Colloidal Lithography Technique Research Articles

Large-Scale Formation of a Close-Packed Monolayer of Spheres Using Different Colloidal Lithography Techniques.

The possibility of using colloidal lithography at the industrial level depends on the ability to form defect-free coatings over large areas. The spin-coating method has not yet shown acceptable results, but a more detailed studying of the regularities of this process may improve the quality of masks. The Langmuir-Blodgett method is expected to be the most preferable for forming high-quality large-scale monolayers. Real-time controlling the surface pressure of the monolayer can allow to obtain close-packed arrays with long-range order. In this work, to develop the spin-coating technology, the influence of technological parameters (spin-coating speed and time, concentrations of components in suspension) on the substrate coverage area with a monolayer of polystyrene spheres (1.25 μm) was studied. An original automated Langmuir-Blodgett system was developed to study the influence of the monolayer surface pressure on its quality using polystyrene spheres (1.25, 1.8, 2.1 μm). The developed spin-coating technology resulted in a record coverage area (90%) of Si substrate (76 mm) and a defect-free hexagonally ordered domain area of 500 μm2. As a result of the developed Langmuir-Blodgett technique, a close-packed monolayer coating was obtained over the entire substrate area (coverage area 99.5%, defect-free domain area 3000 μm2) without the use of any surfactants.

Accessible Double Nanohole Raman Tweezer Analysis of Single Nanoparticles.

Raman spectroscopy allows for material characterization of nanoparticles; however, probing individual nanoparticles requires an efficient way of isolating and enhancing the signal. Past works have used optical trapping with nanoapertures in metal films to measure the Raman spectra of individual nanoparticles; however, those works required custom laser tweezer systems that provided a transmission signal to verify trapping events as well as costly top-down nanofabrication. Here, we trapped Titania nanoparticles in a commercial Raman system using double nanoholes (DNH) and measured their spectra while trapped. The microscope camera allowed for measuring the trapping event in reflection mode, and a simultaneous Raman spectrum was recorded to allow for material characterization. The Raman signal was comparable to a past work that used particles a million times larger in volume without utilizing double nanoholes, and all other features were similar. The DNHs were created with a colloidal lithography technique and identified in the microscope, as confirmed by electron microscopy registration. Therefore, this approach allows a simple way of characterizing the Raman signal of individual nanoparticles while in solution by using existing commercial Raman systems.

Unlocking Predictive Capability and Enhancing Sensing Performances of Plasmonic Hydrogen Sensors via Phase Space Reconstruction and Convolutional Neural Networks.

This study innovates plasmonic hydrogen sensors (PHSs) by applying phase space reconstruction (PSR) and convolutional neural networks (CNNs), overcoming previous predictive and sensing limitations. Utilizing a low-cost and efficient colloidal lithography technique, palladium nanocap arrays are created and their spectral signals are transformed into images using PSR and then trained using CNNs for predicting the hydrogen level. The model achieves accurate predictions with average accuracies of 0.95 for pure hydrogen and 0.97 for mixed gases. Performance improvements observed are a reduction in response time by up to 3.7 times (average 2.1 times) across pressures, SNR increased by up to 9.3 times (average 3.9 times) across pressures, and LOD decreased from 16 Pa to an extrapolated 3 Pa, a 5.3-fold improvement. A practical application of remote hydrogen sensing without electronics in hydrogen environments is actualized and achieves a 0.98 average test accuracy. This methodology reimagines PHS capabilities, facilitating advancements in hydrogen monitoring technologies and intelligent spectrum-based sensing.

Plasmonic Nanopyramid Array Enhancing Luminescence of MoS2 Investigated by Cathodoluminescence

AbstractTransition metal dichalcogenides (TMDs) like molybdenum disulfide (MoS2) have unique optical properties such as strong luminescence and a tunable bandgap. However, the small interaction distance due to the atomically thin nature of these materials is a limitation for applications. In this study, a significant enhancement of the A‐ and B‐exciton emission in MoS2 flakes through coupling with plasmonic Au nano‐pyramid arrays fabricated by a colloidal lithography technique is reported. This study experimentally maps local emission enhancement from the structure with a nanometer spatial resolution by cathodoluminescence (CL) technique. Strongly enhanced emission intensity within the MoS2‐Au pyramids is achieved due to the localized surface plasmon resonance confined in nano‐pyramids and its interaction with the periodicity‐based resonance of the array structure. The results provide an approach to significantly improve the luminescence intensity of MoS2 through optical interaction with the local plasmonic field, which is promising for applications in optoelectronic devices and nanophotonics.

