The Surface Modification of Papers Using Laser Processing towards Applications.

This work presents the results of paper laser processing. It begins with the selection and examination of the processing parameters, then an examination of the properties of the modified papers and examples of applications of the developed modification method. The properties of laser-modified paper were studied using reflectance spectrophotometry to examine the colour aspects of the modified papers, scanning electron microscopy (SEM) and confocal microscopy for a morphological analysis, and Raman spectroscopy to analyse the papers under the influence of laser light. The influence of laser processing on the wettability of paper and the evenness of unprinted and printed paper was also investigated. The knowledge gained on paper surface modification with laser light was used to propose several applications, such as methods of marking, tactile detection, the controlled removal of optical brightener, ink, and metallised coatings from paper packaging, highlighting the design and aesthetics of paper. The developed laser-assisted method shows a promising, ecological approach to the design of many value-added paper products.

High-Quality Microprintable and Stretchable Conductors for High-Performance 5G Wireless Communication.

With the advent of 5G wireless and Internet of Things technologies, flexible and stretchable printed circuit boards (PCBs) should be designed to address all the specifications necessary to receive signal transmissions, maintaining the signal integrity, and providing electrical connections. Here, we propose a silver nanoparticle (AgNP)/silver nanowire (AgNW) hybrid conductor and high-quality microprinting technology for fabricating flexible and stretchable PCBs in high-performance 5G wireless communication. A simple and low-cost reverse offset printing technique using a commercial adhesive hand-roller was adapted to ensure high-resolution and excellent pattern quality. The AgNP/AgNW micropatterns were fabricated in various line widths, from 5 µm to 5 mm. They exhibited excellent pattern qualities, such as fine line spacing, clear edge definition and outstanding pattern uniformity. After annealing via intense pulsed light irradiation, they showed outstanding electrical resistivity (15.7 µΩ cm). Moreover, they could withstand stretching up to a strain of 90% with a small change in resistance. As a demonstration of their practical application, the AgNP/AgNW micropatterns were used to fabricate 5G communication antennas that exhibited excellent wireless signal processing at operating frequencies in the C-band (4-8 GHz). Finally, a wearable sensor fabricated with these AgNP/AgNW micropatterns could successfully detected fine finger movements in real time with excellent sensitivity.

Visible-Light-Degradable 3D Microstructures in Aqueous Environments.

The additive manufacturing technique direct laser writing (DLW), also known as two-photon laser lithography, is becoming increasingly established as a technique capable of fabricating functional 3D microstructures. Recently, there has been an increasing effort to impart microstructures fabricated using DLW with advanced functionalities by introducing responsive chemical entities into the underpinning photoresists. Herein, a novel photoresist based on the photochemistry of the bimane group is introduced that can be degraded upon exposure to very mild conditions, requiring only water and visible light (λmax  = 415-435 nm) irradiation. The degradation of the microstructures is tracked and quantified using AFM measurements of their height. The influence of the writing parameters as well as the degradation conditions is investigated, unambiguously evidencing effective visible light degradation in aqueous environments. Finally, the utility of the photodegradable resist system is demonstrated by incorporating it into multimaterial 3D microstructures, serving as a model for future applications.

An On-Chip Liquid Metal Plug Generator.

Gallium-based liquid metal nonspherical droplets (plugs) have seen increasing demand recently mainly because their high aspect ratios make them beneficial for a wide range of applications, including microelectromechanical systems (MEMS), microfluidics, sensor technology, radio-frequency devices, actuators, and switches. However, reproducibility of the generation of such plugs, as well as precise control over their size, is yet challenging. In this work, a simple on-chip liquid metal plug generator using a commercially available 3D microprinter is presented and the plug generator in poly(dimethylsiloxane) is replicated via soft lithography. Liquid metal plugs are generated via a combination of electrochemical oxidation, design of well-defined constrictions based on Laplace pressure, and the application of modulated voltage control signals. It is shown that plugs of various aspect ratios can be generated reproducibly for channel widths of 0.5, 0.8, and 1.5 mm with constriction widths of 0.1 mm at 6 V. Laplace-pressure-controlled plugs in constricted channels are compared to modulated-voltage-generated plugs in straight channels showing that this technique provides significantly enhanced reproducibility and control over the size and spacing between the plugs. This work paves the way to sub-millimeter liquid metal plugs generated directly on-chip for on-demand MEMS and microfluidic applications.

Multiphoton microfabrication and micropatternining (MMM)-based screening of multiplex cell niche factors for phenotype maintenance - Bovine nucleus pulposus cell as an example.

