Periodic Nanopatterns Research Articles

Directed self‐assembly of block copolymer thin films via momentary thickness gradients

AbstractIn this study, a novel method to fabricate highly aligned lamellar nanostructures in a millimeter‐scale large area was demonstrated by directing the self‐assembly of block copolymer (BCP) thin films with a temporary thickness‐gradient micropattern via simple two‐step thermal annealing. In the first step of thermal annealing, the BCP nanostructure is latently guided by a phenomenon known as “geometric anchoring” for the area with a thickness gradient. The second annealing step causes thermal reflow of the height gradient micropattern with a sufficiently large curvature to flatten the micropattern. The shear stress generated by thermal reflow enlarged the grain of the BCP nanostructure, resulting in a highly aligned lamellar pattern over the entire area. Finally, the formation of periodic nanopatterns in large area was ensured by performing grazing‐incidence small‐angle x‐ray scattering. This innovative approach in directing the BCP self‐assembly promotes the fabrication of highly aligned nanostructures in large areas through cost‐effective and simple thermal imprinting method and designed two‐step heat treatment.

Hierarchical Multi-Scale Coupled Periodical Photonic and Plasmonic Nanopatterns Inscribed by Femtosecond Laser Pulses in Lithium Niobate.

The ultrafast interaction of tightly focused femtosecond laser pulses with bulk dielectric media in direct laser writing (inscription) regimes is known to proceed via complex multi-scale light, plasma and material modification nanopatterns, which are challenging for exploration owing to their mesoscopic, transient and buried character. In this study, we report on the first experimental demonstration, analysis and modeling of hierarchical multi-period coupled longitudinal and transverse nanogratings in bulk lithium niobate inscribed in the focal region by 1030 nm, 300 fs laser pulses in the recently proposed sub-filamentary laser inscription regime. The longitudinal Bragg-like topography nanogratings, possessing the laser-intensity-dependent periods ≈ 400 nm, consist of transverse birefringent nanogratings, which are perpendicular to the laser polarization and exhibit much smaller periods ≈ 160 nm. Our analysis and modeling support the photonic origin of the longitudinal nanogratings, appearing as prompt electromagnetic and corresponding ionization standing waves in the pre-focal region due to interference of the incident and plasma-reflected laser pulse parts. The transverse nanogratings could be assigned to the nanoscale material modification by interfacial plasmons, excited and interfered in the resulting longitudinal array of the plasma sheets in the bulk dielectric material. Our experimental findings provide strong support for our previously proposed mechanism of such hierarchical laser nanopatterning in bulk dielectrics, giving important insights into its crucial parameters and opening the way for directional harnessing of this technology.

Hierarchical, Self-Assembled Metasurfaces via Exposure-Controlled Reflow of Block Copolymer-Derived Nanopatterns.

Nanopatterning for the fabrication of optical metasurfaces entails a need for high-resolution approaches like electron beam lithography that cannot be readily scaled beyond prototyping demonstrations. Block copolymer thin film self-assembly offers an attractive alternative for producing periodic nanopatterns across large areas, yet the pattern feature sizes are fixed by the polymer molecular weight and composition. Here, a general strategy is reported which overcomes the limitation of the fixed feature size by treating the copolymer thin film as a hierarchical resist, in which the nanoscale pattern motif is defined by self-assembly. Feature sizes can then be tuned by thermal reflow controlled locally by irradiative cross-linking or chemical alteration using lithographic ultraviolet light or electron beam exposure. Using blends of polystyrene-block-poly(methylmethacrylate) (PS-b-PMMA) with PS and PMMA homopolymers, we demonstrate both self-assembled PS grating and hexagonal hole patterns; exposure-controlled reflow is then used to reduce the hole diameter by as much as 50% or increase the PS grating linewidth by more than 180%. Transferring these nanopatterns, or their inverse obtained by a lift-off approach, into silicon yields structural colors that may be prescriptively controlled based on the nanoscale feature size. Furthermore, patterned exposure enables area-selective feature size control, yielding uniform structural color patterns across centimeter square areas. Electron beam lithography is also used to show that the lithographic resolution of this selective-area control can be extended to the nanoscale dimensions of the self-assembled features. The exposure-controlled reflow approach demonstrated here takes a pivotal step toward fabricating complex, hierarchical optical metasurfaces using scalable self-assembly methods.

Single metal-organic framework-embedded nanopit arrays: A new way to control neural stem cell differentiation.