Correlated Disorder Substrate‐Integrated Nanodisk Scatterers for Light Extraction in Organic Light Emitting Diodes

AbstractA major loss mechanism in organic light emitting diodes (OLEDs) is the coupling of the emitter molecule light field to waveguide modes in the OLED thin film stack. In this work, a disordered 2D array of TiO2 nanodisk scatterers is integrated into the OLED substrate to enable efficient light extraction from these waveguide modes. Fabrication of the nanodisks is based on a bottom‐up, colloidal lithography technique and subsequent pattern transfer into high refractive index TiO2 via reactive ion etching. The substrates are completed by spin‐coating a polymer planarization layer before applying the OLED thin film stack. This ensures reproducible optoelectronic properties of the OLED through leaving the electrically active layers planar. Simultaneously, the nanodisks in close vicinity to the thin film stack ensure efficient out‐of‐plane scattering of waveguide modes. In a monochromatic OLED (center wavelength λ0 = 520 nm), a 44.2%rel increase in external quantum efficiency is achieved in comparison to a device without scattering structure. An in‐depth numerical analysis reveals that this significant enhancement is only partly due to the out‐coupling of waveguide modes. Additional enhancement is suspected to result from out‐coupling of substrate modes through scattering by the nanodisks. Further improvements to the scattering structure are numerically evaluated.

Enhancement of upconversion photoluminescence in phosphor nanoparticle thin films using metallic nanoantennas fabricated by colloidal lithography.

Lanthanide-doped upconversion nanoparticles (UCNPs), as multifunctional light sources, are finding utility in diverse applications ranging from biotechnology to light harvesting. However, the main challenge in realizing their full potential lies in achieving bright and efficient photon upconversion (UC). In this study, we present a novel approach to fabricate an array of gold nanoantennas arranged in a hexagonal lattice using a simple and inexpensive colloidal lithography technique, and demonstrate a significant enhancement of UC photoluminescence (UCPL) by up to 35-fold through plasmon-enhanced photoexcitation and emission. To elucidate the underlying physical mechanisms responsible for the observed UCPL enhancement, we provide a comprehensive theoretical and experimental characterization, including a detailed photophysical description and numerical simulations of the spatial electric field distribution. Our results shed light on the fundamental principles governing the enhanced UCNPs and pave the way for their potential applications in photonic devices.

Plasmonic Sensor and Surface Enhanced Fluorescence Imaging Based on Hollow Nanocone Arrays

Hollow nanocone arrays are fabricated by a low-cost and efficient colloidal lithography (CL) technique. The hollow nanocone arrays are then reversed to make only the tips contact the substrate. The optical properties of the obverse and inverse hollow nanocone arrays are determined by the surrounding environment, showing different reflection spectra and structure dependence. The inverse hollow nanocone arrays show a relative index sensitivity of 70% per RIU with strict linearity. The fluorescence of fluorophore or staining cells can be facilely enhanced by placing them on the tips of the hollow nanocone arrays, while having no quenching effect. The study of the obverse and inverse hollow nanocone arrays can benefit the understanding of the effect of the environment on the plasmonic resonances. The hollow nanocone arrays are promising to serve as high-performance plasmonic sensors and versatile substrates for surface-enhanced fluorescence imaging.

Probing ND7/23 neuronal cells before and after differentiation with SERS using Sharp-tipped Au nanopyramid arrays

The development of local plasmonic nano sensors which are sensitive, whilst remaining non-invasive with high cell viability is challenging but of great interest for the investigation of cellular processes. With this aim, we developed an effective SERS active biointerface to monitor cell activity and discriminate between undifferentiated and differentiated neurons through principal component analysis. We propose a plasmonic tipped Au nanopyramids (Au NPs) array, which benefits from high aspect ratios and sharp tips that are excellent SERS sensors. To realise the structure, we developed a large-scale inexpensive fabrication route based on the assembly of charged nanospheres used as a mask by means of a colloidal lithography technique, to better space and shape the NPs. Here we show that Au NPs with tip curvatures of 10 nm and localized plasmon resonance at 785 nm can non-destructively probe ND7/23 neurons. We prove that these tips allow us to track ND7/23 neurons on the SERS substrate, detecting both the membrane constituents, proteins and lipids, and even intracellular DNA/RNA fragments.

