Nanopatterning Methods Research Articles

Substrate Neutrality for Obtaining Block Copolymer Vertical Orientation.

Nanopatterning methods utilizing block copolymer (BCP) self-assembly are attractive for semiconductor fabrication due to their molecular precision and high resolution. Grafted polymer brushes play a crucial role in providing a neutral surface conducive for the orientational control of BCPs. These brushes create a non-preferential substrate, allowing wetting of the distinct chemistries from each block of the BCP. This vertically aligns the BCP self-assembled lattice to create patterns that are useful for semiconductor nanofabrication. In this review, we aim to explore various methods used to tune the substrate and BCP interface toward a neutral template. This review takes a historical perspective on the polymer brush methods developed to achieve substrate neutrality. We divide the approaches into copolymer and blended homopolymer methods. Early attempts to obtain neutral substrates utilized end-grafted random copolymers that consisted of monomers from each block. This evolved into side-group-grafted chains, cross-linked mats, and block cooligomer brushes. Amidst the augmentation of the chain architecture, homopolymer blends were developed as a facile method where polymer chains with each chemistry were mixed and grafted onto the substrate. This was largely believed to be challenging due to the macrophase separation of the chemically incompatible chains. However, innovative methods such as sequential grafting and BCP compatibilizers were utilized to circumvent this problem. The advantages and challenges of each method are discussed in the context of neutrality and feasibility.

Designed Polymer Ligands for Perovskite Quantum Dots and Their Block Copolymer Nanocomposites

AbstractPerovskite quantum dots (QDs) have efficient optical absorption and emission in the visible range, and show a strong quantum confinement effect and high external quantum efficiency. They have been at the forefront of next‐generation photovoltaics and optoelectronics applications. However, two major challenges associated with perovskites and their nanomaterials are poor stability (such as against moisture and polar solvents), as well as the lack of efficient nanopatterning methods. In this work, a promising approach is provided to address both of those major challenges by molecular engineering and integration of QDs with block copolymers (BCP). The BCP thermoplastic elastomers not only substantially improve the stability of perovskite QDs by encapsulating them in a highly stable and soft matrix, but also enable molecular‐level control of the alignment and assembly of perovskite QDs in the microphase‐separated BCP matrix. It is demonstrated that designing and synthesis of compatible polymer ligands for perovskite QDs is key to enabling their selective and strong interaction with the BCP matrix. The structure and molecular weight of the BCP also play an important role in the interfacial structure and optical properties of the QDs‐BCP nanocomposites. Such soft and flexible optical nanocomposites have potential applications in flexible optoelectronics, optical storage, and displays.

Direct Printing of Ultrathin Block Copolymer Film with Nano-in-Micro Pattern Structures.

Nanotransfer printing (nTP) is one of the most promising nanopatterning methods given that it can be used to produce nano-to-micro patterns effectively with functionalities for electronic device applications. However, the nTP process is hindered by several critical obstacles, such as sub-20nm mold technology, reliable large-area replication, and uniform transfer-printing of functional materials. Here, for the first time, a dual nanopatterning process is demonstrated that creates periodic sub-20nm structures on the eight-inch wafer by the transfer-printing of patterned ultra-thin (<50nm) block copolymer (BCP) film onto desired substrates. This study shows how to transfer self-assembled BCP patterns from the Si mold onto rigid and/or flexible substrates through a nanopatterning method of thermally assisted nTP (T-nTP) and directed self-assembly (DSA) of Si-containing BCPs. In particular, the successful microscale patternization of well-ordered sub-20nm SiOx patterns is systematically presented by controlling the self-assembly conditions of BCP and printing temperature. In addition, various complex pattern geometries of nano-in-micro structures are displayed over a large patterning area by T-nTP, such as angular line, wave line, ring, dot-in-hole, and dot-in-honeycomb structures. This advanced BCP-replicated nanopatterning technology is expected to be widely applicable to nanofabrication of nano-to-micro electronic devices with complex circuits.

Nanopatterning Technologies of 2D Materials for Integrated Electronic and Optoelectronic Devices.