Stable and continuous supply of essential biomolecules is critical to mimic in vivo microenvironments wherein spontaneous generation of various cell types occurs. Here, we report a new platform that enables highly efficient neuronal cell generation of neural stem cells using single metal-organic framework (MOF) nanoparticle–embedded nanopit arrays (SMENA). By optimizing the physical parameters of homogeneous periodic nanopatterns, each nanopit can confine single nMOFs (UiO-67) that are specifically designed for long-term storage and release of retinoic acid (RA). The SMENA platform successfully inhibited physical interaction with cells, which contributed to remarkable stability of the nMOF (RA⊂UiO-67) structure without inducing nanoparticle-mediated toxicity issues. Owing to the continuous and long-term supply of RA, the neural stem cells showed enhanced mRNA expressions of various neurogenesis-related activities. The developed SMENA platform can be applied to other stem cell sources and differentiation lineages and is therefore useful for various stem cell–based regenerative therapies.

Visualization of nonsingular defect enabling rapid control of structural color.

Stimuli-interactive structural color (SC) of a block copolymer (BCP) photonic crystal (PC) uses reversible alteration of the PC using external fluids and applied forces. The origin of the diffusional pathways of a stimulating fluid into a BCP PC has not been examined. Here, we directly visualize the vertically oriented screw dislocations in a one-dimensional lamellar BCP PC that facilitate the rapid response of visible SC. To reveal the diffusional pathway of the solvent via the dislocations, BCP lamellae are swollen with an interpenetrated hydrogel network, allowing fixation of the swollen state and subsequent microscopic examination. The visualized defects are low-energy helicoidal screw dislocations having unique, nonsingular cores. Location and areal density of these dislocations are determined by periodic concentric topographic nanopatterns of the upper surface-reconstructed layer. The nonsingular nature of the interlayer connectivity in the core region demonstrates the beneficial nature of these defects on sensing dynamics.

Mechanisms of surface nanostructuring of Al2O3 and MgO by grazing incidence irradiation with swift heavy ions

We experimentally discovered that Al2O3 and MgO exhibit well-pronounced nanometric modifications on the surfaces when irradiated under grazing incidence with 23 MeV I beam, in contrast to normal incidence irradiation with the same ion beam when no damage was found. Moreover, ions in these two materials produce notably different structures: grooves surrounded with nanohillocks on MgO surfaces vs. smoother, roll-like discontinuous structures on the surfaces of Al2O3. To explain these results, detailed numerical simulations were performed. We identified that a presence of the surface inhibits recrystallization process, thereby preventing transient tracks from recovery, and thus forming observable nanopatterns. Furthermore, a difference in the viscosities in molten states in Al2O3 vs. MgO explains the differences in the created nanostructures. Our results thus provide a deeper understanding of the fundamental processes of surface nanostructuring, potentially allowing for controlled production of periodic surface nanopatterns.

Growth mechanism of periodic nanopattern in metal-oxide composites

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Periodic nanopatterning and reduction of graphene oxide by femtosecond laser to construct high-performance micro-supercapacitors

Reduction and patterning of graphene oxide (GO) have been extensively applied in the field of electronic devices such as sensor, transistors and power source. Surface morphology and reduction level of reduced graphene oxide (rGO) directly influence the performance of devices. Herein, we put forward a new method of one-step periodic nanopatterning and reduction of GO using femtosecond laser pulses in air environment. Three-dimensional (3D) laser induced periodic surface structures (LIPSSs) with subwavelength ripples and flakes were obtained at the irradiation of laser fluences higher than the threshold of GO reduction (∼9 mJ/cm2). Meanwhile, the change in chemical compositions and phase structure transformation of femtosecond laser reduced GO (Fs-LRGO) was identified through X-ray photoelectron spectroscopy, Raman spectroscopy and X-ray diffraction. The excited surface plasma polaritons (SPPs) and photochemical effect were put forward to reveal the mechanism in the formation and reduction of Fs-LRGO with nanopatterns. By virtue of the periodic nanopatterns of Fs-LRGO, we also constructed the all-solid-state interdigital rGO micro-supercapacitors (MSCs) with ultralow electrode interspace of ∼10 μm and different connection ways, indicative of superior flexibility and cycle stability. This work provides new insights into the fundamental mechanism and utility of ultrafast periodic nanopatterning and reduction of GO for the application of multifunctional electronic device engineering.

