Metals by Micro-Scale Additive Manufacturing: Comparison of Microstructure and Mechanical Properties.

Many emerging applications in microscale engineering rely on the fabrication of 3D architectures in inorganic materials. Small-scale additive manufacturing (AM) aspires to provide flexible and facile access to these geometries. Yet, the synthesis of device-grade inorganic materials is still a key challenge toward the implementation of AM in microfabrication. Here, a comprehensive overview of the microstructural and mechanical properties of metals fabricated by most state-of-the-art AM methods that offer a spatial resolution ≤10 µm is presented. Standardized sets of samples are studied by cross-sectional electron microscopy, nanoindentation, and microcompression. It is shown that current microscale AM techniques synthesize metals with a wide range of microstructures and elastic and plastic properties, including materials of dense and crystalline microstructure with excellent mechanical properties that compare well to those of thin-film nanocrystalline materials. The large variation in materials' performance can be related to the individual microstructure, which in turn is coupled to the various physico-chemical principles exploited by the different printing methods. The study provides practical guidelines for users of small-scale additive methods and establishes a baseline for the future optimization of the properties of printed metallic objects-a significant step toward the potential establishment of AM techniques in microfabrication.

Light tunable plasmonic metasurfaces.

Self-assembled plasmonic metasurfaces are promising optical platforms to achieve accessible flat optics, due to their strong light-matter interaction, nanometer length scale precision, large area, light weight, and high-throughput fabrication. Here, using photothermal continuous wave laser lithography, we show the spectral and spatial tuning of metasurfaces comprised of a monolayer of ligand capped hexagonally packed gold nanospheres. To tune the spectral response of the metasurfaces, we show that by controlling the intensity of a laser focused onto the metasurface that the absorption peak can be reconfigured from the visible to near-infrared wavelength. The irreversible spectral tuning mechanism is attributed to photothermal modification of the surface morphology. Combining self-assembled metasurfaces with laser lithography, we demonstrate an optically thin (λ/42), spectrally selective plasmonic Fresnel zone plate. This work establishes a new pathway for creating flat, large area, frequency selective optical elements using self-assembled plasmonic metasurfaces and laser lithography.

Linear and nonlinear optical characterization of self-assembled, large-area gold nanosphere metasurfaces with sub-nanometer gaps: errata.

We correct a nomenclature error for the plasmon ruler equation used to fit the simulation data in Fig. 2(d) [Opt. Express24, 27360 (2016)].

Linear and nonlinear optical characterization of self-assembled, large-area gold nanosphere metasurfaces with sub-nanometer gaps.

We created centimeter-scale area metasurfaces consisting of a quasi-hexagonally close packed monolayer of gold nanospheres capped with alkanethiol ligands on glass substrates using a directed self-assembly approach. We experimentally characterized the morphology and the linear and nonlinear optical properties of metasurfaces. We show these metasurfaces, with interparticle gaps of 0.6 nm, are modeled well using a classical (without charge transfer) description. We find a large dispersion of linear refractive index, ranging from values less than vacuum, 0.87 at 600 nm, to Germanium-like values of 4.1 at 880 nm, determined using spectroscopic ellipsometry. Nonlinear optical characterization was carried out using femtosecond Z-scan and we observe saturation behavior of the nonlinear absorption (NLA) and nonlinear refraction (NLR). We find a negative NLR from these metasurfaces two orders of magnitude larger (n2,sat = -7.94x10-9 cm2/W at Isat,n2 = 0.43 GW/cm2) than previous reports on gold nanostructures at similar femtosecond time scales. We also find the magnitude of the NLA comparable to the largest values reported (ß2,sat = -0.90x105 cm/GW at Isat,ß2 = 0.34 GW/cm2). Precise knowledge of the index of refraction is of crucial importance for emerging dispersion engineering technologies. Furthermore, utilizing this directed self-assembly approach enables the nanometer scale resolution required to develop the unique optical response and simultaneously provides high-throughput for potential device realization.

Laser forward transfer using structured light.

A digital micromirror device (DMD) is used to spatially structure a 532 nm laser beam to print features spatially congruent to the laser spot in a laser-induced forward transfer (LIFT) process known as laser decal transfer (LDT). The DMD is a binary (on/off) spatial light modulator and its resolution, half-toning and beam shaping properties are studied using LDT of silver nanopaste layers. Edge-enhanced "checkerboard" beam profiles led to a ~30% decrease in the laser transfer fluence threshold (compared to a reference "checkerboard" profile) for a 20-pixel bitmap pattern and its resulting 10-µm square feature.

Spatially modulated laser pulses for printing electronics.

