Transferable Optical Enhancement Nanostructures by Gapless Stencil Lithography.

Optical spectroscopy techniques are central for the characterization of two-dimensional (2D) quantum materials. However, the reduced volume of atomically thin samples often results in a cross section that is far too low for conventional optical methods to produce measurable signals. In this work, we developed a scheme based on the stencil lithography technique to fabricate transferable optical enhancement nanostructures for Raman and photoluminescence spectroscopy. Equipped with this new nanofabrication technique, we designed and fabricated plasmonic nanostructures to tailor the interaction of few-layer materials with light. We demonstrate orders-of-magnitude increase in the Raman intensity of ultrathin flakes of 2D semiconductors and magnets as well as selective Purcell enhancement of quenched excitons in WSe2/MoS2 heterostructures. We provide evidence that the method is particularly effective for air-sensitive materials, as the transfer can be performed in situ. The fabrication technique can be generalized to enable a high degree of flexibility for functional photonic devices.

In Situ Dynamic Spectroscopic Ellipsometry Characterization of Cu-Ligated Mercaptoalkanoic Acid "Molecular" Ruler Multilayers.

Hybrid strategies that combine conventional top-down lithography with bottom-up molecular assembly are of interest for a range of applications including nanolithography and sensors. Interest in these strategies stems from the ability to create complex architectures over large areas with molecular-scale control and precision. The molecular-ruler process typifies this approach where the sequential layer-by-layer assembly of mercaptoalkanoic acid molecules and metal ions are combined with conventional top-down lithography to create precise, registered nanogaps. However, the quality of the metal-ligated mercaptoalkanoic acid multilayer is a critical characteristic in generating reproducible and robust nanoscale structures via the molecular-ruler process. Therefore, we explore the assembly of alkanethiolate monolayers, mercaptohexadecanoic acid (MHDA) monolayers, and Cu-ligated MHDA multilayers on Au{111} substrates using atomic force microscopy and in situ dynamic spectroscopic ellipsometry. The chemical film thicknesses in situ dynamic spectroscopic ellipsometry agree with previous ex situ surface analytical methods. Moreover, in situ dynamic spectroscopic ellipsometry provides insight into the assembly process without interrupting the assembly process and potentially altering the characteristics of the resulting chemical film. By following the real-time dynamics of each deposition step, the assembly of the Cu-ligated MHDA multilayers can be optimized to minimize deposition time while having minimal impact to the quality of the chemical film.

Ultrafast Laser 3D Nanolithography of Fiber-Integrated Silica Microdevices.

Fiber-integrated micro/nanostructures play a crucial role in modern industry, mainly owing to their compact size, high sensitivity, and resistance to electromagnetic interference. However, the three-dimensional manufacturing of fiber-tip functional structures beyond organic polymers remains challenging. It is essential to construct fiber-integrated inorganic silica with designed functional nanostructures for microsystem applications. Here, we develop a strategy for the 3D nanolithography of fiber-integrated silica from hybrid organic-inorganic materials by ultrafast laser-induced multiphoton absorption. Without silica nanoparticles and polymer additives, the acrylate-functionalized precursors can be locally cross-linked through a nonlinear effect. Followed by annealing at low temperature, the as-printed micro/nanostructures are transformed to high-quality silica with sub-100 nm resolution. Silica microcantilever probes and microtoroid resonators are directly integrated onto the optical fiber, showing strong thermal stability and quality factors. This work provides a promising strategy for fabricating desired fiber-tip silica micro/nanostructures, which is helpful for the development of integrated functional device applications.

Template-assisted growth of Ga-based nanoparticle clusters on Si: effect of post-annealing process on the Ga ion beam exposed 2D arrays fabricated by focused ion beam nanolithography.