With the reduction of feature size and increase of integration density, traditional 3D semiconductors are unable to meet the future requirements of chip integration. The current semiconductor fabrication technologies are approaching their physical limits based on Moore's law. 2D materials such as graphene, transitional metal dichalcogenides, etc., are of great promise for future memory, logic, and photonic devices due to their unique and excellent properties. To prompt 2D materials and devices from the laboratory research stage to the industrial integrated circuit-level, it is necessary to develop advanced nanopatterning methods to obtain high-quality, wafer-scale, and patterned 2D products. Herein, the recent development of nanopatterning technologies, particularly toward realizing large-scale practical application of 2D materials is reviewed. Based on the technological progress, the unique requirement and advances of the 2D integration process for logic, memory, and optoelectronic devices are further summarized. Finally, the opportunities and challenges of nanopatterning technologies of 2D materials for future integrated chip devices are prospected.

Ligand functionalization of titanium nanopattern enables the analysis of cell-ligand interactions by super-resolution microscopy.

The spatiotemporal aspects of early signaling events during interactions between cells and their environment dictate multiple downstream outcomes. While advances in nanopatterning techniques have allowed the isolation of these signaling events, a major limitation of conventional nanopatterning methods is its dependence on gold (Au) or related materials that plasmonically quench fluorescence and, thus, are incompatible with super-resolution fluorescence microscopy. Here we describe a novel method that integrates nanopatterning with single-molecule resolution fluorescence imaging, thus enabling mechanistic dissection of molecular-scale signaling events in conjunction with nanoscale geometry manipulation. Our method exploits nanofabricated titanium (Ti) whose oxide (TiO2) is a dielectric material with no plasmonic effects. We describe the surface chemistry for decorating specific ligands such as cyclo-RGD (arginine, glycine and aspartate: a ligand for fibronectin-binding integrins) on TiO2 nanoline and nanodot substrates, and demonstrate the ability to perform dual-color super-resolution imaging on these patterns. Ti nanofabrication is similar to other metallic materials like Au, while the functionalization of TiO2 is relatively fast, safe, economical, easy to set up with commonly available reagents, and robust against environmental parameters such as humidity. Fabrication of nanopatterns takes ~2-3 d, preparation for functionalization ~1.5-2 d, and functionalization 3 h, after which cell culture and imaging experiments can be performed. We suggest that this method may facilitate the interrogation of nanoscale geometry and force at single-molecule resolution, and should find ready applications in early detection and interpretation of physiochemical signaling events at the cell membrane in the fields of cell biology, immunology, regenerative medicine, and related fields.

Formation of Surface-Wrinkled Metal Nanosheets via Thermally Assisted Nanotransfer Printing

Nanopatterning methods for pattern formation of high-resolution nanostructures are essential for the fabrication of various electronic devices, including wearable displays, high-performance semiconductor devices, and smart biosensor systems. Among advanced nanopatterning methods, nanotransfer printing (nTP) has attracted considerable attention due to its process simplicity, low cost, and great pattern resolution. However, to diversify the pattern geometries for wide device applications, more effective and useful nTP based patterning methods must be developed. Here, we introduce a facile and practical nanofabrication method to obtain various three-dimensional (3D) ultra-thin metallic films via thermally assisted nTP (T-nTP). We show how to generate surface-wrinkled 3D nanostructures, such as angular line, concave-valley, and convex-hill structures. We also demonstrate the principle for effectively forming 3D nanosheets by T-nTP, using Si master molds with a low aspect ratio (A/R ≤ 1). In addition, we explain how to obtain a 3D wavy structure when using a mold with high A/R (≥ 3), based on the isotropic deposition process. We also produced a highly ordered 3D Au nanosheet on flexible PET over a large area (&gt; 15 µm). We expect that this T-nTP approach using various Si mold shapes will be applied for the useful fabrication of various metal/oxide nanostructured devices with high surface area.

Surface Nano-Patterning for the Bottom-Up Growth of III-V Semiconductor Nanowire Ordered Arrays.

Ordered arrays of vertically aligned semiconductor nanowires are regarded as promising candidates for the realization of all-dielectric metamaterials, artificial electromagnetic materials, whose properties can be engineered to enable new functions and enhanced device performances with respect to naturally existing materials. In this review we account for the recent progresses in substrate nanopatterning methods, strategies and approaches that overall constitute the preliminary step towards the bottom-up growth of arrays of vertically aligned semiconductor nanowires with a controlled location, size and morphology of each nanowire. While we focus specifically on III-V semiconductor nanowires, several concepts, mechanisms and conclusions reported in the manuscript can be invoked and are valid also for different nanowire materials.