Design and analysis of nanopatterned graphene-based structures for trapping applications

Trapping, levitating, and manipulating nanoscale objects with light forces shaped by patterned metamaterials continues to hold great interest for optical and condensed matter physics and engineering. Successful developments to date have concentrated on constraining movement only in one dimension, along the vertical axis to a material plane. Here we propose a realistic structure, consisting of alternating layers of graphene and dielectric, and periodically nanopatterned on the surface, that is capable of levitating and trapping nanoscale particles in two dimensions: one perpendicular and one parallel to the material plane. Repulsive forces arising from high- $k$ modes of the metamaterial provide particle levitation along the vertical axis. At the point where this repulsive force balances the downward gravitational force, the particle is trapped at stable equilibrium. Periodic nanopatterning in the metamaterial surface furnishes the second, horizontal axis constraining particle motion. We show that the equilibrium position above the surface can be controlled by adjusting both the Fermi level and the number of graphene layers. Furthermore, to explicate the role of the high-$k$ modes in generating the repulsive forces, we also propose a semianalytical method to calculate both the potential well and the forces generated by dipole radiation above the nanopatterned surface.

Achromatic Talbot lithography with nano-ring masks for high-throughput periodic patterning

Periodic patterning is important for various scientific and technological applications, especially in the nanoscale. Achromatic Talbot lithography (ATL) utilizing extreme ultraviolet (EUV) wavelengths, notably 13.5 nm, is a powerful lithographic technique enabling high-resolution and high-throughput nanopatterning over large areas. Improving the resolution and the throughput of the technique requires elaborate designs based on simulations and nanofabrication of transmission diffraction gratings on thin silicon nitride membranes. Our simulations point to the fact that compared to conventional ATL masks with hole arrays, masks consisting of annular rings and intersecting annular rings show increased performance in terms of throughput. A set of masks with uncrossed and crossed annular rings have been nanofabricated and exposed with spatially coherent synchrotron EUV light and the experimental results confirm our theoretical predictions that masks with annular rings and crossed rings yield dot arrays with improved throughput. The presented technique may enable applications in science and technology where large-area and periodic nanopatterning is needed.

Biological reaction control using topography regulation of nanostructured titanium

The micro- and nanosize surface topography of dental implants has been shown to affect the growth of surrounding cells. In this study, standardized and controlled periodic nanopatterns were fabricated with nanosized surface roughness on titanium substrates, and their influence on bone marrow stromal cells investigated. Cell proliferation assays revealed that the bare substrate with a 1.7 nm surface roughness has lower hydrophilicity but higher proliferation ability than that with a 0.6 nm surface roughness. Further, with the latter substrate, directional cell growth was observed for line and groove patterns with a width of 100 nm and a height of 50 or 100 nm, but not for those with a height of 10 or 25 nm. With the smooth substrate, time-lapse microscopic analyses showed that more than 80% of the bone marrow cells on the line and groove pattern with a height of 100 nm grew and divided along the lines. As the nanosized grain structure controls the cell proliferation rate and the nanosized line and groove structure (50–100 nm) controls cell migration, division, and growth orientation, these standardized nanosized titanium structures can be used to elucidate the mechanisms by which surface topography regulates tissue responses to biomaterials.

Tailoring of uniaxial magnetic anisotropy in Permalloy thin films using nanorippled Si substrates

In this work the investigation of in-plane uniaxial magnetic anisotropy induced by the morphology due to ion beam erosion of Si(1 0 0) has been done. Ion beam erosion at an oblique angle of incidence generates a well-ordered nanoripple structure on the Si surface and ripple propagates in a direction normal to ion beam erosion. Permalloy thin films grown on such periodic nanopatterns show a strong uniaxial magnetic anisotropy with easy axis of magnetization in a direction normal to the ripple wave vector. The strength of uniaxial magnetic anisotropy is found to be high for the low value of ripple wavelength; it is decreasing with increasing value of ripple wavelength. Similarly, the strength of uniaxial magnetic anisotropy decreases with increasing Permalloy film thickness. Grazing incidence small angle x-ray scattering data reveals an anisotropic growth of Permalloy thin films with preferential orientation of grains in the direction normal to the ripple wave vector. Permalloy thin film growth is highly conformal with the film surface replicating the substrate ripple morphology up to a film thickness of 50 nm has been observed. Correlation between observed uniaxial magnetic anisotropy to surface modification has been addressed.

