Topographical Templates Research Articles

High χ P2PFBEMA-b-P2VP Block Copolymers Forming 6-8 nm Domains for Semiconductor Lithography.

We leveraged the potential of high χ-low N block copolymer (BCP), namely, poly[2-(perfluorobutyl) ethyl methacrylate]-block-poly(2-vinylpyridine) (P2PFBEMA-b-P2VP), and demonstrated its utility in next-generation nanomanufacturing. By combining molecular dynamics simulations with experiments, the χ value was calculated to be as high as 0.4 (at 150 °C), surpassing similar structures. Highly ordered features suitable for application were observed, ranging in periods from 19.0 nm down to 12.1 nm, with feature sizes as small as 6 nm. Transmission electron microscopy images of the BCP solutions indicated that preformed micelles in the solution facilitated the self-assembly process of the thin film. In addition, the vertical or parallel orientation of the cylindrical structure was determined by manipulating the solvent, substrate, and annealing conditions. Finally, guided by a wide topographical template, nearly defect-free directed self-assembly (DSA) lines with a resolution of 8 nm were achieved, highlighting its potential practical application in DSA lithography technology.

Manipulating the processing window of directed self-assembly in contact hole shrinking with binary block copolymer/homopolymer blending

Manipulating the processing window of directed self-assembly in contact hole shrinking with binary block copolymer/homopolymer blending

Control of Self-Assembly and Elemental Mixing of AuNi Bimetallic Nanoparticles via Solid-State and Liquid-State Dewetting of Metal Thin Films

Immiscible Au-Ni alloy thin films undergo phase separation and dewetting because of thermodynamic and morphological instability at elevated temperatures below the miscibility gap. We report the formation and assembly of bimetallic nanoparticles (BNPs) on topographic Si templates. An ordered array of inverted pyramidal pits were produced via solid-state and liquid-state dewetting of a 12-nm-thick Au-Ni thin film by respectively using thermal annealing and laser irradiation. Upon direct thermal annealing at 600 and 800 <sup>o</sup>C, the thin film on the templates self-assembled into an ordered array of BNPs composed of Au-rich and Ni-rich sub-clusters in pits. But the relative proportions of the two sub-clusters varied with annealing temperature due to the additional formation of smaller Ni-rich NPs that were scattered around the BNPs. Laser irradiation of the film, in contrast, formed an ordered array of fully mixed alloy NPs on the template and left no other residues on the surface. Subsequent thermal annealing induced the elements within the NPs to segregate, resulting in Au-rich and Ni-rich sub-clusters. In brief, the combination of solid-state and liquidstate dewetting processes on a topographic template not only enabled the 2-dimesional self-assembly of BNPs but also allowed control of the mixing of alloying elements within the BNPs. These results offer insights into the tailored fabrication of BNPs, which have potential applications in bio-functional catalysts, and plasmonic and chemical sensors.

Estimating neural activity from visual areas using functionally defined EEG templates.

Electroencephalography (EEG) is a common and inexpensive method to record neural activity in humans. However, it lacks spatial resolution making it difficult to determine which areas of the brain are responsible for the observed EEG response. Here we present a new easy-to-use method that relies on EEG topographical templates. Using MRI and fMRI scans of 50 participants, we simulated how the activity in each visual area appears on the scalp and averaged this signal to produce functionally defined EEG templates. Once created, these templates can be used to estimate how much each visual area contributes to the observed EEG activity. We tested this method on extensive simulations and on real data. The proposed procedure is as good as bespoke individual source localization methods, robust to a wide range of factors, and has several strengths. First, because it does not rely on individual brain scans, it is inexpensive and can be used on any EEG data set, past or present. Second, the results are readily interpretable in terms of functional brain regions and can be compared across neuroimaging techniques. Finally, this method is easy to understand, simple to use and expandable to other brain sources.

Nanoparticle contact printing with interfacial engineering for deterministic integration into functional structures.

Deterministic, pristine, and scalable integration of individual nanoparticles onto arbitrary surfaces is an ongoing challenge, yet essential for harnessing their unique properties for functional nanoscale devices. To address this challenge, we present a versatile technique where spatially arranged nanoparticles assembled in a topographical template are printed onto diverse surfaces, through a single contact-and-release step, with >95% transfer yield and <50-nanometer placement accuracy. Through engineering of interfacial interactions, our approach uniquely promotes high-yield transfer of individual particles without needing solvents, surface treatments, and polymer sacrificial layers, which are conventionally inevitable. By avoiding these mediation steps, surfaces can remain damage and contamination free and accessible to integrate into functional structures. We demonstrate this in a particle-on-mirror model system, where >2000 precisely defined nanocavities display a consistent plasmonic response with minimized interstructure variability. Through fabricating arrays of emitter-coupled nanocavities, we further highlight the integration opportunities offered by our contact printing.

