Tommaso Baldacchini’s research while affiliated with Edwards Lifesciences and other places

Three-dimensional (3D) printing of silica glass is dominated by techniques that rely on traditional particle sintering. At the nanoscale, this limits their adoption within microsystem technology, which prevents technological breakthroughs. We introduce the sinterless, two-photon polymerization 3D printing of free-form fused silica nanostructures from a polyhedral oligomeric silsesquioxane (POSS) resin. Contrary to particle-loaded sacrificial binders, our POSS resin itself constitutes a continuous silicon-oxygen molecular network that forms transparent fused silica at only 650°C. This temperature is 500°C lower than the sintering temperatures for fusing discrete silica particles to a continuum, which brings silica 3D printing below the melting points of essential microsystem materials. Simultaneously, we achieve a fourfold resolution enhancement, which enables visible light nanophotonics. By demonstrating excellent optical quality, mechanical resilience, ease of processing, and coverable size scale, our material sets a benchmark for micro- and nano-3D printing of inorganic solids.

Nature provides us with a large number of functional material systems consisting of hierarchical structures, where significant variations in dimensions are present. Such hierarchical structures are difficult to build by traditional manufacturing processes due to manufacturing limitations. Nowadays, three-dimensional (3D) objects with complex structures can be built by gradually accumulating in a layer-based additive manufacturing (AM); however, the hierarchical structure measured from macroscale to nanoscale sizes still raises significant challenges to the AM processes, whose manufacturing capability is intrinsically specified within a certain scope. It is desired to develop a multi-scale AM process to narrow this gap between scales of feature in hierarchical structures. This research aims to investigate an integration approach to fabricate hierarchical objects that have macro-, micro- and nano- scales features in an object. Firstly, the process set-up and the integrated process of Two-Photon Polymerization (TPP), Immersed Surface Accumulation (ISA), and Mask Image Projection-based Stereolithography (MIP-SL) was introduced to address the multi-scale fabrication challenge. Then, special hierarchical design and process planning towards integrating multiple printing processes are demonstrated. Lastly, we present two test cases built by our hierarchical printing method to validate the feasibility and efficiency of the proposed multi-scale hierarchical printing approach. The results demonstrated the capability of the developed multi-scale 3D printing process and showed its future potential in various novel applications, such as optics, microfluidics, cell culture, as well as interface technology.

We introduce techniques for probing the dynamics of triplet states. We employ these tools, with conventional techniques, to develop a detailed understanding of a complex chemical system: a negative-tone, radical photoresist for multiphoton absorption polymerization in which isopropylthioxanthone (ITX) is the photoinitiator. This work reveals that the same color of light used for the 2-photon excitation of ITX, leading to population of the triplet manifold through intersystem crossing, also depletes this triplet population via linear absorption followed by reverse intersystem crossing (RISC). Using spectroscopic tools and kinetic modeling, we identify the reactive triplet state and a non-reactive reservoir triplet state. We present compelling evidence that the deactivation channel involves RISC from an excited triplet state to a highly vibrationally excited level of the electronic ground state. The work described here offers the enticing possibility of understanding, and ultimately controlling, the photochemistry and photophysics of a broad range of triplet processes.

The emerging technique of mid-infrared optical coherence tomography (MIR-OCT) takes advantage of the reduced scattering of MIR light in various materials and devices, enabling tomographic imaging at deeper penetration depths. Because of challenges in MIR detection technology, the image acquisition time is, however, significantly longer than for tomographic imaging methods in the visible/near-infrared. Here we demonstrate an alternative approach to MIR tomography with high-speed imaging capabilities. Through femtosecond nondegenerate two-photon absorption of MIR light in a conventional Si-based CCD camera, we achieve wide-field, high-definition tomographic imaging with chemical selectivity of structured materials and biological samples in mere seconds.

The emerging technique of mid-infrared optical coherence tomography (MIR-OCT) takes advantage of the reduced scattering of MIR light in various materials and devices, enabling tomographic imaging at deeper penetration depths. Because of challenges in MIR detection technology, the image acquisition time is however significantly longer than for tomographic imaging methods in the visible/near-infrared. Here we demonstrate an alternative approach to MIR tomography with high-speed imaging capabilities. Through femtosecond non-degenerate two-photon absorption of MIR light in a conventional Si-based CCD camera, we achieve wide-field, high-definition tomographic imaging with chemical selectivity of structured materials and biological samples in mere seconds.

Laser-based three-dimensional (3D) printing methods, including laser direct-write cell printing and two-photon polymerization, have seen significant advances because of their unique photonic characteristics. Several mechanisms have been developed to increase the overall throughput of two-photon polymerization. Recent efforts to develop complex medically relevant structures using laser direct-write cell printing have also been demonstrated; for example, an ex vivo experimental platform for time-lapse imaging of cancer cell dynamics during angiogenesis within a microvascular network, which combines laser direct-write cell printing into the rat mesentery culture model; a model that simulates a 3D in vivo culture. Laser 3D printing methods hold significant promise for 3D printing of tissue engineering scaffolds, microstructured medical devices, and other medically relevant structures.

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. 10 ⁴ . 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.

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.

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 are 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 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.