Wet Brush Homopolymers as “Smart Solvents” for Rapid, Large Period Block Copolymer Thin Film Self-Assembly

The spontaneous formation of periodic nanopatterns through the self-assembly of block copolymer (BCP) thin films offers an enticing path to engineer functional material properties over large areas, but the prohibitively slow ordering of ultrahigh molecular weight BCPs that generate large pattern periods (>100 nm) severely restricts the design space in which BCPs may be used. Here, we demonstrate that blending lamellae-forming polystyrene-block-poly(methyl methacrylate) diblock copolymers with very low molecular weight polystyrene and poly(methyl methacrylate) homopolymers can reduce by an order-of-magnitude the times required to form ordered large period patterns through solvent vapor annealing. Using in situ grazing-incidence small-angle X-ray scattering and ex situ electron microscopy, we show that the added homopolymer plasticizers act as a “smart solvent”: They increase the mobility of the long BCP chains by amplifying the dilution effect during solvent vapor annealing but segregate to like domains du...

High-Fidelity, Sub-5 nm Patterns from High-χ Block Copolymer Films with Vapor-Deposited Ultrathin, Cross-Linked Surface-Modification Layers.

Despite their capability, sub-10 nm periodic nano-patterns formed by strongly segregating block copolymer (BCP) thin films cannot be easily oriented perpendicular to the substrate due to the huge surface energy differences of the constituent blocks. To produce perpendicular nano-patterns, the interfacial energies of both the substrate and free interfaces should be controlled precisely to induce non-preferential wetting. Unfortunately, high-performance surface modification layers are challenging to design, and different kinds of surface modification methods must be devised respectively for each neutral layer and top coat. Furthermore, conventional approaches, largely based on spin-coating processes, are highly prone to defect formation and may readily cause dewetting at sub-10 nm thickness. To date, these obstacles have hampered the development of high-fidelity, sub-5 nm BCP patterns. Herein, an all-vapor phase deposition approach initiated chemical vapor deposition is demonstrated to form 9-nm-thick, uniform neutral bottom layer and top coat with exquisite control of composition and thickness. These layers are employed in BCP films to produce perpendicular cylinders with a diameter of ≈4 nm that propagate throughout a BCP thickness of up to ≈60 nm, corresponding to five natural domain spacings of the BCP. Such a robust approach will serve as an advancement for the reliable generation of sub-10 nm nano-patterns.

Tuning wettability of Si surface by ion beam induced silicon nitride formation and nanopatterning

The transformation of a hydrophilic surface to a hydrophobic surface due to chemical modification and periodic nano pattern formation on silicon surface by 5–12 keV N+ ion bombardment is reported. The reactive N+ ion bombardment at oblique angle incidence leads to form silicon nitride (Si3N4) on the surface. Also, a periodic wave-like ripple pattern is formed on Si surface at nanoscale range whose wavelength and surface roughness can be regulated by varying the ion energy (5–12 keV). It is found that the contact angle of water droplet on such patterned surface increases with the increase of ripple wavelength and surface roughness. In contrast, the contact angle does not change for the same energy Ar+ bombarded Si surfaces, where such type of surface nano patterns are absent and also surface roughness remains almost the same. The morphologies of the irradiated and un-irradiated Si surfaces are examined by Atomic Force Microscopy (AFM), whereas the surface chemical composition is investigated by X-ray photoelectron spectroscopy (XPS). The chemical modification in terms of Si3N4 formation on the surface, periodic wave-like ripple pattern formation and high increase of root mean square (rms) roughness for N+ bombarded Si surfaces result in hydrophilic to hydrophobic transformation. The tuning of wettability in terms of ion beam parameters for the patterned and chemically modified Si surfaces is discussed in detail.

Displacement Talbot lithography for nano-engineering of III-nitride materials

Nano-engineering III-nitride semiconductors offers a route to further control the optoelectronic properties, enabling novel functionalities and applications. Although a variety of lithography techniques are currently employed to nano-engineer these materials, the scalability and cost of the fabrication process can be an obstacle for large-scale manufacturing. In this paper, we report on the use of a fast, robust and flexible emerging patterning technique called Displacement Talbot lithography (DTL), to successfully nano-engineer III-nitride materials. DTL, along with its novel and unique combination with a lateral planar displacement (D2TL), allow the fabrication of a variety of periodic nanopatterns with a broad range of filling factors such as nanoholes, nanodots, nanorings and nanolines; all these features being achievable from one single mask. To illustrate the enormous possibilities opened by DTL/D2TL, dielectric and metal masks with a number of nanopatterns have been generated, allowing for the selective area growth of InGaN/GaN core-shell nanorods, the top-down plasma etching of III-nitride nanostructures, the top-down sublimation of GaN nanostructures, the hybrid top-down/bottom-up growth of AlN nanorods and GaN nanotubes, and the fabrication of nanopatterned sapphire substrates for AlN growth. Compared with their planar counterparts, these 3D nanostructures enable the reduction or filtering of structural defects and/or the enhancement of the light extraction, therefore improving the efficiency of the final device. These results, achieved on a wafer scale via DTL and upscalable to larger surfaces, have the potential to unlock the manufacturing of nano-engineered III-nitride materials.