Phase-field numerical study on the dynamic process of thermocapillary patterning.

It is well known that surface tension is dependent on temperature, and thus a nonuniform temperature may cause thermocapillary flow which is referred to as the Marangoni effect. For a thin liquid-air film confined between a flat hot plate and a topographical cold template, it undergoes deformation due to thermocapillary flow. This phenomenon is termed as thermocapillary patterning, and has been used to fabricate micro- and nanostructure in polymer films. In most cases, the obtained structure conforms to the template; i.e., it can be considered as a replication technique. In this paper, we developed a two-phase flow numerical model based on the phase field to study the dynamic process of thermocapillary patterning. As a remeshing-free method, the phase field enables the incorporation of thermal field and multiphase flow with free surface deformation. The numerical model was employed to study the dynamic process of thermocapillary patterning. Meanwhile, the effects of some parameters, e.g., temperature, geometry parameters, and contact angle, were also investigated.

Automatized online prediction of slow-wave peaks during non-rapid eye movement sleep in young and old individuals: Why we should not always rely on amplitude thresholds.

Brain-state-dependent stimulation during slow-wave sleep is a promising tool for the treatment of psychiatric and neurodegenerative diseases. A widely used slow-wave prediction algorithm required for brain-state-dependent stimulation is based on a specific amplitude threshold in the electroencephalogram. However, due to decreased slow-wave amplitudes in aging and psychiatric conditions, this approach might miss many slow-waves because they do not fulfill the amplitude criterion. Here, we compared slow-wave peaks predicted via an amplitude-based versus a multidimensional approach using a topographical template of slow-wave peaks in 21 young and 21 older healthy adults. We validate predictions against the gold-standard of offline detected peaks. Multidimensionally predicted peaks resemble the gold-standard regarding spatiotemporal dynamics but exhibit lower peak amplitudes. Amplitude-based prediction, by contrast, is less sensitive, less precise and - especially in the older group - predicts peaks that differ from the gold-standard regarding spatiotemporal dynamics. Our results suggest that amplitude-based slow-wave peak prediction might not always be the ideal choice. This is particularly the case in populations with reduced slow-wave amplitudes, like older adults or psychiatric patients. We recommend the use of multidimensional prediction, especially in studies targeted at populations other than young and healthy individuals.

Patch formation on diblock copolymer micelles confined in templates for inducing patch orientation and cyclic colloidal molecules

HypothesisChemically or physically distinct patches can be induced on the micelles of amphiphilic block copolymers, which facilitate directional binding for the creation of hierarchical structures. Hence, control over the direction of patches on the micelles is a crucial factor to attain the directionality on the interactions between the micelles, particularly for generating colloidal molecules mimicking the symmetry of molecular structures. We hypothesized that direction and combination of the patches could be controlled by physical confinement of the micelles. ExperimentsWe first confined spherical micelles of diblock copolymers in topographic templates fabricated from nanopatterns of block copolymers by adjusting the coating conditions. Then, patch formation was conducted on the confined micelles by exposing them with a core-favorable solvent. Microscopic techniques of SEM, TEM, and AFM were employed to investigate directions of patches and structures of combined micelles in the template. FindingsThe orientation of the patches on the micelles was guided by the physical confinement of the micelles in linear trenches. In addition, by confining the micelles in a circular hole, we obtained a specific polygon arrangement of the micelles depending on the number of micelles in the hole, which enabled the formation of cyclic colloidal molecules consisting of micelles.