Upon monolayer cultures on flat and rigid plastic dishes, many cells de-differentiate and lose their native phenotype. Technologies able to identify and reconstitute the cell niche factors that best maintain the physiological cellular phenotype in cultures are critical. We have developed a multiphoton microfabrication and micropatterning (MMM) technology, a robust 3D micro-printing platform capable to fabricate protein microstructures and micropatterns with quantitative, spatial and independent control of the mechanical, topological and extracellular matrix properties. Here, using bovine nucleus pulposus cells (bNPCs) as an example, we aim to reconstitute a spectrum of individual cell niche factors (2 mechanical, 9 topological and 4 matrices) in vitro for multiplex cell niche factor screening, and fabricate the optimal combinations of a series of shortlisted cell niche factors that best maintain the bNPC phenotype. Among all factors screened, two topological (micropillar array; fiber-bead structure) and two matrix (laminin; vitronectin) factors were shortlisted and the combinatory cell niche factors reconstituted from the shortlisted factors were found to synergistically augmented the expression of selected bNPC phenotype markers (Col II, SNAP25 and Keratin 8) and maintained their morphology and phenotype. These optimal cell niches can be micro-printed on culture dishes for physiologically relevant cultures and contribute to biomimetic scaffold design for intervertebral disc tissue engineering.

3D Printing at Micro-Level: Laser-Induced Forward Transfer and Two-Photon Polymerization.

Laser-induced forward transfer (LIFT) and two-photon polymerization (TPP) have proven their abilities to produce 3D complex microstructures at an extraordinary level of sophistication. Indeed, LIFT and TPP have supported the vision of providing a whole functional laboratory at a scale that can fit in the palm of a hand. This is only possible due to the developments in manufacturing at micro- and nano-scales. In a short time, LIFT and TPP have gained popularity, from being a microfabrication innovation utilized by laser experts to become a valuable instrument in the hands of researchers and technologists performing in various research and development areas, such as electronics, medicine, and micro-fluidics. In comparison with conventional micro-manufacturing methods, LIFT and TPP can produce exceptional 3D components. To gain benefits from LIFT and TPP, in-detail comprehension of the process and the manufactured parts' mechanical-chemical characteristics is required. This review article discusses the 3D printing perspectives by LIFT and TPP. In the case of the LIFT technique, the principle, classification of derivative methods, the importance of flyer velocity and shock wave formation, printed materials, and their properties, as well as various applications, have been discussed. For TPP, involved mechanisms, the difference between TPP and single-photon polymerization, proximity effect, printing resolution, printed material properties, and different applications have been analyzed. Besides this, future research directions for the 3D printing community are reviewed and summarized.

Capillary-Force-Driven Self-Assembly of 4D-Printed Microstructures.

Capillary-force-driven self-assembly is emerging as a significant approach for the massive manufacture of advanced materials with novel wetting, adhesion, optical, mechanical, or electrical properties. However, academic value and practical applications of the self-assembly are greatly restricted because traditional micropillar self-assembly is always unidirectional. In this work, two-photon-lithography-based 4D microprinting is introduced to realize the reversible and bidirectional self-assembly of microstructures. With asymmetric crosslinking densities, the printed vertical microstructures can switch to a curved state with controlled thickness, curvature, and smooth morphology that are impossible to replicate by traditional 3D-printing technology. In different evaporating solvents, the 4D-printed microstructures can experience three states: (I) coalesce into clusters from original vertical states via traditional self-assembly, (II) remain curved, or (III) arbitrarily self-assemble (4D self-assembly) toward the curving directions. Compared to conventional approaches, this 4D self-assembly is distance-independent, which can generate varieties of assemblies with a yield as high as 100%. More importantly, the three states can be reversibly switched, allowing the development of many promising applications such as reversible micropatterns, switchable wetting, and dynamic actuation of microrobots, origami, and encapsulation.

3D Microprinting of Iron Platinum Nanoparticle-Based Magnetic Mobile Microrobots.

Wireless magnetic microrobots are envisioned to revolutionize minimally invasive medicine. While many promising medical magnetic microrobots are proposed, the ones using hard magnetic materials are not mostly biocompatible, and the ones using biocompatible soft magnetic nanoparticles are magnetically very weak and, therefore, difficult to actuate. Thus, biocompatible hard magnetic micro/nanomaterials are essential toward easy-to-actuate and clinically viable 3D medical microrobots. To fill such crucial gap, this study proposes ferromagnetic and biocompatible iron platinum (FePt) nanoparticle-based 3D microprinting of microrobots using the two-photon polymerization technique. A modified one-pot synthesis method is presented for producing FePt nanoparticles in large volumes and 3D printing of helical microswimmers made from biocompatible trimethy- lolpropane ethoxylate triacrylate (PETA) polymer with embedded FePt nanoparticles. The 30 µm long helical magnetic microswimmers are able to swim at speeds of over five body lengths per second at 200 Hz, making them the fastest helical swimmer in the tens of micrometer length scale at the corresponding low- magnitude actuation fields of 5-10 mT. It is also experimentally in vitro verified that the synthesized FePt nanoparticles are biocompatible. Thus, such 3D-printed microrobots are biocompatible and easy to actuate toward creating clinically viable future medical microrobots.

