Nanopatterning Technique Research Articles

Low‐Temperature Dual‐Material Area‐Selective Deposition: Molybdenum Hexafluoride‐Mediated SiO2 Fluorination/Passivation for Self‐Aligned Molybdenum/Metal Oxide Nanoribbons

AbstractArea‐selective deposition (ASD) is a forefront nanopatterning technique gaining substantial attention in the semiconductor industry. While current research primarily addresses single‐material ASD, exploring multi‐material ASD is essential for mitigating complexity in advanced nanopatterning. This study describes molybdenum hexafluoride (MoF6)‐mediated fluorination/passivation of the hydroxylated SiO2 (SiO2‒OH) at 250 °C as a new method to pacify nucleation during subsequent ZnO and TiO2 atomic layer deposition (ALD). In contrast, Al2O3 ALD is not passivated on the fluorinated SiO2 (SiO2‒F). The study further shows that Mo ALD using MoF6 and silane (1 wt% SiH4 in Ar) selectively proceeds on hydrogen‐terminated Si (Si‒H), whereas SiO2‒OH becomes fluorine‐passivated without observable Mo deposition. This enables subsequent ZnO and TiO2 ASD on Mo versus SiO2‒F, as confirmed by X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and scanning transmission electron microscopy (STEM). Proposed growth and inhibition mechanisms highlight the importance of the metal oxide precursor in achieving selectivity. Taken together, self‐aligned Mo/ZnO and Mo/TiO2 nanoribbons are demonstrated on coplanar nanoscale Si‒H/SiO2‒OH patterns by sequentially integrating two individual ASD processes: 1) Mo ASD on Si‒H versus SiO2‒OH; and 2) ZnO or TiO2 ASD on Mo versus SiO2‒F. This work highlights the potential for this approach in new ASD systems.

Area-selective atomic layer deposition (AS-ALD) of low temperature (300 °C) cobalt thin film using octadecyltrichlorosilane (ODTS) self-assembled monolayers (SAMs)

As the semiconductor industry advances, manufacturing technologies encounter challenges in achieving precise alignment and thickness control with smaller and more intricate 3D structures. Addressing this, Area-selective atomic layer deposition (AS-ALD) emerges as a promising “bottom-up” approach, offering an alternative to current nano-patterning techniques. To achieve AS-ALD, self-assembled monolayers (SAMs) are employed as inhibitor agents. In this study, we employed plasma-enhanced atomic layer deposition (PEALD) to promote self-limiting surface reactions and enable low-temperature processing, thereby facilitating the implementation of high purity cobalt (Co) film through AS-ALD using octadecyltrichlorosilane (ODTS) SAM as an inhibitor. The selective deposition is achieved by employing SAMs as an inhibitor, belonging to the deactivation process, a common method for realizing a bottom-up approach. SAMs can form a thin organic film on a solid surface, allowing for surface modifications to become hydrophobic or hydrophilic. Through the selective deposition of Co in the PEALD low-temperature process (300 °C), we successfully addressed the degradation issue of ODTS SAM and verified the successful achievement of a high-purity selectively deposited 13.4 nm Co film. Our findings highlight the potential of selective Co deposition for realizing complex 3D structures and narrow interconnection layers.

Optically Controlled Nano-Transducers Based on Cleaved Superlattices for Monitoring Gigahertz Surface Acoustic Vibrations.

Surface acoustic waves (SAWs) convey energy at subwavelength depths along surfaces. Using interdigital transducers (IDTs) and opto-acousto-optic transducers (OAOTs), researchers have harnessed coherent SAWs with nanosecond periods and micrometer localization depth for various applications. These applications include the sensing of small amount of materials deposited on surfaces, assessing surface roughness and defects, signal processing, light manipulation, charge carrier and exciton transportation, and the study of fundamental interactions with thermal phonons, photons, magnons, and more. However, the utilization of cutting-edge OAOTs produced through surface nanopatterning techniques has set the upper limit for coherent SAW frequencies below 100 GHz, constrained by factors such as the quality and pitch of the surface nanopattern, not to mention the electronic bandwidth limitations of the IDTs. In this context, unconventional optically controlled nanotransducers based on cleaved superlattices (SLs) are here presented as an alternative solution. To demonstrate their viability, we conducted proof-of-concept experiments using ultrafast lasers in a pump-probe configuration on SLs made of alternating AlxGa1-xAs and AlyGa1-yAs layers with approximately 70 nm periodicity and cleaved along their growth direction to produce a periodic nanostructured surface. The acoustic vibrations, generated and detected by laser beams incident on the cleaved surface, span a range from 40 to 70 GHz, corresponding to the generalized surface Rayleigh mode and bulk modes within the dispersion relation. This exploration shows that, in addition to SAWs, cleaved SLs offer the potential to observe surface-skimming longitudinal and transverse acoustic waves at GHz frequencies. This proof-of-concept demonstration below 100 GHz in nanoacoustics using such an unconventional platform might be useful for realizing sub-THz to THz coherent surface acoustic vibrations in the future, as SLs can be epitaxially grown with atomic-scale layer width and quality.