From Single-Nanowire Biosensors to Nanowire Networks for Transparent Electrodes: A Framework to Reduce Fabrication Cost and Improve Device Functionality

Abstract Field-assisted nanowire positioning is a cost-effective technique that uses an AC electric field for fabricating nanowire devices. The values of several variables involved, such as the electrode geometry and the frequency and magnitude of the applied field, need to be chosen to increase overall area coverage, while maintaining functionality. Insufficient understanding of the effect of each variable can escalate disruptive forces and effects, e.g. electroosmotic flow and electrode polarization, that hinder nanowire positioning. We introduce a quantitative guideline for calculating variable values to fabricate nanowire devices, which replaces a tedious and costly trial-and-error process. Earlier experimental demonstrations of attogram-level mass sensitivity with nanoresonators were made using nanopatterning methods, cost-prohibitive for commercial application. We demonstrate a low-cost method for making biosensors of the same sensitivity, with high yield, and for large transparent electrodes with high transmissivity and conductivity.

Sub-10-pW/Hz0.5Uncooled Micro-Bolometer With a Vacuum Micro-Package

This paper presents a very low noise suspended micro-bolometer with an in-situ vacuum micro-package so as to prevent thermal loss to the surrounding area and minimize the thermal conductivity of the ambient. Bolometer thermal models with respect to vacuum pressure are developed and verified by finite-element method (FEM) simulations. It is found that with the vacuum micro-package, a micro-scale (and not a nano-scale) size bolometer can achieve a noise equivalent power (NEP) close to the theoretical limit. Vacuum packaged Ni micro-bolometers with a sheet resistance of 6.2-6.5 Q/sq, widths of 1.3 and 2.3 μm, and a micro-vacuum ambient of 1 torr are fabricated using advanced micro-machining techniques. The measured responsivity (RESP) of a room-temperature micro-bolometer with w <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">b</sub> = 1.3 μm is 922 V/W (β = 1.54 MQ/W) for R <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">b</sub> = 275 Ω and I <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">b</sub> = 0.6 mA. The measured best NEP is 7.2 pW/Hz <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">0.5</sup> at 3-kHz modulation frequency for w <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">b</sub> = 1.3 μm, l <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">b</sub> = 40 μm, and R <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">b</sub> = 230 Ω, and is the first demonstration resulting in <;10 pW/Hz <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">0.5</sup> performance among uncooled micro-bolometers without any nano-patterning methods. The application areas are in low-cost THz imaging systems and wideband THz detectors.

Fabrication of a Au–polystyrene sphere substrate with three-dimensional nanofeatures for surface-enhanced Raman spectroscopy

Methods for fabricating three-dimensional nanofeature arrays for surface-enhanced Raman spectroscopy (SERS) substrates were explored by combining the self-assembly of nanoscale polystyrene (PS) spheres with subsequent Au film ion sputter coating modulation. The substrate's nanoscale hot-spot features were controlled using the Au coating film thickness regulation and focused ion beam (FIB) nano-patterning regulation methods. Scanning electron microscopy and Raman spectroscopy were employed to analyze the substrate morphology and the enhancement mechanism of the three-dimensional SERS substrate. PS microspheres with diameters of 151nm and 360nm were coated with Au layers of different thicknesses ranging from 10nm to 270nm. The configuration of the Au–PS spheres can be regulated to hexagonal close packing with nanoscale V-shaped slits with a 10–20nm gap pattern. Nanoscale Au particles and clusters with a clear outline covered the surface of the PS spheres, in which the multiple-scale structures increase the specific surface area of the SERS-active substrate. Nanoscale cracks formed on the smaller Au–PS spheres with a diameter of 151nm, which also exhibited strong SERS activity. The substrate surface temperature regularly increased after Au coating, and the thermal expansion coefficient difference and PS glass transition properties were studied to explain the Au–PS spheres nanofeature configuration development. The fabricated Au–PS spheres SERS feature is a type of three-dimensional and highly ordered array, which can show Raman scattering characteristics by providing a SERS enhancement factor of greater than 107.