We demonstrate template-assisted growth of gallium-based nanoparticle clusters on silicon substrate using a focused ion beam (FIB) nanolithography technique. The nanolithography counterpart of the technique steers a focussed 30 kV accelerated gallium ion beam on the surface of Si to create template patterns of two-dimensional dot arrays. Growth of the nanoparticles is governed by two vital steps namely implantation of gallium into the substrate via gallium beam exposure and formation of the stable nanoparticles on the surface of the substrate by subsequent annealing at elevated temperature in ammonia atmosphere. The growth primarily depends on the dose of implanted gallium which is in the order of 107atoms per spot and it is also critically influenced by the temperature and duration of the post-annealing treatment. By controlling the growth parameters, it is possible to obtain one particle per spot and particle densities as high as 109particles per square centimetre could be achieved in this case. The demonstrated growth process, utilizing the advantages of FIB nanolithography, is categorized under the guided organization approach as it combines both the classical top-down and bottom-up approaches. Patterned growth of the particles could be utilized as templates or nucleation sites for the growth of an organized array of nanostructures or quantum dot structures.

X-Ray Multibeam Ptychography at up to 20 keV: Nano-Lithography Enhances X-Ray Nano-Imaging.

Hard X-rays are needed for non-destructive nano-imaging of solid matter. Synchrotron radiation facilities (SRF) provide the highest-quality images with single-digit nm resolution using advanced techniques such as X-ray ptychography. However, the resolution or field of view is ultimately constrained by the available coherent flux. To address this, the beam's incoherent fraction can be exploited using multiple parallel beams in an X-ray multibeam ptychography (MBP) approach. This expands the domain of X-ray ptychography to larger samples or more rapid measurements. Both qualities favor the study of complex composite or functional samples, such as catalysts, energy materials, or electronic devices. The challenge of performing ptychography at high energy and with many parallel beams must be overcome to extract the full advantages for extended samples while minimizing beam attenuation. Here, that challenge is overcome by creating a lens array using cutting-edge laser printing technology and applying it to perform scanning with MBP with up to 12 beams and at photon energies of 13 and 20 keV. This exceeds the measurement limits of conventional hard X-ray ptychography without compromising image quality for various samples: Siemens star test pattern, Ni/Al2O3 catalyst, microchip, and gold nano-crystal clusters.

A Multifunctional Nanostructured Hydrogel as a Platform for Deciphering Niche Interactions of Hematopoietic Stem and Progenitor Cells.

For over half a century, hematopoietic stem cells (HSCs) have been used for transplantation therapy to treat severe hematologic diseases. Successful outcomes depend on collecting sufficient donor HSCs as well as ensuring efficient engraftment. These processes are influenced by dynamic interactions of HSCs with the bone marrow niche, which can be revealed by artificial niche models. Here, a multifunctional nanostructured hydrogel is presented as a 2D platform to investigate how the interdependencies of cytokine binding and nanopatterned adhesive ligands influence the behavior of human hematopoietic stem and progenitor cells (HSPCs). The results indicate that the degree of HSPC polarization and motility, observed when cultured on gels presenting the chemokine SDF-1α and a nanoscale-defined density of a cellular (IDSP) or extracellular matrix (LDV) α4ß1 integrin binding motif, are differently influenced on hydrogels functionalized with the different ligand types. Further, SDF-1α promotes cell polarization but not motility. Strikingly, the degree of differentiation correlates negatively with the nanoparticle spacing, which determines ligand density, but only for the cellular-derived IDSP motif. This mechanism potentially offers a means of predictably regulating early HSC fate decisions. Consequently, the innovative multifunctional hydrogel holds promise for deciphering dynamic HSPC-niche interactions and refining transplantation therapy protocols.

Membrane Fluctuation Model for Understanding the Effect of Receptor Nanoclustering on the Activation of Natural Killer Cells through Biomechanical Feedback.

We investigated the role of ligand clustering and density in the activation of natural killer (NK) cells. To that end, we designed reductionist arrays of nanopatterned ligands arranged with different cluster geometries and densities and probed their effects on NK cell activation. We used these arrays as an artificial microenvironment for the stimulation of NK cells and studied the effect of the array geometry on the NK cell immune response. We found that ligand density significantly regulated NK cell activation while ligand clustering had an impact only at a specific density threshold. We also rationalized these findings by introducing a theoretical membrane fluctuation model that considers biomechanical feedback between ligand-receptor bonds and the cell membrane. These findings provide important insight into NK cell mechanobiology, which is fundamentally important and essential for designing immunotherapeutic strategies targeting cancer.