Performance of laser patterned copper plasmonic photocathodes

We study ultrafast laser surface nanopatterning as an alternative to improve the photo-emissive properties of metallic photocathodes. By tailoring the physical dimensions of these surface nanostructures, one can localize the optical field intensity and exploit plasmonic effects occurring in such nanostructures. As a result, this surface nanopatterning technique can become a great tool for improving metallic photocathodes photoemission behavior enabling their use for next generation high brightness electron sources. Our goal is to investigate such surface-plasmon assisted photoemission processes with a view on simplifying the photocathode production at CERN while extending the lifetime of existing photoinjectors. The performance of two different femtosecond laser nanopatterned plasmonic photocathodes was analyzed by measuring the quantum yield with a 65kV DC electron gun utilizing 266nm laser excitation generated by a nanosecond laser with 5ns pulse duration and 10Hz repetition rate. By comparing the electron emission of the copper surface nanostructured areas with that of a flat area, our results suggest quantum yield enhancements of up to a factor of 5.

Molecular Mechanism of Selective Al2O3 Atomic Layer Deposition on Self-Assembled Monolayers.

Area-selective atomic layer deposition (AS-ALD) of insulating metallic oxide layers could be a useful nanopatterning technique for making increasingly complex semiconductor circuits. Although the alkanethiol self-assembled monolayer (SAM) has been considered promising as an ALD inhibitor, the low inhibition efficiency of the SAM during ALD processes makes its wide application difficult. We investigated the deposition mechanism of Al2O3 on alkanethiol-SAMs using temperature-dependent vibrational sum-frequency-generation spectroscopy. We found that the thermally induced formation of gauche defects in the SAMs is the main causative factor deteriorating the inhibition efficiency. Here, we demonstrate that a discontinuously temperature-controlled ALD technique involving self-healing and dissipation of thermally induced stress on the structure of SAM substantially enhances the SAM's inhibition efficiency and enables us to achieve 60 ALD cycles (6.6 nm). We anticipate that the present experimental results on the ALD mechanism on the SAM surface and the proposed ALD method will provide clues to improve the efficiency of AS-ALD, a promising nanoscale patterning and manufacturing technique.

Toward Single Cell Tattoos: Biotransfer Printing of Lithographic Gold Nanopatterns on Live Cells.

Lithographic nanopatterning techniques such as photolithography, electron-beam lithography, and nanoimprint lithography (NIL) have revolutionized modern-day electronics and optics. Yet, their application for creating nanobio interfaces is limited by the cytotoxic and two-dimensional nature of conventional fabrication methods. Here, we present a biocompatible and cost-effective transfer process that leverages (a) NIL to define sub-300 nm gold (Au) nanopattern arrays, (b) amine functionalization of Au to transfer the NIL-arrays from a rigid substrate to a soft transfer layer, (c) alginate hydrogel as a flexible, degradable transfer layer, and (d) gelatin conjugation of the Au NIL-arrays to achieve conformal contact with live cells. We demonstrate biotransfer printing of the Au NIL-arrays on rat brains and live cells with high pattern fidelity and cell viability and observed differences in cell migration on the Au NIL-dot and NIL-wire printed hydrogels. We anticipate that this nanolithography-compatible biotransfer printing method could advance bionics, biosensing, and biohybrid tissue interfaces.

Microfabrication Process Development for a Polymer-Based Lab-on-Chip Concept Applied in Attenuated Total Reflection Fourier Transform Infrared Spectroelectrochemistry.

