Ross Lundy

Polymer brushes are widely used to control the surface chemistry of substrates and selectively block or allow metal deposition on samples. Polymer brushes have advantages such as the possibility of conformal coatings and chemical binding to surfaces, thus improving stability. Despite progress in the application of polymer brushes such as poly­(methyl methacrylate) (PMMA) and polystyrene (PS) for area-selective deposition (ASD), brush removal and activation have not been widely investigated. Herein, we present a method to fabricate a stacked brush APTS-PS or APTS-PMMA composite and investigate brush removal with UV ozone (UVO) treatment and oxygen plasma ashing. We believe this work will lead to improved processing of brushes and allow for the advancement of the ASD field.

Fabrication of ultrathin films of dielectric (with particular reference to materials with high dielectric constants) materials has significance in many advanced technological applications including hard protective coatings, sensors, and next-generation logic devices. Current state-of-the-art in microelectronics for fabricating these thin films is a combination of atomic layer deposition and photolithography. As feature size decreases and aspect ratios increase, conformality of the films becomes paramount. Here, we show a polymer brush template-assisted deposition of highly conformal, ultrathin (sub 5 nm) high-κ dielectric metal oxide films (hafnium oxide and zirconium oxide) on topographically patterned silicon nitride substrates. This technique, using hydroxyl terminated poly-4-vinyl pyridine (P4VP-OH) as the polymer brush, allows for conformal deposition with uniform thickness along the trenches and sidewalls of the substrate. Metal salts are infiltrated into the grafted monolayer polymer brush films via solution deposition. Tailoring specific polymer interfacial chemistries for ion infiltration combined with subsequent oxygen plasma treatment enabled the fabrication of high-quality sub 5 nm metal oxide films.

Research into the fabrication of polymer brushes for use in Area Selective Deposition (ASD) is vital for the understanding of ‘bottom up’ lithographic techniques such as block copolymer (BCP) lithography. Polystyrene has been extensively studied as a blocking material and has been shown to reject both liquid and vapour phase precursors in block copolymer structures. In this work, we demonstrate that thin polystyrene brushes can effectively block atomic layer deposition processes (ALD), offering a route to area deactivation. The effect of varying the molecular weight and fabricating solution concentration of polystyrene (PS) on the overall brush thickness using the grafting-to method is presented in detail. Ellipsometry shows that an increase in molecular weight and solution concentration yields an increase in brush thickness. We demonstarte that PS brush thickness has a significant impact on the blocking efficacy of a HfO₂ ALD process, using X-ray photoelectron spectroscopy as the primary characterisation technique. Results show that the thickest brushes fabricated in this work successfully blocked a process that would result in 19 nm of HfO₂ on native oxide covered Si. Due to the significantly faster fabrication times of PS brushes, this process is deemed a highly competitive alternative to the more widely used ASD methodologies such as self-assembled monolayers (SAMs).

We demonstrate the fabrication of sub-20 nm gate-all-around silicon (Si) nanowire field effect transistor structures using self-assembly. To create nanopatterned Si feature arrays, a block-copolymer-assisted hard mask approach was utilized using a topographically patterned substrate with well-defined Si₃N₄ features for graphoepitaxially alignment of the self-assembled patterns. Microphase-separated long-range ordered polystyrene-b-poly(ethylene oxide) (PS-b-PEO) block-copolymer-derived dot and line nanopatterns were achieved by a thermo-solvent approach within the substrate topographically defined channels of various widths and lengths. Solvent annealing parameters (temperature, annealing time, etc.) were varied to achieve the desired patterns. The BCP structures were modified by anhydrous ethanol to facilitate insertion of iron oxide features within the graphoepitaxial trenches that maintained the parent BCP arrangements. Vertical and horizontal ordered Si nanowire structures within trenches were fabricated using the iron oxide features as hard masks in an inductively coupled plasma (ICP) etch process. Cross-sectional micrographs depict wires of persistent width and flat sidewalls indicating the effectiveness of the mask. The aspect ratios could be varied by varying etch times. The sharp boundaries between the transistor components was also examined through the elemental mapping.

We present a highly scalable, room-temperature strategy for fabricating vertical silicon nanotube arrays derived from a toroidal micelle pattern via a water vapor-induced block copolymer (BCP) self-assembly mechanism. A polystyrene-b-poly(ethylene oxide) (PS-b-PEO) BCP system can be self-assembled into toroidal micelle structures (diameter: 400–600 nm) on a PS-OH-modified substrate in a facile manner contrasting with other complex processes described in the literature. It was found that a minimum PS-b-PEO thickness of ∼86 nm is required for the toroidal self-assembly. Furthermore, a water vapor annealing treatment at room conditions (∼25 °C, 60 min) is shown to vastly enhance the ordering of micellar structures. A liquid-phase infiltration process was used to generate arrays of iron and nickel oxide nanorings. These oxide structures were used as templates for pattern transfer into the underlying silicon substrate via plasma etching, resulting in large-area 3D silicon nanotube arrays. The overall simplicity of this technique, as well as the wide potential versatility of the resulting metal structures, proves that such room-temperature synthesis routes are a viable pathway for complex nanostructure fabrication, with potential applicability in fields such as optics or catalysis.

