On Au@PdNPs, 3-MBA could be reduced to 3-mercaptophenylmethanol (3-MPM), the yield of which was also directly dependent on the light intensity.

Optimization of tip-enhanced Raman spectroscopy for probing the chemical structure of DNA.

Tip-enhanced Raman (TER) spectroscopy combines the nanometric spatial resolution of atomic force microscopy (AFM) and the chemical sensitivity of Raman spectroscopy. Thus, it provides a unique possibility to obtain spectroscopic information on individual, nanometre-size molecules. The enhancement of Raman scattering cross-section requires modification of the AFM tip apex with a plasmonic nanostructure. Despite numerous advances of TERS research, attaining good reproducibility and stable enhancement is still challenging mainly due to the lack of optimized probes and sample preparation procedures. Moreover, current nanospectroscopic standard samples - carbon nanotubes (CNTs) have relatively simple chemical structure, and therefore, they are far from real-life analytes, especially biological samples. In this work we focus on the optimization of TERS technique for efficient DNA measurements, including: a preparation of atomically-flat gold substrates, fixative free deposition of DNA and optimization of TERS probe preparation. Here we demonstrate a comprehensive comparison of the efficacy of several types of TERS probes. Applying the systematic approach, we obtained reliable and reproducible TER spectra of DNA. Thus, we provide preparation procedures of a new standard TERS sample, TERS substrates and TERS probes. Our research provides a solid foundation for further research on DNA and its interaction with other biomolecules upon biologically significant processes such as DNA damage and repair.

Surface- and Tip-Enhanced Raman Scattering by CdSe Nanocrystals on Plasmonic Substrates.

This work presents an overview of the latest results and new data on the optical response from spherical CdSe nanocrystals (NCs) obtained using surface-enhanced Raman scattering (SERS) and tip-enhanced Raman scattering (TERS). SERS is based on the enhancement of the phonon response from nanoobjects such as molecules or inorganic nanostructures placed on metal nanostructured substrates with a localized surface plasmon resonance (LSPR). A drastic SERS enhancement for optical phonons in semiconductor nanostructures can be achieved by a proper choice of the plasmonic substrate, for which the LSPR energy coincides with the laser excitation energy. The resonant enhancement of the optical response makes it possible to detect mono- and submonolayer coatings of CdSe NCs. The combination of Raman scattering with atomic force microscopy (AFM) using a metallized probe represents the basis of TERS from semiconductor nanostructures and makes it possible to investigate their phonon properties with nanoscale spatial resolution. Gap-mode TERS provides further enhancement of Raman scattering by optical phonon modes of CdSe NCs with nanometer spatial resolution due to the highly localized electric field in the gap between the metal AFM tip and a plasmonic substrate and opens new pathways for the optical characterization of single semiconductor nanostructures and for revealing details of their phonon spectrum at the nanometer scale.