Micro electro-mechanical systems (MEMS) combining sensing and microfluidics functionalities, as are common in Lab-on-Chip (LoC) devices, are increasingly based on polymers. Benefits of polymers include tunable material properties, the possibility of surface functionalization, compatibility with many micro and nano patterning techniques, and optical transparency. Often, additional materials, such as metals, ceramics, or silicon, are needed for functional or auxiliary purposes, e.g., as electrodes. Hybrid patterning and integration of material composites require an increasing range of fabrication approaches, which must often be newly developed or at least adapted and optimized. Here, a microfabrication process concept is developed that allows one to implement attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and electrochemistry on an LoC device. It is designed to spatially resolve chemical sensitivity and selectivity, which are instrumental for the detection of chemical distributions, e.g., during on-flow chemical and biological reaction chemistry. The processing sequence involves (i) direct-write and soft-contact UV lithography in SUEX dry resist and replication in polydimethylsiloxane (PDMS) elastomers as the fluidic structure; (ii) surface functionalization of PDMS with oxygen plasma, 3-aminopropyl-triethoxysilane (APTES), and a UV-curable glue (NOA 73) for bonding the fluidic structure to the substrate; (iii) double-sided patterning of silicon nitride-coated silicon wafers serving as the ATR-FTIR-active internal reflection element (IRE) on one side and the electrode-covered substrate for microfluidics on the back side with lift-off and sputter-based patterning of gold electrodes; and (iv) a custom-designed active vacuum positioning and alignment setup. Fluidic channels of 100 μm height and 600 μm width in 5 mm thick PDMS were fabricated on 2" and 4" demonstrators. Electrochemistry on-chip functionality was demonstrated by cyclic voltammetry (CV) of redox reactions involving iron cyanides in different oxidation states. Further, ATR-FTIR measurements of laminar co-flows of H2O and D2O demonstrated the chemical mapping capabilities of the modular fabrication concept of the LoC devices.

Thermal Nanoimprint Lithography-A Review of the Process, Mold Fabrication, and Material.

Micro- and nanopatterns perform unique functions and have attracted attention in various industrial fields, such as electronic devices, microfluidics, biotechnology, optics, sensors, and smart and anti-adhesion surfaces. To put fine-patterned products to practical use, low-cost patterning technology is necessary. Nanoimprint lithography (NIL) is a promising technique for high-throughput nanopattern fabrication. In particular, thermal nanoimprint lithography (T-NIL) has the advantage of employing flexible materials and eliminating chemicals and solvents. Moreover, T-NIL is particularly suitable for compostable and recyclable materials, especially when applying biobased materials for use in optics and electronics. These attributes make T-NIL an eco-friendly process. However, the processing time of normal T-NIL is longer than that of ultraviolet (UV) NIL using a UV-curable resin because the T-NIL process requires heating and cooling time. Therefore, many studies focus on improving the throughput of T-NIL. Specifically, a T-NIL process based on a roll-to-roll web system shows promise for next-generation nanopatterning techniques because it enables large-area applications with the capability to process webs several meters in width. In this review, the T-NIL process, roll mold fabrication techniques, and various materials are introduced. Moreover, metal pattern transfer techniques using a combination of nanotransfer printing, T-NIL, and a reverse offset are introduced.

Multiscale CFD Modeling of Area-Selective Atomic Layer Deposition: Application to Reactor Design and Operating Condition Calculation

Area-selective atomic layer deposition (ASALD) as a bottom-up nanopatterning technique has gained recognition for its ability to address misalignment issues in semiconductor manufacturing. This in silico study investigates process operation conditions for ASALD of SiO2/Al2O3 and reactor optimization by using multiscale computational fluid dynamics (CFD) modeling. Several reactor designs were modeled in Ansys Workbench and their results compared to ensure effective reagent separation and homogeneous exposure to reagents across the wafer. Annular reaction zones and asymmetrical inlets enhanced uniform exposure to reagents and minimized reagent intermixing, which allowed the reactor to tolerate higher rotational speeds. Additionally, low rotation speeds and high species mole fractions were required for complete deposition of a cycle of the ASALD process. This research provides insight into the ASALD process operation and contributes to further industrial versatility.

