“Multipoint Force Feedback” Leveling of Massively Parallel Tip Arrays in Scanning Probe Lithography

Nanoscale patterning with massively parallel 2D array tips is of significant interest in scanning probe lithography. A challenging task for tip‐based large area nanolithography is maintaining parallel tip arrays at the same contact point with a sample substrate in order to pattern a uniform array. Here, polymer pen lithography is demonstrated with a novel leveling method to account for the magnitude and direction of the total applied force of tip arrays by a multipoint force sensing structure integrated into the tip holder. This high‐precision approach results in a 0.001° slope of feature edge length variation over 1 cm wide tip arrays. The position sensitive leveling operates in a fully automated manner and is applicable to recently developed scanning probe lithography techniques of various kinds which can enable “desktop nanofabrication.”     

Graphite patterning in a controlled gas environment

Although a number of methods using scanning probe lithography to pattern graphene have already been introduced, the fabrication of real devices still faces limitations. We report graphite patterning using scanning probe lithography with control of the gas environment. Patterning processes using scanning probe lithography of graphite or graphene are normally performed in air because water molecules forming the meniscus between the tip and the sample mediate the etching reaction. This water meniscus, however, may prevent uniform patterning due to its strong surface tension or large contact angle on surfaces. To investigate this side effect of water, our experiment was performed in a chamber where the gas environment was controlled with methyl alcohol, oxygen or isopropanol gases. We found that methyl alcohol facilitates graphite etching, and a line width as narrow as 3?nm was achieved as methyl alcohol also contains an oxygen atom which gives rise to the required oxidation. Due to its low surface tension and highly adsorptive behavior, methyl alcohol has advantages for a narrow line width and high speed etching conditions.     

Graphene‐Assisted Antioxidation of Tungsten Disulfide Monolayers: Substrate and Electric‐Field Effect

Transition metal dichalcogenides (TMDs) have emerged as promising materials to complement graphene for advanced optoelectronics. However, irreversible degradation of chemical vapor deposition‐grown monolayer TMDs via oxidation under ambient conditions limits applications of TMD‐based devices. Here, the growth of oxidation‐resistant tungsten disulfide (WS₂) monolayers on graphene is demonstrated, and the mechanism of oxidation of WS₂ on SiO₂, graphene/SiO₂, and on graphene suspended in air is elucidated. While WS₂ on a SiO₂ substrate begins oxidation within weeks, epitaxially grown WS₂ on suspended graphene does not show any sign of oxidation, attributed to the screening effect of surface electric field caused by the substrate. The control of a local oxidation of WS₂ on a SiO₂ substrate by a local electric field created using an atomic force microscope tip is also demonstrated.     

Adjustable Intermolecular Interactions Allowing 2D Transition Metal Dichalcogenides with Prolonged Scavenging Activity for Reactive Oxygen Species

There is an increasing demand for control over the dimensions and functions of transition metal dichalcogenides (TMDs) in aqueous solution toward biological and medical applications. Herein, an approach for the exfoliation and functionalization of TMDs in water via modulation of the hydrophobic interaction between poly(ε‐caprolactone)‐b‐poly(ethylene glycol) (PCL‐b‐PEG) and the basal planes of TMDs is reported. Decreasing the hydrophobic PCL length of PCL‐b‐PEG from 5000 g mol^?1 (PCL₅₀₀₀) to 460 g mol^?1 (PCL₄₆₀) significantly increases the exfoliation efficiency of TMD nanosheets because the polymer–TMD hydrophobic interaction becomes dominant over the polymer–polymer interaction. The TMD nanosheets exfoliated by PCL₄₆₀‐b‐PEG₅₀₀₀ (460‐WS₂, 460‐WSe₂, 460‐MoS₂, and 460‐MoSe₂) show excellent and prolonged scavenging activity for reactive oxygen species (ROS), but each type of TMD displays a different scavenging tendency against hydroxyl, superoxide, and 2,2′‐azino‐bis(3‐ethylbenzothiazoline‐6‐sulfonic acid) radicals. A mechanistic study based on electron paramagnetic resonance spectroscopy and density functional theory simulations suggests that radical‐mediated oxidation of TMDs and hydrogen transfer from the oxidized TMDs to radicals are crucial steps for ROS scavenging by TMD nanosheets. As‐prepared 460‐TMDs are able to effectively scavenge ROS in HaCaT human keratinocytes, and also exhibit excellent biocompatibility.     