Unconventional tailorable patterning by solvent-assisted surface-tension-driven lithography

Unconventional nanopatterning methods are emerging as powerful tools for the development of controlled shapes and ordered morphology of nanostructured materials with novel properties and tailorable functions. Here, we report a simple yet straightforward and efficient approach for patterning through unconventional dewetting that involves surface tension driven process. Using this innovative approach, we have successfully demonstrated to be able to prepare surface micro-patterns over large areas deposited through Eu3+:TiO2 nanoparticles providing rational control over the local nucleation of nanoparticles. Remarkably, these features could be addressed by polar or apolar solvents, suggesting potential applications in bottom-up nanodevices. This paper represents the first such attempt to create an inorganic materials non-lithographic template for the directed deposition of Eu3+:TiO2 or related metal oxides. The technique, which is driven by the unique chemical properties and geometrical layout of the underlying patterned micrometer-sized templates, enables the construction of micro- and nano-structuration of dispersed inorganic functional materials suitable for electrooptical and photonic applications.

Optical properties of ultra-thin silicon films deposited on nanostructured anodic alumina surfaces

Light trapping is crucial for thin film silicon solar cells and is often achieved by expensive, clean-room intensive nano-patterning methods. In this work, nanostructured silicon thin films were realized by direct deposition on substrates with nanoscale features prepared by simple and scalable fabrication based on electrochemical methods and wet etching. A broadband and angle-insensitive absorption enhancement of thin film silicon was observed. The photocurrent density shows improvements up to ∼40% in the AM 1.5 spectrum when comparing to the same thin film silicon deposited on smooth substrates. This approach not only demonstrates the advantage of simple fabrication but also has potential for ultra thin film photovoltaic applications.

Breakthroughs in photonics 2012: Nano-structuring and nano-fabrication enabled by extreme ultraviolet laser sources

Two- and three-dimensional structures with submicron dimensions, such as photonic crystals, patterned magnetic media, micro- and nano-electromechanical systems (MEMs/NEMs), microfluidics chips, etc., are becoming ubiquitous in multiple applications across many research fields. The necessity to engineer these devices has inspired the development of novel nanofabrication and nano-patterning methods. This review describes major accomplishments in laser-based nano-patterning and nano-fabrication methods. In particular, it focuses on newly developed nano-patterning techniques based on the use of extreme ultraviolet laser light that contributes to the rapid and efficient fabrication of periodic nano-structures.

Fabrication of ordered bulk heterojunction organic photovoltaic cells using nanopatterning and electrohydrodynamic spray deposition methods

Organic photovoltaic cells with an ordered heterojunction (OHJ) active layer are expected to show increased performance. In the study described here, OHJ cells were fabricated using a combination of nanoimprinting and electrohydrodynamic (EHD) spray deposition methods. After an electron donor material was nanoimprinted with a PDMS stamp (valley width: 230 nm, period: 590 nm) duplicated from a Si nanomold, an electron acceptor material was deposited onto the nanoimprinted donor layer using an EHD spray deposition method. The donor-acceptor interface layer was observed by obtaining cross-sectional images with a focused ion beam (FIB) microscope. The photocurrent generation performance of the OHJ cells was evaluated with the current density-voltage curve under air mass (AM) 1.5 conditions. It was found that the surface morphology of the electron acceptor layer affected the current and voltage outputs of the photovoltaic cells. When an electron acceptor layer with a smooth thin (250 nm above the valley of the electron donor layer) surface morphology was obtained, power conversion efficiency was as high as 0.55%. The electrohydrodynamic spray deposition method used to produce OHJ photovoltaic cells provides a means for the adoption of large area, high throughput processes.

Research Progress in Application of Nanomaterials for Deoxyribonucleic Acid Detection

Abstract Recent progress in application of nanomaterials for DNA detection, except for PCR systems, was reviewed. Nanomaterial-based (nanoparticles and nanowires/tubes) or nanofabrication-based DNA detection methods were introduced. Studies revealed that nanomaterial-based DNA detection methods offer several advantages over the traditional PCR technology in terms of orientation, visualization, and multiplexed detection. Especially, with regard to nanomaterial-based detection, methods using nanoparticles were studied most extensively, including colorimetrical detection, fluorescent detection, resonance light scattering detection, surface-enhanced Raman scattering detection, electrochemical detection, MALDI-TOF MS detection, and elemental analysis detection. For the nanofabrication-based DNA detection, four methods were presented: nanopatterning, nanoelectromechnical devices, nanopore, and microarray detection methods.