Recyclable SERS substrate: Optimised by reducing masking effect through colloidal lithography

Surface-enhanced Raman spectroscopy (SERS) has attracted much attention as it can deliver “fingerprint” type selectivity and detect organic compounds and other analytes down to single molecules. Conventional methods to produce reliable SERS sensors require high cost and control in the morphology and topology of the sensors. The lack of recyclability makes these high-cost sensors one-time use only. In this research, we have employed unconventional colloidal lithography techniques to develop a reliable and reproducible SERS sensor with self-cleaning capabilities. The sensor is developed via chemical vapour deposition of titania (TiO2) on 2D colloidal crystal monolayers to form Long-Range Ordered Crystals (LROCs) followed by controlled electroless deposition of silver nanoparticles. The fabricated surfaces are highly ordered and reproducible and the topology of the surface is uniform across the surface due to the seamless formation of TiO2/Ag LROCs. The developed sensors have shown self–cleaning properties from their TiO2 based layers and the formation of Schottky heterojunction between TiO2 sublayers and decorated Ag nanoparticles. Thus, the developed sensors show high sensitivity as well as recyclability enabling these sensors to perform multicycle measurements.

The effects of controlled nanotopography, machined topography and their combination on molecular activities, bone formation and biomechanical stability during osseointegration

The initial cellular and molecular activities at the bone interface of implants with controlled nanoscale topography and microscale roughness have previously been reported. However, the effects of such surface modifications on the development of osseointegration have not yet been determined. This study investigated the molecular events and the histological and biomechanical development of the bone interface in implants with nanoscale topography, microscale roughness or a combination of both. Polished and machined titanium implants with and without controlled nanopatterning (75 nm protrusions) were produced using colloidal lithography and coated with a thin titanium layer to unify the chemistry. The implants were inserted in rat tibiae and subjected to removal torque (RTQ) measurements, molecular analyses and histological analyses after 6, 21 and 28 days. The results showed that nanotopography superimposed on microrough, machined, surfaces promoted an early increase in RTQ and hence produced greater implant stability at 6 and 21 days. Two-way MANOVA revealed that the increased RTQ was influenced by microscale roughness and the combination of nanoscale and microscale topographies. Furthermore, increased bone-implant contact (BIC) was observed with the combined nanopatterned machined surface, although MANOVA results implied that the increased BIC was mainly dependent on microscale roughness. At the molecular level, the nanotopography, per se, and in synergy with microscale roughness, downregulated the expression of the proinflammatory cytokine tumor necrosis factor alpha (TNF-α). In conclusion, controlled nanotopography superimposed on microrough machined implants promoted implant stability during osseointegration. Nanoscale-driven mechanisms may involve attenuation of the inflammatory response at the titanium implant site. Statement of SignificanceThe role of combined implant microscale and nanotopography features for osseointegration is incompletely understood. Using colloidal lithography technique, we created an ordered nanotopography pattern superimposed on screwshaped implants with microscale topography. The midterm and late molecular, bone-implant contact and removal torque responses were analysed in vivo. Nanotopography superimposed on microrough, machined, surfaces promoted the implant stability, influenced by microscale topography and the combination of nanoscale and microscale topographies. Increased bone-implant contact was mainly dependent on microscale roughness whereas the nanotopography, per se, and in synergy with microscale roughness, attenuated the proinflammatory tumor necrosis factor alpha (TNF-α) expression. It is concluded that microscale and nanopatterns provide individual as well as synergistic effects on molecular, morphological and biomechanical implant-tissue processes in vivo.

Sunflower-Like Nanostructure with Built-In Hotspots for Alpha-Fetoprotein Detection.

In the present study, a sunflower-like nanostructure array composed of a series of synaptic nanoparticles and nanospheres was manufactured through an efficient and low-cost colloidal lithography technique. The primary electromagnetic field contribution generated by the synaptic nanoparticles of the surface array structures was also determined by a finite-difference time-domain software to simulate the hotspots. This structure exhibited high repeatability and excellent sensitivity; hence, it was used as a surface-enhanced Raman spectroscopy (SERS) active substrate to achieve a rapid detection of ultra-low concentrations of Alpha-fetoprotein (AFP). This study demonstrates the design of a plasmonic structure with strong electromagnetic coupling, which can be used for the rapid detection of AFP concentration in clinical medicine.