Tip-based Lithography with a Sacrificial Layer.

The fabrication of a highly controlled gold (Au) nanohole (NH) array via tip-based lithography is improved by incorporating a sacrificial layer-a tip-crash buffer layer. This inclusion mitigates scratches during the nano-indentation process by employing a 300 nm thick poly(methyl methacrylate) layer as a sacrificial layer on top of the Au film. Such a precaution ensures minimal scratches on the Au film, facilitating the creation of sub-50 nm Au NHs with a 15 nm gap between the Au NHs. The precision of this method exceeds that of fabricating Au NHs without a sacrificial layer. Demonstrating its versatility, this Au NH array is utilized in two distinct applications: as a dry etching mask to form a molybdenum disulfide hole array and as a catalyst in metal-assisted chemical etching, resulting in conical-shaped silicon nanostructures. Additionally, a significant electric field is generated when Au nanoparticles (NPs) are placed within the Au NHs. This effect arises from coupling electromagnetic waves, concentrated by the Au NHs and amplified by the Au NPs. A notable result of this configuration is the enhancement factor of surface-enhanced Raman scattering, which is an order of magnitude greater than that observed with just Au NHs and Au NPs alone.

Exploring the Surface Oxidation and Environmental Instability of 2H-/1T'-MoTe2 Using Field Emission-Based Scanning Probe Lithography.

An unconventional approach for the resistless nanopatterning 2H- and 1T'-MoTe2 by means of scanning probe lithography is presented. A Fowler-Nordheim tunneling current of low energetic electrons (E = 30-60 eV) emitted from the tip of an atomic force microscopy (AFM) cantilever is utilized to induce a nanoscale oxidation on a MoTe2 nanosheet surface under ambient conditions. Due to the water solubility of the generated oxide, a direct pattern transfer into the MoTe2 surface can be achieved by a simple immersion of the sample in deionized water. The tip-grown oxide is characterized using Auger electron and Raman spectroscopy, revealing it consists of amorphous MoO3 /MoOx as well as TeO2 /TeOx . With the presented technology in combination with subsequent AFM imaging it is possible to demonstrate a strong anisotropic sensitivity of 1T'-/(Td )-MoTe2 to aqueous environments. Finally the discussed approach is used to structure a nanoribbon field effect transistor out of a few-layer 2H-MoTe2 nanosheet.

Massively Scalable Self-Assembly of Nano and Microparticle Monolayers via Aerosol Assisted Deposition.

An extremely rapid process for self-assembling well-ordered, nano, and microparticle monolayers via a novel aerosolized method is presented. The novel technique can reach monolayer self-assembly rates as high as 268 cm2 min-1 from a single aerosolizing source and methods to reach faster monolayer self-assembly rates are outlined. A new physical mechanism describing the self-assembly process is presented and new insights enabling high-efficiency nanoparticle monolayer self-assembly are developed. In addition, well-ordered monolayer arrays from particles of various sizes, surface functionality, and materials are fabricated. This new technique enables a 93× increase in monolayer self-assembly rates compared to the current state of the art and has the potential to provide an extremely low-cost option for submicron nanomanufacturing.

Forty-Nanometer Plasmonic Lithography Resolution with Two-Stage Bowtie Lens.