Enhancing Performance and Function of Polymethacrylate Extreme Ultraviolet Resists Using Area-Selective Deposition

Extreme ultraviolet (EUV) lithography is a critical enabler in next-generation technology, although the low etch resistance of conventional organic EUV resists results in low resolution pattern transfer, particularly for smaller features. In this work, we integrate area-selective deposition (ASD), a bottom-up nanopatterning technique, with EUV resists of industrially relevant thicknesses (<50 nm thick) to form resist hardening or tone inverting layers for improved resolution. We utilize TiO2 ASD via atomic layer deposition on 25–35 nm thin photosensitive polymethacrylate-based EUV materials. By tuning the polymer structure and functionality, we enable different scenarios for selective deposition on top of the resist, infiltrated into the bulk resist, or selective to the resist. We find that a cyclohexyl protecting group causes TiO2 inhibition, thus showing promise for tone inversion applications with oxide underlayers. In contrast, resist materials containing a tert-butyl protecting group are good candidates for resist hardening because they enable TiO2 deposition on both EUV exposed and unexposed polymers. Furthermore, we report the integration of a dimethylamino-trimethylsilane inhibitor with the resists to inhibit TiO2 surface nucleation and facilitate subsurface diffusion, thus further broadening potential applications. The results described here establish an important baseline for utilizing ASD on various organic resists to achieve tone inversion or resist hardening and hence improve EUV pattern resolution.

Laser Constructing Short‐Range Disordered Metagratings for Visible Near‐Infrared Polarization‐Independent Absorption

AbstractSubwavelength‐structured metasurfaces working in visible and near‐infrared bands present a high challenge in large‐scale device fabrication. In this study, a scalable, high‐efficient, and low‐cost laser‐induced nanopatterning technique is exploited to fabricate a kind of short‐range disordered metagratings, which enables broadband polarization‐independent absorption in the visible to near‐infrared wavelength. The short‐range disorder of the laser‐induced nanogratings originates from the laser‐induced thermal effect and can be spontaneously organized during laser nanopatterning. The unique disorder can break the unidirectional characteristics of the nanogratings, which empowers the metagratings to excite coupled resonance modes. This helps to achieve near‐perfect absorption in the visible to near‐infrared band (400–1100 nm) with an excellent angular tolerance (up to 60°) and average absorptivities of 96.3% and 93.5% under the TM and TE modes, respectively. These low‐cost metagratings can potentially inspire wide applications in the fields of solar cells, sensing, and thermal emitters.

Investigation of the Effects of Pulse-Atomic Force Nanolithography Parameters on 2.5D Nanostructures' Morphology.

In recent years, Atomic Force Microscope (AFM)-based nanolithography techniques have emerged as a very powerful approach for the machining of countless types of nanostructures. However, the conventional AFM-based nanolithography methods suffer from low efficiency, low rate of patterning, and high complexity of execution. In this frame, we first developed an easy and effective nanopatterning technique, termed Pulse-Atomic Force Lithography (P-AFL), with which we were able to pattern 2.5D nanogrooves on a thin polymer layer. Indeed, for the first time, we patterned nanogrooves with either constant or varying depth profiles, with sub-nanometre resolution, high accuracy, and reproducibility. In this paper, we present the results on the investigation of the effects of P-AFL parameters on 2.5D nanostructures' morphology. We considered three main P-AFL parameters, i.e., the pulse's amplitude (setpoint), the pulses' width, and the distance between the following indentations (step), and we patterned arrays of grooves after a precise and well-established variation of the aforementioned parameters. Optimizing the nanolithography process, in terms of patterning time and nanostructures quality, we realized unconventional shape nanostructures with high accuracy and fidelity. Finally, a scanning electron microscope was used to confirm that P-AFL does not induce any damage on AFM tips used to pattern the nanostructures.

Geometric Control of Cell Behavior by Biomolecule Nanodistribution.