Resolution Limit in Plasmonic Lithography for Practical Applications beyond 2x‐nm Half Pitch

A theoretical model is introduced to evaluate the ultimate resolution of plasmonic lithography using a ridge aperture. The calculated and experimental results of the line array pattern depth are compared for various half pitches. The theoretical analysis predicts that the resolution of plasmonic lithography strongly depends on the ridge gap, achieving values under 1x nm with a ridge gap smaller than 10 nm. A micrometer‐scale circular contact probe is fabricated for high speed patterning with high positioning accuracy, which can be extended to a high‐density probe array. Using the circular contact probe, high‐density line array patterns are recorded with a half pitch up to 22 nm and good agreement is obtained between the theoretical model and experiment. To record the high density line array patterns, the line edge roughness (LER) is reduced to ≈17 nm from 29 nm using a well‐controlled developing process with a smaller molecular weight KOH‐based developer at a temperature below 10°C.     

Unveiling Active Sites for the Hydrogen Evolution Reaction on Monolayer MoS2

Here, the hydrogen evolution reaction (HER) activities at the edge and basal‐plane sites of monolayer molybdenum disulfide (MoS₂) synthesized by chemical vapor deposition (CVD) are studied using a local probe method enabled by selected‐area lithography. Reaction windows are opened by e‐beam lithography at sites of interest on poly(methyl methacrylate) (PMMA)‐covered monolayer MoS₂ triangles. The HER properties of MoS₂ edge sites are obtained by subtraction of the activity of the basal‐plane sites from results containing both basal‐plane and edge sites. The catalytic performances in terms of turnover frequencies (TOFs) are calculated based on the estimated number of active sites on the selected areas. The TOFs follow a descending order of 3.8 ± 1.6, 1.6 ± 1.2, 0.008 ± 0.002, and 1.9 ± 0.8 × 10^?4 s^?1, found for 1T′‐, 2H‐MoS₂ edges, and 1T′‐, 2H‐MoS₂ basal planes, respectively. Edge sites of both 2H‐ and 1T′‐MoS₂ are proved to have comparable activities to platinum (≈1–10 s^?1). When fitted into the HER volcano plot, the MoS₂ active sites follow a trend distinct from conventional metals, implying a possible difference in the reaction mechanism between transition‐metal dichalcogenides (TMDs) and metal catalysts.     

Scanning probe microscope lithography at the micro- and nano-scales

Scanning probe microscopy (SPM)-based lithography at the micro- and nano-scales is presented. Our method in SPM local oxidation involves two SPM tips, one having a robust blunt tip, a "micrometer tip," and the other having a sharp tip, a "nanometer tip." In tapping-mode SPM local oxidation experiments, Si oxide wires with sub-10 nm resolution were produced by precisely tuning the dynamic properties of the nanometer tip such as drive amplitude and quality factor. On the other hand, in order to perform large-scale oxidation, SPM tip with a contact area of microm2, which is about 10(4) times larger than that of the conventional nanometer tip, was prepared. We propose and demonstrate a method of performing micrometer-scale SPM local oxidation using the micrometer tip under contact-mode operation. The width of the Si oxide produced was clearly determined by the contact length of the tip. Furthermore, we explore the possibility of performing the sub-20 nm lithography of Si surfaces using SPM scratching with a diamond-coated tip. The influence of various scan parameters on the groove size was investigated. The groove size could be precisely controlled by the applied force, scan direction, and the number of scan cycles. There is no effect of the scan speed on the groove size. It is concluded that high-speed nanolithography can be achieved without the degradation of patterns by SPM scratching. SPM-based lithography has the advantage of being able to fabricate a desired structure at an arbitrary position on a surface and plays an important role for bridging the gap between micro- and nano-scales.     