Biodegradable Defined Shaped Printed Polymer Microcapsules for Drug Delivery.

This work describes the preparation and characterization of printed biodegradable polymer (polylactic acid) capsules made in two different shapes: pyramid and rectangular capsules about 1 and 11 µm in size. Obtained core-shell capsules are described in terms of their morphology, loading efficiency, cargo release profile, cell cytotoxicity, and cell uptake. Both types of capsules showed monodisperse size and shape distribution and were found to provide sufficient stability to encapsulate small water-soluble molecules and to retain them for several days and ability for intracellular delivery. Capsules of 1 µm size can be internalized by HeLa cells without causing any toxicity effect. Printed capsules show unique characteristics compared with other drug delivery systems such as a wide range of possible cargoes, triggered release mechanism, and highly controllable shape and size.

Extended field-of-view ultrathin microendoscopes for high-resolution two-photon imaging with minimal invasiveness.

Imaging neuronal activity with high and homogeneous spatial resolution across the field-of-view (FOV) and limited invasiveness in deep brain regions is fundamental for the progress of neuroscience, yet is a major technical challenge. We achieved this goal by correcting optical aberrations in gradient index lens-based ultrathin (≤500 µm) microendoscopes using aspheric microlenses generated through 3D-microprinting. Corrected microendoscopes had extended FOV (eFOV) with homogeneous spatial resolution for two-photon fluorescence imaging and required no modification of the optical set-up. Synthetic calcium imaging data showed that, compared to uncorrected endoscopes, eFOV-microendoscopes led to improved signal-to-noise ratio and more precise evaluation of correlated neuronal activity. We experimentally validated these predictions in awake head-fixed mice. Moreover, using eFOV-microendoscopes we demonstrated cell-specific encoding of behavioral state-dependent information in distributed functional subnetworks in a primary somatosensory thalamic nucleus. eFOV-microendoscopes are, therefore, small-cross-section ready-to-use tools for deep two-photon functional imaging with unprecedentedly high and homogeneous spatial resolution.

Direct Femtosecond Laser Printing of Silk Fibroin Microstructures.

Fabrication of functional silk fibroin microstructures has extensive applications in biotechnology and photonics. Considerable progress has been made based on lithographic methods and self-assembly approaches. However, most methods require chemical modification of silk fibroin, which restricts the functionalities of the designed materials. At the same time, femtosecond laser-induced forward transfer (fs-LIFT) has been explored as a simple and attractive processing tool for microprinting of high-resolution structures. In this paper, we propose the use of LIFT with fs-pulses for creating high-resolution structures of regenerated silk fibroin (SF). Furthermore, upon adding Eu3+/Tb3+ complexes to SF, we have been able to demonstrate the printing by LIFT of luminescent SF structures with a resolution on the order of 2 µm and without material degradation. This approach provides a facile method for printing well-defined two-dimensional (2D) micropatterns of pure and functionalized SF, which can be used in a wide range of optical and biomedical applications.

3D Two-Photon Microprinting of Nanoporous Architectures.

A photoresist system for 3D two-photon microprinting is presented, which enables the printing of inherently nanoporous structures with mean pore sizes around 50 nm by means of self-organization on the nanoscale. A phase separation between polymerizable and chemically inert photoresist components leads to the formation of 3D co-continuous structures. Subsequent washing-out of the unpolymerized phase reveals the porous polymer structures. To characterize the volume properties of the printed structures, scanning electron microscopy images are recorded from ultramicrotome sections. In addition, the light-scattering properties of the 3D-printed material are analyzed. By adjusting the printing parameters, the porosity can be controlled during 3D printing. As an application example, a functioning miniaturized Ulbricht light-collection sphere is 3D printed and tested.

Multi-Electrode Array with a Planar Surface for Cell Patterning by Microprinting.