Gold Nanoframe Array Electrode for Straightforward Detection of Hydrogen Peroxide

The nanostructuring of a sensing membrane is performed through colloidal nanosphere lithography (NSL) techniques with a tiny polystyrene nanobead template 100 nm in size. The solvent ratio adjustment has been proven to be effective in assisting the monolayer deposition of small templating particles with minimal defects. Two distinct structures, namely, a billowy gold nanostructure (BGN) where the nanobead template is left unetched and a gold nanoframe array (GNA) with a regular ring-like structure after template removal, are used for the extended-gate field-effect transistor (EGFET) electrodes. The GNA structure generates an electroactive surface area significantly (~20%) larger than its geometrical area as well as a greater surface roughness than the BGN. When integrated with the portable constant voltage–constant current (CVCC) FET circuitry for pH screening to determine the optimized measurement conditions for H2O2 sensing, the GNA sensing membrane also shows more improved Nernstian sensitivity at ~50 mV/pH than the BGN electrode. The more optimized sensitivity is then proven using the GNA in the detection of H2O2, the most common representative reactive oxygen species (ROS) involved in the environment, food, and neurodegenerative diseases, such as Parkinson´s and Alzheimer´s diseases. The GNA electrode has a sensitivity of 70.42 mV/log µM [H2O2] and a limit of detection (LoD) of 1.183 µM H2O2. The integrated ion sensing system employing unique, highly ordered gold array gate electrodes and a portable CVCC circuit system has shown a stable real-time output voltage signal, representing an alternative to bulky conventional FET devices for potential on-site H2O2 detection.

Epoxy thermoset coatings with fine controllable hierarchical structures prepared from bio-inspired photo-/colloidal lithography technique for anticorrosion application

Several epoxy thermoset (ET) composite coatings with artificial fine controllable micro/nano hierarchical structures were prepared through photolithography/colloidal lithography and subsequently applied in anticorrosion field. Firstly, several silicon wafers with fine controllable interspacing and width of micro-scaled cylindrical structures were fabricated through conventional photolithography. Subsequently, nano-scaled tips were fabricated upon a smooth clean surface on the previous silicon wafer with micro-scaled cylinders to generate nano-scaled tips through colloidal lithography. Moreover, ET coatings were duplicated by nano-casting technique with polydimethylsiloxane (PDMS) as a soft negative template. Surface morphology and contact angle (CA) of as-prepared hard silicon template and ET coatings were identified. The CA of water droplets on ET coating with bio-inspired micro/nano hierarchical structures (denoted by BET) was 160°, which meant that this coating was more hydrophobic than ET coatings with distinctive surface structures. Anticorrosion studies of as-prepared ET coating with/without distinctive structures showed that cold rod steel (CRS) electrode coated with BET had better anticorrosion performance than other ET coating for short- and long-term studies. This procedure of fine controllable micro/nano structure coatings opens the door for further innovative investigations of corrosion protection methods and material designs.

Plasmonic structure with nanocavity cavities for SERS detection of pesticide thiram

Excessive thiram residues in food have the potential to negatively impact human health. Hence, the development of a convenient and fast detection method is highly desirable. In this study, an efficient, repeatable, and sensitive surface-enhanced Raman scattering (SERS) active chip was manufactured via a low-cost colloidal lithography technique. The plasmonic structure was composed of a series of silver nanospheres and nanowires. Interestingly, this type structure creates a nanocavity space with a characteristic geometry generating a strong electromagnetic field coupling. The finite-different time-domain software was employed to simulate the electromagnetic field distribute on the nanocavity. Accordingly, SERS active chip that displays ultra-low concentration detection of thiram (10−11 M) was realized. Moreover, the excellent reproducibility of thiram (10−6 M) practical detection on an apple pericarp has great potential for application in food safety.

Chiral Plasmonic Metamaterials with Tunable Chirality

Chiral hollow nanovolcano array (HNVA) film and chiral hollow nanoshells (HNSs) are simultaneously fabricated via a new strategy of colloidal lithography technique. The chirality of both chiral plasmonic nanostructures, which arises from the asymmetric charge oscillation and electric field distributions, can be well controlled by regulating the opening-angle of the nanounits during the metal depositions. The large-area HNVA films exhibit strong chiroptical responses in the ultraviolet-visible region with g-factor of 0.15 and possess remarkable transferability for better adaptability of different application situations. The chiral HNSs, which are simultaneously obtained during the deposition, is equipped with adjustable chirality and integrability. The obtained HNVA films were transferred to specific substrates, e.g., polydimethylsiloxane (PDMS), hydrogels, and high-curvature surfaces, maintaining the original chiroptical properties and excellent mechanical strength. Deformable chiral flexible metamaterial is obtained by incorporating the chiral HNSs in the hydrogel, enabling the ultrasensitive detection of water content in the hydrogel. Overall, this work will contribute to the study of chiral metamaterials by providing two kinds of newly developed chiral plasmonic metamaterials with tunable chirality and inspiring progressing ways for the flexible devices of artificial chirality.