Preparation of High‐Percentage 1T‐Phase Transition Metal Dichalcogenide Nanodots for Electrochemical Hydrogen Evolution

Nanostructured transition metal dichalcogenides (TMDs) are proven to be efficient and robust earth‐abundant electrocatalysts to potentially replace precious platinum‐based catalysts for the hydrogen evolution reaction (HER). However, the catalytic efficiency of reported TMD catalysts is still limited by their low‐density active sites, low conductivity, and/or uncleaned surface. Herein, a general and facile method is reported for high‐yield, large‐scale production of water‐dispersed, ultrasmall‐sized, high‐percentage 1T‐phase, single‐layer TMD nanodots with high‐density active edge sites and clean surface, including MoS₂, WS₂, MoSe₂, Mo_0.5W_0.5S₂, and MoSSe, which exhibit much enhanced electrochemical HER performances as compared to their corresponding nanosheets. Impressively, the obtained MoSSe nanodots achieve a low overpotential of ?140 mV at current density of 10 mA cm^?2, a Tafel slope of 40 mV dec^?1, and excellent long‐term durability. The experimental and theoretical results suggest that the excellent catalytic activity of MoSSe nanodots is attributed to the high‐density active edge sites, high‐percentage metallic 1T phase, alloying effect and basal‐plane Se‐vacancy. This work provides a universal and effective way toward the synthesis of TMD nanostructures with abundant active sites for electrocatalysis, which can also be used for other applications such as batteries, sensors, and bioimaging.     

Recent Developments in Controlled Vapor‐Phase Growth of 2D Group 6 Transition Metal Dichalcogenides

An overview of recent developments in controlled vapor‐phase growth of 2D transition metal dichalcogenide (2D TMD) films is presented. Investigations of thin‐film formation mechanisms and strategies for realizing 2D TMD films with less‐defective large domains are of central importance because single‐crystal‐like 2D TMDs exhibit the most beneficial electronic and optoelectronic properties. The focus is on the role of the various growth parameters, including strategies for efficiently delivering the precursors, the selection and preparation of the substrate surface as a growth assistant, and the introduction of growth promoters (e.g., organic molecules and alkali metal halides) to facilitate the layered growth of (Mo, W)(S, Se, Te)₂ atomic crystals on inert substrates. Critical factors governing the thermodynamic and kinetic factors related to chemical reaction pathways and the growth mechanism are reviewed. With modification of classical nucleation theory, strategies for designing and growing various vertical/lateral TMD‐based heterostructures are discussed. Then, several pioneering techniques for facile observation of structural defects in TMDs, which substantially degrade the properties of macroscale TMDs, are introduced. Technical challenges to be overcome and future research directions in the vapor‐phase growth of 2D TMDs for heterojunction devices are discussed in light of recent advances in the field.     

10 micrometer-scale SPM local oxidation lithography

10 micrometer-scale scanning probe microscopy (SPM) local oxidation lithography was performed on Si. In order to realize large-scale oxidation, an SPM tip with a contact length of 15 microm was prepared by focused-ion-beam (FIB) etching. The oxidation was carried out in contact mode operation with the contact force ranging from 0.1 to 2.1 microN. The applied bias voltage was 50 V, and scanning speed was varied from 10 to 200 microm/s. The scan length was 15 microm for one cycle. The influence of contact force on the large-scale oxidation was investigated. At high contact force, the Si oxide with good size uniformity was obtained even with high scanning speed. The SPM tip with larger contact length may increase the spatial dimensions of the water meniscus between the SPM tip and sample surface, resulting in the larger dimensions of the fabricated oxide. Furthermore, the throughput of large-scale oxidation reached about 10(3) microm2/s by controlling the scanning speed and contact force of the SPM tip. It is suggested that SPM local oxidation can be upscaled by using a SPM tip with large contact length.     