Precise Capillary‐Assisted Nanoparticle Assembly in Reusable Templates

AbstractCapillary‐assisted particle assembly (CAPA) in predefined topographical templates is a scalable method for the precise positioning of nanoscale objects on various surfaces. High‐resolution CAPA templates are typically fabricated by expensive electron‐beam lithography and are used for a single assembly process. To increase the scalability and reduce the costs of the CAPA technique, the fabrication and characterization of reusable templates with nanoscale funnel‐shaped traps for repetitive precise nanoparticle placement are demonstrated. The yield of the first assembly of 100 nm gold nanoparticles (AuNPs) is as high as 94% with a median position offset of about 10 nm. The subsequent transfer process of the AuNPs from the silicon assembly template onto polymer surfaces, such as the elastic polydimethylsiloxane or the inelastic OrmoComp, shows a transfer yield larger than 99%. After the first transfer process, the assembly template is reused, resulting in a position offset and an assembly and transfer yield of this second assembly/transfer step that are comparable to the first ones. The obtained results demonstrate that the nanotemplates made by electron‐beam lithography can be reused for repeatable CAPA processes and thereby eliminate the need for recurring lithography steps for each assembly and thus make the CAPA technique more cost‐efficient.

Template Dissolution Interfacial Patterning of Single Colloids for Nanoelectrochemistry and Nanosensing.

Deterministic positioning and assembly of colloidal nanoparticles (NPs) onto substrates is a core requirement and a promising alternative to top-down lithography to create functional nanostructures and nanodevices with intriguing optical, electrical, and catalytic features. Capillary-assisted particle assembly (CAPA) has emerged as an attractive technique to this end, as it allows controlled and selective assembly of a wide variety of NPs onto predefined topographical templates using capillary forces. One critical issue with CAPA, however, lies in its final printing step, where high printing yields are possible only with the use of an adhesive polymer film. To address this problem, we have developed a template dissolution interfacial patterning (TDIP) technique to assemble and print single colloidal AuNP arrays onto various dielectric and conductive substrates in the absence of any adhesion layer, with printing yields higher than 98%. The TDIP approach grants direct access to the interface between the AuNP and the target surface, enabling the use of colloidal AuNPs as building blocks for practical applications. The versatile applicability of TDIP is demonstrated by the creation of direct electrical junctions for electro- and photoelectrochemistry and nanoparticle-on-mirror geometries for single-particle molecular sensing.

Commensurability-Driven Orientation Control during Block Copolymer Directed Self-Assembly.

In this study, the orientation of block copolymer (BCP) patterns in topographical templates is controlled using a simple template design rule. The orientation of the pattern is selected by using a template with one commensurate dimension and one incommensurate dimension. An array of binary states of a BCP pattern can be programmed into a desired layout by tuning of the template wall thickness.

Nano-confined crystallization of organic ultrathin nanostructure arrays with programmable geometries

Fabricating ultrathin organic semiconductor nanostructures attracts wide attention towards integrated electronic and optoelectronic applications. However, the fabrication of ultrathin organic nanostructures with precise alignment, tunable morphology and high crystallinity for device integration remains challenging. Herein, an assembly technique for fabricating ultrathin organic single-crystal arrays with different sizes and shapes is achieved by confining the crystallization process in a sub-hundred nanometer space. The confined crystallization is realized by controlling the deformation of the elastic topographical templates with tunable applied pressures, which produces organic nanostructures with ordered crystallographic orientation and controllable thickness from less than 10 nm to ca. 1 μm. The generality is verified for patterning various typical solution-processable materials with long-range order and pure orientation, including organic small molecules, polymers, metal-halide perovskites and nanoparticles. It is anticipated that this technique with controlling the crystallization kinetics by the governable confined space could facilitate the electronic integration of organic semiconductors.

Random Organic Nanolaser Arrays for Cryptographic Primitives.

Next-generation high-security cryptography and communication call for nondeterministic generation and efficient authentication of unclonable bit sequences. Physical unclonable functions using inherent randomness in material and device fabrication process have emerged as promising candidates for realizing one-way cryptographic systems that avoid duplication and attacks. However, previous approaches suffer from the tradeoffs between low-efficiency fabrication and complicated authentication. Here, all-photonic cryptographic primitives by solution printing of organic nanolaser arrays with size-dependent dual lasing emission are reported. The stochastic distribution of organic solution into discrete capillary bridges, triggered by high-rate solvent evaporation, on a periodic topographical template yields organic single crystals with regulated position, alignment, and random size, which ensures high entropy. Stimulated emission from different vibrational sublevels and the intrinsic self-absorption effect permit size-dependent dual-wavelength lasing emission at wavelengths of 660 and/or 720 nm, which can be efficiently encoded into quaternary cryptographic keys with high reliability. High entropy, solution-processed programming and all-photonic authentication of random organic nanolaser arrays facilitate their cryptographic implementation in secure communication with high throughput, efficiency, and low cost.