Optical imaging and photolithography hold the promise of extensive applications in the branch of nano-electronics, metrology, and the intricate domain of single-molecule biology. Nonetheless, the phenomenon of light diffraction imposes a foundational constraint upon optical resolution, thus presenting a significant barrier to the downscaling aspirations of nanoscale fabrication. The strategic utilization of surface plasmons has emerged as an avenue to overcome this diffraction-limit problem, leveraging their inherent wavelengths. In this study, we designed a pioneering and two-staged resolution, by adeptly compressing optical energy at profound sub-wavelength dimensions, achieved through the combination of propagating surface plasmons (PSPs) and localized surface plasmons (LSPs). By synergistically combining this plasmonic lens with parallel patterning technology, this economic framework not only improves the throughput capabilities of prevalent photolithography but also serves as an innovative pathway towards the next generation of semiconductor fabrication.

Replicated biopolymer pattern on PLLA-Ag basis with an excellent antibacterial response.

The design of functional micro or nanostructured surfaces is undergoing extensive research for their intriguing multifunctional properties and for large variety of potential applications in biomedical field (tissue engineering or cell adhesion), electronics, optics or microfluidics. Such nanosized topographies can be easily fabricated by various lithography techniques and can be also further reinforced by synergic effect by combining aforementioned structures along materials with already outstanding antibacterial properties. In this work we fabricated novel micro/nanostructured substrates using soft lithography replication method and subsequent thermal nanoimprint lithography method, creating nanostructured films based on poly (l-lactic acid) (PLLA) fortified by thin silver films deposited by PVD. Main nanoscale patterns were fabricated by replicating surface patterns of optical discs (CDs and DVDs), which proved to be easy, fast and inexpensive method for creating relatively large area patterned surfaces. Their antimicrobial activity was examined in vitro against the bacteria Escherichia coli and Staphylococcus epidermidis strains. The results demonstrated that nanopatterned films actually improved the conditions for bacterial growth compared to pristine PLLA films, the novelty is based on formation of Ag nanoparticles on the surface/and in bulk, while silver nanoparticle enhanced and nanopatterned films exhibited excellent antibacterial activity against both bacterial strains, with circa 80 % efficacy in 4 h and complete bactericidal effect in span of 24 h.

Modeling the co-assembly of binary nanoparticles.

In this work, we present a binary assembly model that can predict the co-assembly structure and spatial frequency spectra of monodispersed nanoparticles with two different particle sizes. The approach relies on an iterative algorithm based on geometric constraints, which can simulate the assembly patterns of particles with two distinct diameters, size distributions, and at various mixture ratios on a planar surface. The two-dimensional spatial-frequency spectra of the modeled assembles can be analyzed using fast Fourier transform analysis to examine their frequency content. The simulated co-assembly structures and spectra are compared with assembled nanoparticles fabricated using transfer coating method are in qualitative agreement with the experimental results. The co-assembly model can also be used to predict the peak spatial frequency and the full-width at half-maximum bandwidth, which can lead to the design of the structure spectra by selection of different monodispersed particles. This work can find applications in fabrication of non-periodic nanostructures for functional surfaces, light extraction structures, and broadband nanophotonics.

Calligraphy of Nanoplasmonic Bioink-Based Multiplex Immunosensor for Precision Immune Monitoring and Modulation.

Immunomodulation therapies have attracted immense interest recently for the treatment of immune-related diseases, such as cancer and viral infections. This new wave of enthusiasm for immunomodulators, predominantly revolving around cytokines, has spurred emerging needs and opportunities for novel immune monitoring and diagnostic tools. Considering the highly dynamic immune status and limited window for therapeutic intervention, precise real-time detection of cytokines is critical to effectively monitor and manage the immune system and optimize the therapeutic outcome. The clinical success of such a rapid, sensitive, multiplex immunoanalytical platform further requires the system to have ease of integration and fabrication for sample sparing and large-scale production toward massive parallel analysis. In this article, we developed a nanoplasmonic bioink-based, label-free, multiplex immunosensor that can be readily "written" onto a glass substrate via one-step calligraphy patterning. This facile nanolithography technique allows programmable patterning of a minimum of 3 µL of nanoplasmonic bioink in 1 min and thus enables fabrication of a nanoplasmonic microarray immunosensor with 2 h simple incubation. The developed immunosensor was successfully applied for real-time, parallel detection of multiple cytokines (e.g., interleukin-6 (IL-6), tumor necrosis factor-alpha (TNF-α), and transforming growth factor-beta (TGF-ß)) in immunomodulated macrophage samples. This integrated platform synergistically incorporates the concepts of nanosynthesis, nanofabrication, and nanobiosensing, showing great potential in the scalable production of label-free multiplex immunosensing devices with superior analytical performance for clinical applications in immunodiagnostics and immunotherapy.