The use of a digital micromirror device (DMD) in laser-induced forward transfer (LIFT) is reviewed. Combining this technique with high-viscosity donor ink (silver nanopaste) results in laser-printed features that are highly congruent in shape and size to the incident laser beam spatial profile. The DMD empowers LIFT to become a highly parallel, rapidly reconfigurable direct-write technology. By adapting half-toning techniques to the DMD bitmap image, the laser transfer threshold fluence for 10 µm features can be reduced using an edge-enhanced beam profile. The integration of LIFT with this beam-shaping technique allows the printing of complex large-area patterns with a single laser pulse.

Fabrication of terahertz metamaterials by laser printing.

A laser printing technique was used to fabricate split-ring resonators (SRRs) on Si substrates for terahertz (THz) metamaterials and their resonance behavior evaluated by THz time-domain spectroscopy. The laser-printed Ag SRRs exhibited sharp edge definition and excellent thickness uniformity, which resulted in an electromagnetic response similar to that from identical Au SRR structures prepared by conventional photolithography. These results demonstrate that laser printing is a practical alternative to conventional photolithography for fabricating metamaterial structures at terahertz frequencies, since it allows their design to be easily modified and optimized.

ZnO Nanoparticle/Graphene Hybrid Photodetectors via Laser Fragmentation in Liquid.

By combining the enhanced photosensitive properties of zinc oxide nanoparticles and the excellent transport characteristics of graphene, UV-sensitive, solar-blind hybrid optoelectronic devices have been demonstrated. These hybrid devices offer high responsivity and gain, making them well suited for photodetector applications. Here, we report a hybrid ZnO nanoparticle/graphene phototransistor that exhibits a responsivity up to 4 × 104 AW-1 and gain of up to 1.3 × 105 with high UV wavelength selectivity. ZnO nanoparticles were synthesized by pulsed laser fragmentation in liquid to attain a simple, efficient, ligand-free method for nanoparticle fabrication. By combining simple fabrication processes with a promising device architecture, highly sensitive ZnO nanoparticle/graphene UV photodetectors were successfully demonstrated.

Nanosecond mid-infrared pulse generation via modulated thermal emissivity.

We demonstrate the generation of nanosecond mid-infrared pulses via fast modulation of thermal emissivity enabled by the absorption of visible pump pulses in unpatterned silicon and gallium arsenide. The free-carrier dynamics in these materials result in nanosecond-scale modulation of thermal emissivity, which leads to nanosecond pulsed thermal emission. To our knowledge, the nanosecond thermal-emissivity modulation in this work is three orders of magnitude faster than what has been previously demonstrated. We also indirectly observed subnanosecond thermal pulses from hot carriers in semiconductors. The experiments are well described by our multiphysics model. Our method of converting visible pulses into the mid infrared using modulated emissivity obeys different scaling laws and can have significant wavelength tunability compared to approaches based on conventional nonlinearities.

VO2-based switchable radiator for spacecraft thermal control.

Direct calorimetric measurements of a solid state passive switchable radiator for spacecraft thermal control have been performed in a simulated space environment. Dynamic emissivity control is provided by the thermochromic phase change in a multilayer VO2 thin film based resonant absorber. The measured radiated power difference between 300 K and 373 K was 480 W/m2 corresponding to a 7× difference in radiative cooling power. We present theoretical and experimental radiator values for both normal and hemispherical as well the optical properties of VO2 as determined via infrared spectroscopic ellipsometry.

A Novel Method for In Situ Electromechanical Characterization of Nanoscale Specimens.

Electrically assisted deformation (EAD) is increasingly being used to improve the formability of metals during processes such as sheet metal rolling and forging. Adoption of this technique is proceeding despite disagreement concerning the underlying mechanism responsible for EAD. The experimental procedure described herein enables a more explicit study compared to previous EAD research by removing thermal effects, which are responsible for disagreement in interpreting previous EAD results. Furthermore, as the procedure described here enables EAD observation in situ and in real time in a transmission electron microscope (TEM), it is superior to existing post-mortem methods that observe EAD effects post-test. Test samples consist of a single crystal copper (SCC) foil having a free-standing tensile test section of nanoscale thickness, fabricated using a combination of laser and ion beam milling. The SCC is mounted to an etched silicon base that provides mechanical support and electrical isolation while serving as a heat sink. Using this geometry, even at high current density (~3,500 A/mm2), the test section experiences a negligible temperature increase (<0.02 °C), thus eliminating Joule heating effects. Monitoring material deformation and identifying the corresponding changes to microstructures, e.g. dislocations, are accomplished by acquiring and analyzing a series of TEM images. Our sample preparation and in situ experiment procedures are robust and versatile as they can be readily utilized to test materials with different microstructures, e.g., single and polycrystalline copper.

Strain Effects in Epitaxial VO2 Thin Films on Columnar Buffer-Layer TiO2/Al2O3 Virtual Substrates.