Sub‐5 nm Dendrimer Directed Self‐Assembly with Large‐Area Uniform Alignment by Graphoepitaxy

AbstractDirected self‐assembly (DSA) using soft materials is an important method for producing periodic nanostructures because it is a simple, cost‐effective process for fabricating high‐resolution patterns. Most of the previously reported DSA methods exploit the self‐assembly of block copolymers, which generates a wide range of nanostructures. In this study, cylinders obtained from supramolecular dendrimer films with a high resolution (&lt;5 nm) exhibit planar ordering over a macroscopic area via guiding topographical templates with a high aspect ratio (&gt;10) and high spatial resolution (≈20 nm) of guiding line patterns. Theoretical and experimental studies reveal that this property is related to geometrical anchoring on the meniscus region and physical surface anchoring on the sidewall. Furthermore, this DSA of dendrimer cylinders is demonstrated by the non‐regular geometry of the patterned template. The macroscopic planar alignment of the dendrimer nanostructure reveals an extremely small feature size (≈4.7 nm) on the wafer scale (&gt;16 cm2). This study is expected to open avenues for the production of a large family of supramolecular dendrimers with different phases and feature dimensions oriented by the DSA approach.

Stable α‐CsPbI3 Perovskite Nanowire Arrays with Preferential Crystallographic Orientation for Highly Sensitive Photodetectors

AbstractAll‐inorganic metal‐halide perovskites CsPbX3 (X = Cl, Br, I) exhibit higher stability than their organic–inorganic hybrid counterparts, but the thermodynamically instable perovskite α phase at room temperature of CsPbI3 restricts the practical optoelectronic applications. Although the stabilization of α‐CsPbI3 polycrystalline thin films is extensively studied, the creation of highly crystalline micro/nanostructures of α‐CsPbI3 with large grain size and suppressed grain boundary remains challenging, which impedes the implementations of α‐CsPbI3 for lateral devices, such as photoconductor‐type photodetectors. In this work, stable α‐CsPbI3 perovskite nanowire arrays are demonstrated with large grain size, high crystallinity, regulated alignment, and position by controlling the dewetting dynamics of precursor solution on an asymmetric‐wettability topographical template. The correlation between the higher photoluminescence (PL) intensity and longer PL lifetime indicates the nanowires exhibit stable α phase and suppressed trap density. The preferential (100) orientation is characterized by discrete diffraction spots in grazing incidence wide‐angle scattering patterns, suggesting the long‐range crystallographic order of these nanowires. Based on these high‐quality nanowire arrays, highly sensitive photodetectors are realized with a responsivity of 1294 A W−1 and long‐term stability with 90% performance retention after 30‐day ambient storage.

Customizing topographical templates for aperiodic nanostructures of block copolymers via inverse design.

The limited complexity of self-assembled nanostructures of block copolymers seriously impedes their potential utility in the semiconductor industry. Therefore, the customizability of complex nanostructures has been a long-standing goal for the utilization of directed self-assembly in nanolithography. Herein, we integrated an advanced inverse design algorithm with a well-developed theoretical model to deduce inverse solutions of topographical templates to direct the self-assembly of block copolymers into reproducible target structures. The deduced templates were optimized by finely tuning the input parameters of the inverse design algorithm and through symmetric operation as well as nanopost elimination. More importantly, our developed algorithm has the capability to search inverse solutions of topographical templates for aperiodic nanostructures over exceptionally large areas. These results reveal design rules for guiding templates for the device-oriented nanostructures of block copolymers with prospective applications in nanolithography.

Arrangement of self-assembled ZnO-NiO nanostructures using topographical templates towards oxide directed self-assembly

Self-assembled oxide composite nanostructures offer novel functionalities and three-dimensional architectures, such as vertical pillars and matrix structures. One of the challenges in this field is to precisely control the positional arrangement of oxide pillars embedded in a matrix. Here, we report on an early proof-of-concept demonstration for positioning and arranging self-assembled NiO pillars in a ZnO matrix. SrTiO3 templates with artificial line groove patterns were fabricated by nanoimprint lithography (NIL). High-density NiO pillars were observed on both sides of the template line edges as well as a single array of NiO pillars in the middle of each line groove for a 90 nm line width. This simple technique provides a path towards the development of nanoscale design and applications for memory devices.Self-assembled oxide composite nanostructures offer novel functionalities and three-dimensional architectures, such as vertical pillars and matrix structures. One of the challenges in this field is to precisely control the positional arrangement of oxide pillars embedded in a matrix. Here, we report on an early proof-of-concept demonstration for positioning and arranging self-assembled NiO pillars in a ZnO matrix. SrTiO3 templates with artificial line groove patterns were fabricated by nanoimprint lithography (NIL). High-density NiO pillars were observed on both sides of the template line edges as well as a single array of NiO pillars in the middle of each line groove for a 90 nm line width. This simple technique provides a path towards the development of nanoscale design and applications for memory devices.