Nanobubble and nanodroplet template growth of particle nanorings versus nanoholes in drying nanofluids and polymer films

Here we demonstrate how confined nanobubbles and nanodroplets, which can either form spontaneously at the suspension/substrate interface, or can more interestingly be purposely introduced in the system, allow assembly of nanoparticles (NPs) into nanoring-like structures with a flexible control of both the size and distribution. As with most wetting-mediated nanopatterning methods, this approach provides an alternative to direct replication from templates. The formation of two-dimensional ring-shaped nanostructures was obtained by drying a nanocolloidal gold (Au) suspension drop confining nanobubbles (or nanodroplets) that are settled at a solid substrate. AFM investigation of the dry nanostructures showed the formation of isolated Au NPs rings having diameters ranging from 200 nm to 500 nm along the dewetting-drying path of the suspension drop. The flexibility of these wetting processes for the variation of the spatial features of the nanoring (size and shape resolution) essentially depends on physical parameters such as the nanobubble/nanodroplet size and concentration, the wettability, and the evaporation rate of the nanofluid drop on the substrate. Furthermore, we show that the underpinning mechanism of this evaporation-assisted assembly of Au NPs into supported functional nanoring patterns is fairly similar to that at work in the spontaneous formation of nanoholes in drying polymer thin films. Finally, the method proves to be a simple and flexible nanofabrication tool to be extended to various nanosize objects, towards specific optical and sensing applications.

Van derWaals enhancement of optical atom potentials via resonant coupling to surface polaritons

Contemporary experiments in cavity quantum electrodynamics (cavity QED) with gas-phase neutral atoms rely increasingly on laser cooling and optical, magneto-optical or magnetostatic trapping methods to provide atomic localization with sub-micron uncertainty. Difficult to achieve in free space, this goal is further frustrated by atom-surface interactions if the desired atomic placement approaches within several hundred nanometers of a solid surface, as can be the case in setups incorporating monolithic dielectric optical resonators such as microspheres, microtoroids, microdisks or photonic crystal defect cavities. Typically in such scenarios, the smallest atom-surface separation at which the van der Waals interaction can be neglected is taken to be the optimal localization point for associated trapping schemes, but this sort of conservative strategy generally compromises the achievable cavity QED coupling strength. Here we suggest a new approach to the design of optical dipole traps for atom confinement near surfaces that exploits strong surface interactions, rather than avoiding them, and present the results of a numerical study based on (39)K atoms and indium tin oxide (ITO). Our theoretical framework points to the possibility of utilizing nanopatterning methods to engineer novel modifications of atom-surface interactions.

Dynamic Shadow Mask Technique: A Universal Tool for Nanoscience

A comprehensive instrument, designed for fabricating nanostructures by evaporation through a dynamic shadow mask in ultrahigh vacuum, is described. The versatility and performance of the instrument is demonstrated through a series of examples, allowing for applications that are impossible to achieve with traditional nanopatterning methods. Clean nanostructures or entire devices made of different materials and on various substrates can be fabricated. The technique is compatible with fundamental surface science and can be easily interfaced with other fabrication and characterization techniques.

Integration Of Carbon Nanotubes Into Device Structures

ABSTRACTCarbon nanotubes have shown promising properties for applications in electronic circuits and other device structures. Several device structures have been demonstrated in recent years by manual manipulation of single nanotubes. The integration of large numbers of nanotubes on wafer size substrates, however, has been a challenge.Our approach addressing this issue utilizes nano-patterning methods in combination with plasma enhanced chemical vapor deposition to directly assemble carbon nanotubes on wafer structures. A secondary formation step is used to actually form device structures connecting the nanotubes to electrode structures. We present first results demonstrating the feasibility of our approach. Electrode structures were prepared using multi-step electron beam lithography processes. Carbon nanotubes were grown in pre-defined locations, and contact formation procedures were carried out to establish multi-terminal contact structures.

Real-time studies of Ge growth on nanostructured Si substrates

Nanostructured substrates are an interesting path towards the production of quantum dots devoted to microelectronic applications. In this work we report results on the effects of different nanopatterning methods to obtain lateral ordering of Ge islands grown on Si. By using Scanning Tunneling Microscopy we have studied in real-time the wetting layer growth and islands formation on nanopatterned Si substrates at 500 °C. We compare results obtained on Si substrates nanopatterned by using two different techniques: STM lithography and natural patterning induced by surface instabilities such as step bunching. Different issues on both cases have been addressed: substrate preparation, Ge dots placement and growth mode. We have observed that, on Si(001), the Ge islands nucleate near the holes and on Si(111) step bunching can guide the growth of aligned rows of islands.