Epitaxial VO2/TiO2 thin film heterostructures were grown on (100) (m-cut) Al2O3 substrates via pulsed laser deposition. We have demonstrated the ability to reduce the semiconductor-metal transition (SMT) temperature of VO2 to ∼44 °C while retaining a 4 order of magnitude SMT using the TiO2 buffer layer. A combination of electrical transport and X-ray diffraction reciprocal space mapping studies help examine the specific strain states of VO2/TiO2/Al2O3 heterostructures as a function of TiO2 film growth temperatures. Atomic force microscopy and transmission electron microscopy analyses show that the columnar microstructure present in TiO2 buffer films is responsible for the partially strained VO2 film behavior and subsequently favorable transport characteristics with a lower SMT temperature. Such findings are of crucial importance for both the technological implementation of the VO2 system, where reduction of its SMT temperature is widely sought, as well as the broader complex oxide community, where greater understanding of the evolution of microstructure, strain, and functional properties is a high priority.

Laser-induced Forward Transfer of Ag Nanopaste.

Over the past decade, there has been much development of non-lithographic methods(1-3) for printing metallic inks or other functional materials. Many of these processes such as inkjet(3) and laser-induced forward transfer (LIFT)(4) have become increasingly popular as interest in printable electronics and maskless patterning has grown. These additive manufacturing processes are inexpensive, environmentally friendly, and well suited for rapid prototyping, when compared to more traditional semiconductor processing techniques. While most direct-write processes are confined to two-dimensional structures and cannot handle materials with high viscosity (particularly inkjet), LIFT can transcend both constraints if performed properly. Congruent transfer of three dimensional pixels (called voxels), also referred to as laser decal transfer (LDT)(5-9), has recently been demonstrated with the LIFT technique using highly viscous Ag nanopastes to fabricate freestanding interconnects, complex voxel shapes, and high-aspect-ratio structures. In this paper, we demonstrate a simple yet versatile process for fabricating a variety of micro- and macroscale Ag structures. Structures include simple shapes for patterning electrical contacts, bridging and cantilever structures, high-aspect-ratio structures, and single-shot, large area transfers using a commercial digital micromirror device (DMD) chip.

Reconfigurable acquisition system with integrated optics for a portable flow cytometer.

Portable and inexpensive scientific instruments that are capable of performing point of care diagnostics are needed for applications such as disease detection and diagnosis in resource-poor settings, for water quality and food supply monitoring, and for biosurveillance activities in autonomous vehicles. In this paper, we describe the development of a compact flow cytometer built from three separate, customizable, and interchangeable modules. The instrument as configured in this work is being developed specifically for the detection of selected Centers for Disease Control (CDC) category B biothreat agents through a bead-based assay: E. coli O157:H7, Salmonella, Listeria, and Shigella. It has two-color excitation, three-color fluorescence and light scattering detection, embedded electronics, and capillary based flow. However, these attributes can be easily modified for other applications such as cluster of differentiation 4 (CD4) counting. Proof of concept is demonstrated through a 6-plex bead assay with the results compared to a commercially available benchtop-sized instrument.

Functionalization of indium tin oxide.

The preparation and functionalization of ITO surfaces has been studied using primarily X-ray photoemission spectroscopy and infrared reflection-absorption spectroscopy (IRRAS) and the reagents n-hexylamine and n-octyltrimethoxysilane (OTMS). Particular attention has been paid to characterization of the surfaces both before and after functionalization. Surfaces cleaned by ultraviolet (UV)/ozone treatment and subsequently exposed to room air have approximately 0.5-0.8 monolayers (ML) of adsorbed impurity C. Most is in the form of aliphatic species, but as much as one-half is partially oxidized and consists of C-OH, C-O-C, and/or >C=O groups. The coverage of these species can be reduced by cleaning in organic solvents prior to UV/ozone treatment. The OH coverage on the ITO surfaces studied here is relatively small (approximately 1.0 OH nm-2), based on the Si coverage after reaction with OTMS. A satellite feature in the O 1s XPS spectrum, often suggested to be a quantitative measure of adsorbed OH, receives a significant contribution from sources not directly related to hydroxylated ITO. n-Hexylamine adsorbs, at a saturation coverage of approximately 0.08 ML, via a Lewis acid-base interaction. The particular acid site has not been conclusively identified, but it is speculated that surface Sn sites may be involved. For OTMS, a saturation coverage of about 0.21 ML is found, and the C/Si atom ratios suggest that some displacement of preadsorbed organic impurities occurs during adsorption. The alkyl chain of adsorbed OTMS is disordered, with no preferred stereoisomer. However, the chain appears to lie mainly parallel to the surface with the plane defined by the terminal CH3-CH2-CH2- segment oriented essentially perpendicular to the surface.