Step and repeat UV nanoimprint lithography on pre-spin coated resist film: a promising route for fabricating nanodevices

A step and repeat UV nanoimprint lithography process on pre-spin coated resist film is demonstrated for patterning a large area with features sizes down to sub-15 nm. The high fidelity between the template and imprinted structures is verified with a difference in their line edge roughness of less than 0.5 nm (3σ deviation value). The imprinted pattern's residual layer is well controlled to allow direct pattern transfer from the resist into functional materials with very high resolution. The process is suitable for fabricating numerous nanodevices.     

Chemically Functionalized Surface Patterning

Patterning substrates with versatile chemical functionalities from micro‐ to nanometer scale is a long‐standing and interesting topic. This review provides an overview of a range of techniques commonly used for surface patterning. The first section briefly introduces conventional micropatterning tools, such as photolithography and microcontact printing. The second section focuses on the currently used nanolithographic techniques, for example, scanning probe lithography (SPL), and their applications in surface patterning. Their advantages and disadvantages are also demonstrated. In the last section, dip‐pen nanolithography (DPN) is emphatically illustrated, with a particular stress on the patterning and applications of biomolecules.     

Nanoimprint Lithography: Methods and Material Requirements

Nanoimprint lithography (NIL) is a nonconventional lithographic technique for high‐throughput patterning of polymer nanostructures at great precision and at low costs. Unlike traditional lithographic approaches, which achieve pattern definition through the use of photons or electrons to modify the chemical and physical properties of the resist, NIL relies on direct mechanical deformation of the resist material and can therefore achieve resolutions beyond the limitations set by light diffraction or beam scattering that are encountered in conventional techniques. This Review covers the basic principles of nanoimprinting, with an emphasis on the requirements on materials for the imprinting mold, surface properties, and resist materials for successful and reliable nanostructure replication.     

Electronic‐Reconstruction‐Enhanced Tunneling Conductance at Terrace Edges of Ultrathin Oxide Films

Quantum mechanical tunneling of electrons across ultrathin insulating oxide barriers has been studied extensively for decades due to its great potential in electronic‐device applications. In the few‐nanometers‐thick epitaxial oxide films, atomic‐scale structural imperfections, such as the ubiquitously existed one‐unit‐cell‐high terrace edges, can dramatically affect the tunneling probability and device performance. However, the underlying physics has not been investigated adequately. Here, taking ultrathin BaTiO₃ films as a model system, an intrinsic tunneling‐conductance enhancement is reported near the terrace edges. Scanning‐probe‐microscopy results demonstrate the existence of highly conductive regions (tens of nanometers wide) near the terrace edges. First‐principles calculations suggest that the terrace‐edge geometry can trigger an electronic reconstruction, which reduces the effective tunneling barrier width locally. Furthermore, such tunneling‐conductance enhancement can be discovered in other transition metal oxides and controlled by surface‐termination engineering. The controllable electronic reconstruction can facilitate the implementation of oxide electronic devices and discovery of exotic low‐dimensional quantum phases.     

Half‐Metallic Behavior in 2D Transition Metal Dichalcogenides Nanosheets by Dual‐Native‐Defects Engineering

Two‐dimensional transition metal dichalcogenides (TMDs) have been regarded as one of the best nonartificial low‐dimensional building blocks for developing spintronic nanodevices. However, the lack of spin polarization in the vicinity of the Fermi surface and local magnetic moment in pristine TMDs has greatly hampered the exploitation of magnetotransport properties. Herein, a half‐metallic structure of TMDs is successfully developed by a simple chemical defect‐engineering strategy. Dual native defects decorate titanium diselenides with the coexistence of metal‐Ti‐atom incorporation and Se‐anion defects, resulting in a high‐spin‐polarized current and local magnetic moment of 2D Ti‐based TMDs toward half‐metallic room‐temperature ferromagnetism character. Arising from spin‐polarization transport, the as‐obtained T‐TiSe_1.8 nanosheets exhibit a large negative magnetoresistance phenomenon with a value of ?40% (5T, 10 K), representing one of the highest negative magnetoresistance effects among TMDs. It is anticipated that this dual regulation strategy will be a powerful tool for optimizing the intrinsic physical properties of TMD systems.     