Colloidal Quantum Dot Nanolithography: Direct Patterning via Electron Beam Lithography.

Micro/nano patterns based on quantum dots (QDs) are of great interest for applications ranging from electronics to photonics to sensing devices for biomedical purposes. Several patterning methods have been developed, but all lack the precision and reproducibility required to fabricate precise, complex patterns of less than one micrometer in size, or require specialized crosslinking ligands, limiting their application. In this study, we present a novel approach to directly pattern QD nanopatterns by electron beam lithography using commercially available colloidal QDs without additional modifications. We have successfully generated reliable dot and line QD patterns with dimensions as small as 140 nm. In addition, we have shown that using a 10 nm SiO2 spacer layer on a 50 nm Au layer substrate can double the fluorescence intensity compared to QDs on the Au layer without SiO2. This method takes advantage of traditional nanolithography without the need for a resist layer.

Quantitative nanopatterning of fg-scale liquids with dip-pen nanolithography.

The ability to precisely pattern nanoscale amounts of liquids is essential for biotechnology and high-throughput chemistry, but controlling fluid flow on these scales is very challenging. Scanning probe lithography methods such as dip-pen nanolithography (DPN) provide a mechanism to write fluids at the nanoscale, but this is an open loop process as methods to provide feedback while patterning sub-pg features have yet to be reported. Here, we demonstrate a novel method for programmably nanopatterning liquid features at the fg-scale through a combination of ultrafast atomic force microscopy probes, the use of spherical tips, and inertial mass sensing. We begin by investigating the required probe properties that would provide sufficient mass responsivity to detect fg-scale mass changes and find ultrafast probes to be capable of this resolution. Further, we attach a spherical bead to the tip of an ultrafast probe as we hypothesize that the spherical tip could hold a drop at its apex which both facilitates interpretation of inertial sensing and maintains a consistent fluid environment for reliable patterning. We experimentally find that sphere-tipped ultrafast probes are capable of reliably patterning hundreds of features in a single experiment. Analyzing the changes in the vibrational resonance frequency during the patterning process, we find that drift in the resonance frequency complicates analysis, but that it can be removed through a systematic correction. Subsequently, we quantitatively study patterning using sphere-tipped ultrafast probes as a function of retraction speed and dwell time to find that the mass of fluid transferred can be modulated by greater than an order of magnitude and that liquid features as small as 6 fg can be patterned and resolved. Taken together, this work addresses a persistent concern in DPN by enabling quantitative feedback for nanopatterning of aL-scale features and lays the foundation for programmably nanopatterning fluids.

Approaches for Memristive Structures Using Scratching Probe Nanolithography: Towards Neuromorphic Applications.

This paper proposes two different approaches to studying resistive switching of oxide thin films using scratching probe nanolithography of atomic force microscopy (AFM). These approaches allow us to assess the effects of memristor size and top-contact thickness on resistive switching. For that purpose, we investigated scratching probe nanolithography regimes using the Taguchi method, which is known as a reliable method for improving the reliability of the result. The AFM parameters, including normal load, scratch distance, probe speed, and probe direction, are optimized on the photoresist thin film by the Taguchi method. As a result, the pinholes with diameter ranged from 25.4 ± 2.2 nm to 85.1 ± 6.3 nm, and the groove array with a depth of 40.5 ± 3.7 nm and a roughness at the bottom of less than a few nanometers was formed. Then, based on the Si/TiN/ZnO/photoresist structures, we fabricated and investigated memristors with different spot sizes and TiN top contact thickness. As a result, the HRS/LRS ratio, USET, and ILRS are well controlled for a memristor size from 27 nm to 83 nm and ranged from ~8 to ~128, from 1.4 ± 0.1 V to 1.8 ± 0.2 V, and from (1.7 ± 0.2) × 10-10 A to (4.2 ± 0.6) × 10-9 A, respectively. Furthermore, the HRS/LRS ratio and USET are well controlled at a TiN top contact thickness from 8.3 ± 1.1 nm to 32.4 ± 4.2 nm and ranged from ~22 to ~188 and from 1.15 ± 0.05 V to 1.62 ± 0.06 V, respectively. The results can be used in the engineering and manufacturing of memristive structures for neuromorphic applications of brain-inspired artificial intelligence systems.