Many dynamic interactions within the cell microenvironment modulate cell behavior and cell fate. However, the pathways and mechanisms behind cell-cell or cell-extracellular matrix interactions remain understudied, as they occur at a nanoscale level. Recent progress in nanotechnology allows for mimicking of the microenvironment at nanoscale in vitro; electron-beam lithography (EBL) is currently the most promising technique. Although this nanopatterning technique can generate nanostructures of good quality and resolution, it has resulted, thus far, in the production of only simple shapes (e.g., rectangles) over a relatively small area (100 × 100 μm), leaving its potential in biological applications unfulfilled. Here, we used EBL for cell-interaction studies by coating cell-culture-relevant material with electron-conductive indium tin oxide, which formed nanopatterns of complex nanohexagonal structures over a large area (500 × 500 μm). We confirmed the potential of EBL for use in cell-interaction studies by analyzing specific cell responses toward differentially distributed nanohexagons spaced at 1000, 500, and 250 nm. We found that our optimized technique of EBL with HaloTags enabled the investigation of broad changes to a cell-culture-relevant surface and can provide an understanding of cellular signaling mechanisms at a single-molecule level.

The Prospects of Colloidal Lithography Towards Low-Cost and Scalable Sensors

Nanosphere lithography (NSL), a colloidal-based nanopatterning technique, has demonstrated versatility for bottom-up and top-down nanofabrication approaches with a simple procedure that can be performed in a standard chemical laboratory. This technique offers versatility for large-area nanopatterning with a low-cost process. Nanopatterned arrays have shown outstanding features in enhancing sensor performance due to their ability to create effective nanoscale physical and chemical changes, high molecular entrapment with the roughened substrate, and means of downscaling toward scalable sensors manufacturing. All these prominent properties have made NSL a promising candidate for scalable biosensors production as its performance is also highly comparable with the pre-existing lithography techniques that mostly require high-cost infrastructure. This mini-review discusses in detail the advantages of colloidal lithography over other lithography techniques from the resolution and scalability of manufacturing. It is emphasized that the cost-competitive NSL technology may be applicable for a broad range of end-users, from high-profit margins, such as communication, technology, and health sectors, to the low-profit margins, such as in food industries. The combinational strategies in NSL are presented, including polystyrene nanotemplating of the substrate, feasible integration with metallic film deposition technologies, and potential application in various sensing platforms.

Versatile Micro and Nano Patterning Technique for TiO2 and TiN‐Based Sol–Gel Thin Films

AbstractThis paper describes a tailored and versatile technology route to achieve micro and nanopatterning of both TiO2 and TiN thin films using a direct photo patternable sol–gel approach combined with a rapid thermal annealing and nitridation process. The approach consists in multi‐scale structuring TiO2 using laser direct writing or mask/colloidal lithography on a wide range of substrates including materials and of diverse geometry. These patterned TiO2 layers can subsequently be converted into a micro‐structured metallic TiN layer using a direct rapid thermal nitridation process that results in metallic thin films (TiN). This work demonstrates the versatility of this complete chain of soft chemistry based new process for patterning TiO2 and TiN thin films thereby avoiding expensive processes such as etching and lift‐off, while preserving their diffractive properties and high thermal stability, that is, up to 1000 °C under vacuum. The process is compatible with different kinds of substrates of different shapes and sizes. These results pave the way for developing a cost‐effective and time‐saving approach to different cutting‐edge applications such as metasurfaces, sensors, and applications in the luxury and decoration sector.

Area‐Selective Atomic Layer Deposition on Functionalized Graphene Prepared by Reversible Laser Oxidation

AbstractArea‐selective atomic layer deposition (ALD) is a promising “bottom‐up” alternative to current nanopatterning techniques. While it has been successfully implemented in traditional microelectronic processes, selective nucleation of ALD on 2D materials has so far remained an unsolved challenge. In this article, a precise control of the selective deposition of ZnO on graphene at low temperatures (&lt;250 °C) is demonstrated. Maskless femtosecond laser writing is used to locally activate predefined surface areas (down to 300 nm) by functionalizing graphene to achieve excellent ALD selectivity (up to 100%) in these regions for 6‐nm‐thick ZnO films. The intrinsic conductive properties of graphene can be restored by thermal annealing at low temperature (300 °C) without destroying the deposited ZnO patterns. As the graphene layer can be transferred onto other material surfaces, the present patterning technique opens new attractive ways for various applications in which the functionalized graphene is utilized as a template layer for selective deposition of desired materials.