Regulated Dewetting for Patterning Organic Single Crystals with Pure Crystallographic Orientation toward High Performance Field‐Effect Transistors

AbstractFabrication of high‐quality organic single‐crystalline semiconductors and their deterministic patterning are core opportunities as well as challenges for large‐scale integration of functional devices with high efficiency and boosted performance. Previous approaches on solution patterning of organic semiconductors have achieved efficient and versatile control of the position, alignment, and size of organic structures. However, the poorly controllable dewetting dynamics of organic solution gives rise to low crystallinity and disordered crystallographic orientation of generated organic architectures that limit their device performance. Here, 1D organic single‐crystal arrays with high crystallinity, strict crystallographic alignment, precise position, tunable, and homogeneous size are fabricated by exploiting an asymmetric‐wettability topographical template. Periodically arranged micropillars with lyophobic sidewalls and lyophilic tops permit the generation of capillary bridges, which enable unidirectional dewetting of organic solution and ordered packing of molecules. The 1D arrays present pure (100) crystallographic orientation with π–π stacking of molecules in the optimal direction of carrier transport, leading to high carrier mobility of 8.7 cm2 V−1 s−1 in the field‐effect transistor measurements. A facile pressure sensor based on the patterned belt arrays is fabricated, exhibiting high sensitivity and long‐term stability.

Programmable Assembly of Hybrid Nanoclusters.

Hybrid nanoparticle clusters (often metallic) are interesting plasmonic materials with tunable resonances and a near-field electromagnetic enhancement at interparticle junctions. Therefore, in recent years, we have witnessed a surge in both the interest in these materials and the efforts to obtain them. However, a versatile fabrication of hybrid nanoclusters, that is, combining more than one material, still remains an open challenge. Current lithographical or self-assembly methods are limited to the preparation of hybrid clusters with up to two different materials and typically to the fabrication of hybrid dimers. Here, we provide a novel strategy to deposit and align not only hybrid dimers but also hybrid nanoclusters possessing more complex shapes and compositions. Our strategy is based on the downscaling of sequential capillarity-assisted particle assembly over topographical templates. As a proof of concept, we demonstrate dimers, linear trimers, and 2D nanoclusters with programmable compositions from a range of metallic nanoparticles. Our process does not rely on any specific chemistry and can be extended to a large variety of particles and shapes. The template also simultaneously aligns the hybrid (often anisotropic) nanoclusters, which could facilitate device integration, for example, for optical readout after transfer to other substrates by a printing step. We envisage that this new fabrication route will enable the assembly and positioning of complex hybrid nanoclusters of different functional nanoparticles to study coupling effects not only locally but also at larger scales for new nanoscale optical devices.

An embedded neutral layer for advanced surface affinity control in grapho-epitaxy directed self-assembly.

Advanced surface affinity control for grapho-epitaxy directed self-assembly (DSA) patterning is essential for providing reliable DSA-based solutions for the development of semiconductor patterning. Independent control of surface affinity between the bottom and the sidewalls of a topographical guiding structure was achieved by embedding an ultrathin layer in the guiding template stack. The implementation of an embedded layer with tunable surface properties for DSA grapho-epitaxy was evaluated and optimized on 300 mm wafers by critical dimension SEM characterization. It was demonstrated that a thin protective layer, placed between the hard mask guiding template and the embedded layer, allows the preservation of the surface properties of the embedded layer during guiding template etching. The DSA performances of this novel grapho-epitaxy integration, using a topographical template patterned with 193 nm immersion lithography, were evaluated by monitoring the success rate and the critical dimension uniformity of the shrunk contacts. FIB-STEM analyses were further carried out to analyze the residual polymer thickness on the resulting contacts. This new integration leads to the control of the polymer residual thickness (a few nanometers) and uniformity (inferior to 1 nm) at the bottom of the guiding template which will facilitate the subsequent DSA pattern transfer.