Multielectrode arrays (MEAs) are devices for non-invasive electrophysiological measurements of cell populations. This paper describes a novel fabrication method of MEAs with a fully planar surface. The surface of the insulation layer and the surface of the electrodes were on one plane; we named this device the planar MEA (pMEA). The main advantage of the pMEA is that it allows uniform contact between the pMEA surface and a substrate for positioning of microfluidic channels or microprinting of a cell adhesive layer. The fabrication of the pMEA is based on a low adhesive Au sacrificial peel-off layer. In divergence from conventional MEAs with recessed electrodes, the electrodes of the pMEA lead across the sloped edge of the insulation layer. To make this, the profile of the edge of the insulation layer was measured and the impedance of the planar electrodes was characterized. The impedance of the pMEA was comparable with the impedance of conventional MEA electrodes. The pMEA was tested for patterning HL-1 cells with a combination of imprinting fibronectin and coating by antifouling poly (l-lysine)-graft-poly(ethylene glycol) (PLL-g-PEG). The HL-1 cells remained patterned even at full confluency and presented spontaneous and synchronous beating activity.

Additive Manufacturing of Sub-Micron to Sub-mm Metal Structures with Hollow AFM Cantilevers.

We describe our force-controlled 3D printing method for layer-by-layer additive micromanufacturing (µAM) of metal microstructures. Hollow atomic force microscopy cantilevers are utilized to locally dispense metal ions in a standard 3-electrode electrochemical cell, enabling a confined electroplating reaction. The deflection feedback signal enables the live monitoring of the voxel growth and the consequent automation of the printing protocol in a layer-by-layer fashion for the fabrication of arbitrary-shaped geometries. In a second step, we investigated the effect of the free parameters (aperture diameter, applied pressure, and applied plating potential) on the voxel size, which enabled us to tune the voxel dimensions on-the-fly, as well as to produce objects spanning at least two orders of magnitude in each direction. As a concrete example, we printed two different replicas of Michelangelo's David. Copper was used as metal, but the process can in principle be extended to all metals that are macroscopically electroplated in a standard way.

Femtosecond Laser Microprinting of a Polymer Optical Fiber Interferometer for High-Sensitivity Temperature Measurement.

Femtosecond laser induced multi-photon polymerization technique can be applied to fabricate an ultracompact polymer optical fiber interferometer which was embedded in a section of hollow core fiber. The production of the photoresin, used in this work, is described. Such a device has been used for temperature measurement, due to its excellent thermal properties. Transmission spectrum, structural morphology, and temperature response of the polymer optical fiber interferometer are experimentally investigated. A high wavelength sensitivity of 6.5 nm/°C is achieved over a temperature range from 25 °C to 30 °C. The proposed polymer optical fiber interferometer exhibits high temperature sensitivity, excellent mechanical strength, and ultra-high integration. More complex fiber-integrated polymer function micro/nano structures produced by this technique may result in more applications in optical fiber communication and optical fiber sensors.

Easy Printing of High Viscous Microdots by Spontaneous Breakup of Thin Fibers.

Electrohydrodynamic jetting is emerging as a successful technique for printing inks with resolutions well beyond those offered by conventional inkjet printers. However, the variety of printable inks is still limited to those with relatively low viscosities (typically <20 mPa s) due to nozzle clogging problems. Here, we show the possibility of printing ordered microdots of high viscous inks such as poly(lactic-co-glycolic acid) (PLGA) by exploiting the spontaneous breakup of a thin fiber generated through nozzle-free pyro-electrospinning. The PLGA fiber is deposited onto a partially wetting surface, and the breakup is achieved simply by applying an appropriate thermal stimulation, which is able to induce polymer melting and hence a mechanism of surface area minimization due to the Plateau-Rayleigh instability. The results show that this technique is a good candidate for extending the printability at the microscale to high viscous inks, thus extending their applicability to additional applications, such as cell behavior under controlled morphological constraints.

Micropatterning of 3D Microenvironments for Living Biosensor Applications.

Micro-scale printing and patterning of living cells has multiple applications including tissue engineering, cell signaling assays, and the fabrication of cell-based biosensors. In this work, a molecular printing instrument, the Bioforce Nano eNabler, was modified to enable micron-scale -quill-pen based printing of mammalian cells in a 3D hyaluronan/gelatin based hydrogel. Specifically, photo-initiated -thiol-ene click chemistry was used to couple the thiol groups of thiolated hyaluronan/thiolated gelatin to the alkene groups of 4-arm polyethylene glycol (PEG)-norbornene molecules. Rapid photopolymerization enabled direct printing and controlled curing of living cells within the hydrogel matrix. The resulting hydrogels were biocompatible with human adipose-derived stem cells, NIH-3T3 cells, and mouse embryonic stem cells. The utility of this printing approach was also explored for cell-based biosensors. Micro-printed cells expressing a redox sensitive variant of the green fluorescent protein (roGFP-R12) showed a measurable fluorescent response to addition of oxidizing and then reducing agents. This work represents a novel approach to micron-scale cell patterning, and its potential for living, cell-based biosensors.