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We demonstrate the use of tip-enhanced Raman spectroscopy (TERS) on polymeric microstructures fabricated by two-photon polymerization direct laser writing (TPP-DLW). Compared to the signal intensity obtained in confocal Raman microscopy, a linear enhancement of almost two times is measured when using TERS. Because the probing volume is much smaller in TERS than in confocal Raman microscopy, the effective signal enhancement is estimated to be ca. 10⁴. We obtain chemical maps of TPP microstructures using TERS with relatively short acquisition times and with high spatial resolution as defined by the metallic tip apex radius of curvature. We take advantage of this high resolution to study the homogeneity of the polymer network in TPP microstructures printed in an acrylic-based resin. We find that the polymer degree of conversion varies by about 30% within a distance of only 100 nm. The combination of high resolution topographical and chemical data delivered by TERS provides an effective analytical tool for studying TPP-DLW materials in a non-destructive way.

 

The process of tip‐enhanced Raman scattering (TERS) depends critically on the morphology near the apex of the tip used in the experiment. Many tip designs have focused on optimization of electromagnetic enhancement in the near‐field, which is controlled to a large extent by subtle details at the nanoscale that remain difficult to reproduce in the tip fabrication process. The use of focused ion beams (FIB) permit modification of larger features on the tip in a reproducible manner, yet this approach cannot produce sub‐20‐nm structures important for optimum near‐field enhancement. Nonetheless, FIB milling offers excellent opportunities for improving the far‐field radiation properties of the tip‐antenna, a feature that has received relatively little attention in the TERS research community. In this work, we use finite‐difference time‐domain (FDTD) simulations to study both the near‐field and far‐field radiation efficiency of several tip‐antenna systems that can be constructed with FIB techniques in a feasible manner. Starting from blunt etched tips, we find that excellent overall enhancement of the TERS signal can be obtained with pillar‐type tips. Furthermore, by applying vertical grooves on the tip's shaft, the overall efficiency can be improved even more, producing TERS signals that are up to 10‐fold stronger than signals obtained from an ideal (unmodified) sharp tip of 10‐nm radius. The proposed designs constitute a feasible route toward a tip fabrication process that not only yields more reproducible tips but also promises much stronger TERS signals.

 

We theoretically show that the optical chiral properties of tightly focused laser beams can be characterized by means of force detection. To measure the chiral properties of a beam of given handedness in the microscopic focal volume, we determine the photoinduced force exerted on a sharp tip, which is illuminated first by the beam of interest and second by an auxiliary beam of opposite handedness, in a sequential manner. We show that the difference between the force measurements is directly proportional to the chiral properties of the beam of interest. In particular, the gradient force difference Δ⟨Fgrad ,z⟩ is found to have exclusive correspondence to the time-averaged helicity density of the incident light, whereas the differential scattering force provides information about the spin angular momentum density of light. We further characterize and quantify the helicity-dependent Δ⟨Fgrad ,z⟩ using a Mie scattering formalism complemented with full wave simulations, underlining that the magnitude of the difference force is within an experimentally detectable range. 

Photo-induced force microscopy (PiFM) is a scan probe technique that offers images with spectroscopic contrast at a spatial resolution in the nanometer range. PiFM utilizes the non-propagating, enhanced near field at the apex of a sharp tip to locally induce a polarization in the sample, which in turn produces an additional force acting on the cantilevered tip. This photo-induced force, though in the pN range or less, can be extracted from the oscillation properties of the cantilever, thus enabling the generation of photo-induced force maps. Since its inception in 2010, the PiFM technique has grown into a useful nano-spectrocopic tool that has expanded its reach in terms of imaging capabilities and applications. In this review, we present various technical implementations of the PiFM approach. In addition, we discuss the physical origin of the PiFM signal, highlighting the contributions from dipole–dipole forces as well as forces that derive from photo-thermal processes. 

Abstract Ultrafast laser 3D lithography based on non-linear light–matter interactions, widely known as multi-photon lithography (MPL), offers unrivaled precision rapid prototyping and flexible additive manufacturing options. 3D printing equipment based on MPL is already commercially available, yet there is still no comprehensive understanding of factors determining spatial resolution, accuracy, fabrication throughput, repeatability, and standardized metrology methods for the accurate characterization of the produced 3D objects and their functionalities. The photoexcitation mechanisms, spatial-control or photo-modified volumes, and the variety of processable materials are topics actively investigated. The complexity of the research field is underlined by a limited understanding and fragmented knowledge of light-excitation and material response. Research to date has only provided case-specific findings on photoexcitation, chemical modification, and material characterization of the experimental data. In this review, we aim to provide a consistent and comprehensive summary of the existing literature on photopolymerization mechanisms under highly confined spatial and temporal conditions, where, besides the excitation and cross-linking, parameters such as diffusion, temperature accumulation, and the finite amount of monomer molecules start to become of critical importance. Key parameters such as photoexcitation, polymerization kinetics, and the properties of the additively manufactured materials at the nanoscale in 3D are examined, whereas, the perspectives for future research and as well as emerging applications are outlined. 

Two-photon polymerization direct laser writing (TPP-DLW) is one of the most versatile technologies to additively manufacture complex parts with nanoscale resolution. However, the wide range of mechanical properties that results from the chosen combination of multiple process parameters imposes an obstacle to its widespread use. Here we introduce a thermal post-curing route as an effective and simple method to increase the mechanical properties of acrylate-based TPP-DLW-derived parts by 20-250% and to largely eliminate the characteristic coupling of processing parameters, material properties and part functionality. We identify the underlying mechanism of the property enhancement as a self-initiated thermal curing reaction, which robustly facilitates the high property reproducibility that is essential for any application of TPP-DLW.