Superconducting W-C nanopillars fabricated by Ga+ focused ion beam induced deposition

Ga+ Focused Ion Beam Induced Deposition (FIBID) is a highly flexible, single-step nanopatterning technique that makes use of a focused beam of Ga+ ions to locally induce the decomposition of a gaseous precursor material. In combination with the W(CO)6 precursor, Ga+ FIBID is known to yield a W–C compound that is superconducting below 4.7 ​K. While most reports on Ga+ FIBID-grown W–C focus on in-plane patterning, we demonstrate here that growth along the vertical direction may also be achieved by successively stacking a series of individual patterns that get deposited on top of each other. The nanopillars obtained following this procedure reach up to 10 ​μm in height, and have an aspect ratio of around 50. They exhibit a 68% of metallic W in terms of atomic content, higher than the 40% detected in their in-plane counterparts, while maintaining the superconducting properties. This approach also opens up the possibility of tuning their height and growth angle with respect to the substrate, exhibiting potential applicability in the design of 3D superconducting devices.

On the Electron-Induced Reactions of (CH3)AuP(CH3)3: A Combined UHV Surface Science and Gas-Phase Study.

Focused-electron-beam-induced deposition (FEBID) is a powerful nanopatterning technique where electrons trigger the local dissociation of precursor molecules, leaving a deposit of non-volatile dissociation products. The fabrication of high-purity gold deposits via FEBID has significant potential to expand the scope of this method. For this, gold precursors that are stable under ambient conditions but fragment selectively under electron exposure are essential. Here, we investigated the potential gold precursor (CH3)AuP(CH3)3 using FEBID under ultra-high vacuum (UHV) and spectroscopic characterization of the corresponding metal-containing deposits. For a detailed insight into electron-induced fragmentation, the deposit’s composition was compared with the fragmentation pathways of this compound through dissociative ionization (DI) under single-collision conditions using quantum chemical calculations to aid the interpretation of these data. Further comparison was made with a previous high-vacuum (HV) FEBID study of this precursor. The average loss of about 2 carbon and 0.8 phosphor per incident was found in DI, which agreed well with the carbon content of the UHV FEBID deposits. However, the UHV deposits were found to be as good as free of phosphor, indicating that the trimethyl phosphate is a good leaving group. Differently, the HV FEBID experiments showed significant phosphor content in the deposits.

Electric-Field and Mechanical Vibration-Assisted Atomic Force Microscope-Based Nanopatterning

Abstract Atomic force microscope (AFM)-based nanolithography is a cost-effective nanopatterning technique that can fabricate nanostructures with arbitrary shapes. However, existing AFM-based nanopatterning approaches have limitations in the patterning resolution and efficiency. Minimum feature size and machining performance in the mechanical force-induced nanofabrication process are limited by the radius and sharpness of the AFM tip. Electric-field-assisted atomic force microscope (E-AFM) nanolithography can fabricate nanopatterns with features smaller than the tip radius, but it is very challenging to find the appropriate input parameter window. The tip bias range in E-AFM process is typically very small and varies for each AFM tip due to the variations in tip geometry, tip end diameter, and tip conductive coating thickness. This paper demonstrates a novel electric-field and mechanical vibration-assisted AFM-based nanofabrication approach, which enables high-resolution (sub-10 nm toward sub-5 nm) and high-efficiency nanopatterning processes. The integration of in-plane vibration with the electric field increases the patterning speed, broadens the selectable ranges of applied voltages, and reduces the minimum tip bias required for nanopatterning as compared with E-AFM process, which significantly increases the versatility and capability of AFM-based nanopatterning and effectively avoids the tip damage.

Drawing at the Nanoscale through Macroscopic Movement.

Nanopatterns are important for applications in various nanodevice fields. Existing nanopatterning techniques mainly directly manufacture the nanopatterns through various lithographic methods, which usually are laborious, time-consuming, and need expensive equipment. Here, an extremely simple drawing at the nanoscale (DAN) concept to indirectly fabricate rational nanopatterns through controlling the macroscopic movement of the substrate , is demonstrated. The structure of the nanopatterns is completely determined by and can be shrunk by millions of times from the moving track of the substrate. Multiple surface nanopatterns of different materials with accurately tailorable relative positions can be simply stacked together by moving the substrate by macroscopic distances during different DAN processes. In combination with sophisticated lithographic methods, the DAN method is anticipated to enable substantial advances in nanofabrication.