Recent Progress in Simple and Cost-Effective Top-Down Lithography for ≈10 nm Scale Nanopatterns: From Edge Lithography to Secondary Sputtering Lithography

The development of a simple and cost-effective method for fabricating ≈10 nm scale nanopatterns over large areas is an important issue, owing to the performance enhancement such patterning brings to various applications including sensors, semiconductors, and flexible transparent electrodes. Although nanoimprinting, extreme ultraviolet, electron beams, and scanning probe litho-graphy are candidates for developing such nanopatterns, they are limited to complicated procedures with low throughput and high startup cost, which are difficult to use in various academic and industry fields. Recently, several easy and cost-effective lithographic approaches have been reported to produce ≈10 nm scale patterns without defects over large areas. This includes a method of reducing the size using the narrow edge of a pattern, which has been attracting attention for the past several decades. More recently, secondary sputtering lithography using an ion-bombardment technique was reported as a new method to create high-resolution and high-aspect-ratio structures. Recent progress in simple and cost-effective top-down lithography for ≈10 nm scale nanopatterns via edge and secondary sputtering techniques is reviewed. The principles, technical advances, and applications are demonstrated. Finally, the future direction of edge and secondary sputtering lithography research toward issues to be resolved to broaden applications is discussed.     

One‐Step Solution Phase Growth of Transition Metal Dichalcogenide Thin Films Directly on Solid Substrates

Ultrathin transition metal dichalcogenides (TMDs) have exotic electronic properties. With success in easy synthesis of high quality TMD thin films, the potential applications will become more viable in electronics, optics, energy storage, and catalysis. Synthesis of TMD thin films has been mostly performed in vacuum or by thermolysis. So far, there is no solution phase synthesis to produce large‐area thin films directly on target substrates. Here, this paper reports a one‐step quick synthesis (within 45–90 s) of TMD thin films (MoS₂, WS₂, MoSe₂, WSe₂, etc.) on solid substrates by using microwave irradiation on a precursor‐containing electrolyte solution. The numbers of the quintuple layers of the TMD thin films are precisely controllable by varying the precursor's concentration in the electrolyte solution. A photodetector made of MoS₂ thin film comprising of small size grains shows near‐IR absorption, supported by the first principle calculation, exhibits a high photoresponsivity (>300 mA W^?1) and a fast response (124 µs). This study paves a robust way for the synthesis of various TMD thin films in solution phases.     

Optical control of edge chirality in graphene

We performed optical annealing experiments at the edges of nanopatterned graphene to study the resultant edge reconstruction. The lithographic patterning direction was orthogonal to a zigzag edge. μ-Raman spectroscopy shows an increase in the polarization contrast of the G band as a function of annealing time. Furthermore, transport measurements reveal a 50% increase of the GNR energy gap after optical exposure, consistent with an increased percentage of armchair segments. These results suggest that edge chirality of graphene devices can be optically purified post electron beam lithography, thereby enabling the realization of chiral graphene nanoribbons and heterostructures.     

Molecular layer deposition of functional thin films for advanced lithographic patterning

Photoresist materials comprise one of the main challenges faced by lithography to meet the requirements of electronic device size scaling. Here we report for the first time the use of molecular layer deposition (MLD) to produce photoresist materials with controllable placement of functional moieties. Polyurea resists films are deposited by MLD using urea coupling reactions between 1,4-phenylene diisocyanate (PDIC) and ethylenediamine (ED) or 2,2'-(propane-2,2-diylbis(oxy))diethanamine (PDDE) monomers in a layer-by-layer fashion with a linear growth rate, allowing acid-labile groups to be incorporated into the film at well-controlled positions. The films are deposited with stoichiometric compositions and have highly uniform surface morphology as investigated using atomic force microscopy. We show that acid treatment can cleave the backbone of the polyurea film at positions where the acid-labile groups are embedded. We further show that after soaking the polyurea film with photoacid generator (PAG), it acts as a photoresist material and we present several UV patterning demonstrations. This approach presents a new way to make molecularly designed resist films for lithography.