"Double" displacement Talbot lithography: fast, wafer-scale, direct-writing of complex periodic nanopatterns.

We describe a new low-cost nanolithographic tool for creating periodic arrays of complex, nano-motifs, across large areas within minutes. Displacement Talbot lithography is combined with lateral nanopositioning to enable large-area patterning with the flexibility of a direct-write system. In this way, we can create different periodic patterns in short timescales using a single mask with no mask degradation. We demonstrate multiple exposures, combined with discrete lateral displacements, and single exposures, with continuous displacements, to achieve image inversion, pitch reduction, and nanogaps between metal nanoparticles. Our approach provides a flexible route to create large-area nanopatterned materials and devices in high volumes.

Maskless laser nano-lithography of glass through sequential activation of multi-threshold ablation

Controllable nanofabrication is at the very foundation of nano-science and nano-technology. Today, ultrafast laser writing has been broadly adopted for micro-fabrication because of its ability to make precise and rapid processing of almost all types of materials in an ambient environment. However, direct laser writing is typically unsuitable for high-quality 2D nano-patterning. In this work, we introduce a maskless laser nano-lithographic technique that allows us to create regular 2D periodic nanopatterns on glass. Glass is a particularly challenging material since it does not absorb light readily. Our strategy starts with a glass sample being coated with a thin layer of metal, and then irradiated with a series of pulse bursts at progressively increasing fluence levels. This process allows us to sequentially activate a series of tailored physical processes that lead to the formation of regular 2D periodic nanopatterns on glass. The formation mechanism of this nano-patterning is also simulated numerically and further corroborated by a series of control experiments. We also show controllability in forming various shapes and sizes of nanopatterns through tailored fluence doses. Our technique provides a high-speed and low-cost method for glass nanofabrication.

Coherent Tabletop EUV Ptychography of Nanopatterns

Coherent diffraction imaging (CDI) or lensless X-ray microscopy has become of great interest for high spatial resolution imaging of, e.g., nanostructures and biological specimens. There is no optics required in between an object and a detector, because the object can be fully recovered from its far-field diffraction pattern with an iterative phase retrieval algorithm. Hence, in principle, a sub-wavelength spatial resolution could be achieved in a high-numerical aperture configuration. With the advances of ultrafast laser technology, high photon flux tabletop Extreme Ultraviolet (EUV) sources based on the high-order harmonic generation (HHG) have become available to small-scale laboratories. In this study, we report on a newly established high photon flux and highly monochromatic 30 nm HHG beamline. Furthermore, we applied ptychography, a scanning CDI version, to probe a nearly periodic nanopattern with the tabletop EUV source. A wide-field view of about 15 × 15 μm was probed with a 2.5 μm−diameter illumination beam at 30 nm. From a set of hundreds of far-field diffraction patterns recorded for different adjacent positions of the object, both the object and the illumination beams were successfully reconstructed with the extended ptychographical iterative engine. By investigating the phase retrieval transfer function, a diffraction-limited resolution of reconstruction of about 32 nm is obtained.

Resonance characteristics of localized plasmonic structures with periodic ZnO nano-patterns

Localized plasmonic structures with the periodic ZnO nano-patterns are demonstrated to increase the sensing characteristics of plasmonic sensor. The ZnO nano-patterns with 30 and 50 nm thicknesses are formed on the Au thin film of 50 nm, which have the periodic nano-patterns of 300 nm. Localized plasmonic structures are optimized using the three-dimensional finite-difference time-domain method as a function of incident angle for the width and thickness of the ZnO nano-structures. Localized plasmonic structures with the periodic ZnO nano-holes are fabricated using the double exposure technique by laser interference lithography. The measured resonance angles of 47.5° and 54° are obtained in the localized plasmonic structures with the periodic ZnO nano-patterns of 30 and 50 nm thicknesses, respectively.