Doxorubicin hydrochloride loaded nanotextured films as a novel drug delivery platform for ovarian cancer treatment

An approach for cancer treatment is modulation of tumor microenvironment. Based on the role of extracellular matrix in cell modulation, fabrication of textured materials mimicking extracellular matrix could provide novel opportunities such as determining cancer cell behaviour. With this background, in this work, we have fabricated doxorubicin hydrochloride loaded nanotextured films which promote topographical attachment of cancer cells to film surface, and eliminate cells by release of the anti-cancer drug encapsulated within the films. These films are designed to be placed during surgical removal of the tumor with the intent to prevent ovarian cancer recurrence by capturing cancer cell residuals. With this aim, hemispherical protrusion shaped surface textures were acquired using colloidal lithography technique using 280 nm, 210 nm or 99 nm polystyrene particles. Once moulds were formed, nanotextured films were obtained by casting water-in-oil stable polycaprolactone emulsions encapsulating doxorubicin hydrochloride. Films were then characterized, and evaluated as drug delivery systems. According to results, we found that template morphologies were successfully transferred to films by atomic force microscopy studies. Hydrophilic surfaces were formed with contact angle values around 40°. In-vitro drug release studies indicated that nanotextured films best fit into the Higuchi model, and ∼30% of the drug is released from the films within 60 days. Cell culture results indicated increases in the attachment and viability of human ovarian cancer cells to nanotextured surfaces, particularly to the film fabricated using 99 nm particles. Our results demonstrated that delivery of anti-cancer drugs by use of nanotextured materials could be efficient in cancer therapy, and may offer new possibilities for cancer treatment.

Long-range ordered TiO2/Au hollow urchins: topology control for maskless electrodeposition

We present a novel approach for fabricating multicomponent ordered nanostructures using colloidal lithography and electrodeposition techniques, enabling maskless, targeted and uniform material deposition.

Architecture design and applications of nanopatterned arrays based on colloidal lithography

Nanopatterned arrays have potential applications in diverse devices, including high-density memory, wettability control, electronic chips, biochips, plasmonics (such as plasmon sensors, plasmon-enhanced molecular spectroscopy, and plasmon-mediated chemical reactions), and so on. In this tutorial, we first introduce colloidal lithography (CL) technique as an important method to prepare nanopatterned arrays. Based on the formation of a mask by self-assembly of polystyrene (PS) colloid spheres, the nanopatterned arrays can be achieved by following a series of various deposition, etching, transfer, and their combination steps. According to the structural differences of the acquired surface patterns, diverse nanopatterned arrays are fabricated by controlling the fabrication routes. Technical issues are discussed in detail, such as preparation and modification of the large-area and ordered PS colloid sphere arrays and design and hybridization of nanostructured arrays of films with various shapes. In the meantime, the potential applications of these nanopatterned array films are reviewed and summarized. Hopefully, the present tutorial will inspire more ingenious designs of nanopatterned arrays and developments of using CL technique in potential applications.

Indium⁻Tin⁻Oxide Nanostructures for Plasmon-Enhanced Infrared Spectroscopy: A Numerical Study.

Plasmonic nanoantennas can significantly enhance the light–matter interactions at the nanoscale, and as a result have been used in a variety of applications such as sensing molecular vibrations in the infrared range. Indium–tin–oxide (ITO) shows metallic behavior in the infrared range, and can be used for alternative plasmonic materials. In this work, we numerically studied the optical properties of hexagonal ITO nanodisk and nanohole arrays in the mid-infrared. Field enhancement up to 10 times is observed in the simulated ITO nanostructures. Furthermore, we demonstrated the sensing of the surface phonon polariton from a 2-nm thick SiO2 layer under the ITO disk arrays. Such periodic arrays can be readily fabricated by colloidal lithography and dry etching techniques; thus, the results shown here can help design efficient ITO nanostructures for plasmonic infrared applications.

Single molecule protein patterning using hole mask colloidal lithography.

The ability to manipulate single protein molecules on a surface is useful for interfacing biology with many types of devices in optics, catalysis, bioengineering, and biosensing. Control of distance, orientation, and activity at the single molecule level will allow for the production of on-chip devices with increased biological activity. Cost effective methodologies for single molecule protein patterning with tunable pattern density and scalable coverage area remain a challenge. Herein, Hole Mask Colloidal Lithography is presented as a bench-top colloidal lithography technique that enables a glass coverslip to be patterned with functional streptavidin protein onto patches from 15-200 nm in diameter with variable pitch. Atomic force microscopy (AFM) was used to characterize the size of the patterned features on the glass surface. Additionally, single-molecule fluorescence microscopy was used to demonstrate the tunable pattern density, measure binding controls, and confirm patterned single molecules of functional streptavidin.