Fabrication of Nanoscale Arrays to Study the Effect of Ligand Arrangement on Inhibitory Signaling in NK Cells.

Molecular scale nanopatterns of bioactive molecules have been used to study the effect of transmembrane receptor arrangement on a variety of cell types, including immune cells and their immune response in particular. However, state-of-the-art fabrication approaches have thus far enabled the production of patterns with control over one receptor type only. Herein, we describe a protocol to fabricate arrays for the molecular scale control of the segregation between activating and inhibitory receptors in NK cells. We used this platform to study how ligand segregation regulates NK cell inhibitory signaling and function. The arrays are based on patterns of nanodots of two metals, selectively functionalized with activating and inhibitory ligands. Due to the versatility of our functionalization approach, this protocol can be applied to configurate virtually any combination of extracellular ligands into controlled multifunctional arrays.

Morphology Engineering in Multicomponent Hollow Metal Chalcogenide Nanoparticles.

Hollow metal chalcogenide nanoparticles are widely applicable in environmental and energy-related processes. Herein, we synthesized such particles with large compositional and morphological diversity by combining scanning probe block copolymer lithography with a Kirkendall effect-based sulfidation process. We explored the influence of temperature-dependent diffusion kinetics, elemental composition and miscibility, and phase boundaries on the resulting particle morphologies. Specifically, CoNi alloys form single-shell sulfides for the synthetic conditions explored because Co and Ni exhibit similar diffusion rates, while CuNi alloys form sulfides with various types of morphologies (yolk-shell, double-shell, and single-shell) because Cu and Ni have different diffusion rates. In contrast, Co-Cu heterodimers form hollow heterostructured sulfides with varying void numbers and locations depending on synthesis temperature and phase boundary. At higher temperatures, the increased miscibility of CoS2 and CuS makes it energetically favorable for the heterostructure to adopt a single alloy shell morphology, which is rationalized using density functional theory-based calculations.

Patterning of Hydrophilic and Hydrophobic Gold and Magnetite Nanoparticles by Dip Pen Nanolithography.

Nanoparticles offer unique physical and chemical properties. Dip pen nanolithography of nanoparticles enables versatile patterning and nanofabrication with potential application in electronics and sensing, but is not well studied yet. Herein, the patterned deposition of various nanoparticles onto unmodified silicon substrates is presented. It is shown that aqueous solutions of hydrophilic citrate and cyclodextrin functionalized gold nanoparticles as well as poly(acrylic) acid decorated magnetite nanoparticles are feasible for writing nanostructures. Both smaller and larger nanoparticles can be patterned. Hydrophobic oleylamine or n-dodecylamine capped gold nanoparticles and oleic acid decorated magnetite nanoparticles are deposited from toluene. Tip loading is carried out by dip-coating, and writing succeeds fast within 0.1 s. Also, coating with longer tip dwell times, at different relative humidity and varying frequency are studied for deposition of nanoparticle clusters. The resulting feature size is between 300 and 1780 nm as determined by scanning electron microscopy. Atomic force microscopy confirms that the heights of the deposited structures correspond to a single or double layer of nanoparticles. Higher writing speeds lead to smaller line thicknesses, offering possibilities to more complex structures. Dip pen nanolithography can hence be used to pattern nanoparticles on silicon substrates independent of the surface chemistry.