The self-assembly of ultra-high molecular weight (UHMW) block copolymers (BCPs) remains a complex and time-consuming endeavor owing to the high kinetic penalties associated with long polymer chain entanglement. In this work, we report a unique strategy of overcoming these kinetic barriers through precision solvent annealing of an UHMW polystyrene-block-poly(2-vinylpyridine) BCP system (M_w: ∼800 kg/mol) by fast swelling to very high levels of solvent concentration (ϕ_s). Phase separation on timescales of ∼10 min is demonstrated once a thickness-dependent threshold ϕ_s value of ∼0.80–0.86 is achieved, resulting in lamellar feature spacings of over 190 nm. The threshold ϕ_s value was found to be greater for films with higher dry thickness (D₀) values. Tunability of the domain morphology is achieved through controlled variation of both D₀ and ϕ_s, with the kinetically unstable hexagonal perforated lamellar (HPL) phase observed at ϕ_s values of ∼0.67 and D₀ values of 59–110 nm. This HPL phase can be controllably induced into an order–order transition to a lamellar morphology upon further increase of ϕ_s to 0.80 or above. As confirmed by grazing-incidence small-angle X-ray scattering, the lateral ordering of the lamellar domains is shown to improve with increasing ϕ_s up to a maximum value at which the films transition to a disordered state. Thicker films are shown to possess a higher maximum ϕ_s value before transitioning to a disordered state. The swelling rate is shown to moderately influence the lateral ordering of the phase-separated structures, while the amount of hold time at a particular value of ϕ_s does not notably enhance the phase separation process. These large period self-assembled lamellar domains are then employed to facilitate pattern transfer using a liquid-phase infiltration method, followed by plasma etching, generating ordered, high aspect ratio Si nanowall structures with spacings of ∼190 nm and heights of up to ∼500 nm. This work underpins the feasibility of a room-temperature, solvent-based annealing approach for the reliable and scalable fabrication of sub-wavelength nanostructures via BCP lithography.

Developing vapor phase infiltration (VPI) processes for area selective polymer nanopatterning requires substantial advancement in understanding precursor infiltration, precursor–polymer interaction and process parameters. In this work, infiltration receptive poly(2-vinylpyridine) (P2VP) and poly(4-vinylpyridine) (P4VP) brushes were exposed to a trimethylaluminum (TMA) VPI process and compared to a non-receptive polystyrene (PS) system. The interaction that takes place between TMA and P2VP/P4VP was analysed in detail and we report on notable advantages in the use of P4VP, arising from the difference in position of the pyridinic nitrogen. The VPI process was performed in a commercial atomic layer deposition reactor and the effects of the fundamental process parameters on the three polymer brushes were investigated to ensure optimal area selectivity. In situ X-ray photoelectron spectroscopy (XPS) measurements were supported by grazing angle Fourier transform infrared spectroscopy (GA-FTIR) and hard X-ray photoelectron spectroscopy (HAXPES). The report identifies several important factors when developing a VPI process to ensure area selectivity, while also demonstrating the use of novel pyridine containing polymers for VPI area selective purposes.

In this work, we show that in order to fabricate coherent titania (TiO₂) films with precise thickness control, it is critical to generate a complete polymer brush monolayer. To date, demonstrations of such dense polymer monolayer formation that can be utilized for inorganic infiltration have been elusive. We describe a versatile bottom-up approach to covalently and rapidly (60 s processing) graft hydroxyl-terminated poly(2-vinyl pyridine) (P2VP-OH) polymers on silicon substrates. P2VP-OH monolayer films of varying thicknesses can subsequently be used to fabricate high-quality TiO₂ films. Our innovative strategy is based upon room-temperature titanium vapor-phase infiltration of the grafted P2VP-OH polymer brushes that can produce TiO₂ nanofilms of 2–4 nm thicknesses. Crucial parameters are explored, including molecular weight and solution concentration for grafting dense P2VP-OH monolayers from the liquid phase with high coverage and uniformity across wafer-scale areas (>2 cm²). Additionally, we compare the P2VP-OH polymer systems with another reactive polymer, poly(methyl methacrylate)-OH, and a relatively nonreactive polymer, poly(styrene)-OH. Furthermore, we prove the latter to be effective for surface blocking and deactivation. We show a simple process to graft monolayers for polymers that are weakly interacting with one another but more challenging for reactive systems. Our methodology provides new insight into the rapid grafting of polymer brushes and their ability to form TiO₂ films. We believe that the results described herein are important for further expanding the use of reactive and unreactive polymers for fields including area-selective deposition, solar cell absorber layers, and antimicrobial surface coatings.

A Mn coordination cluster whose core shares some features with the natural oxygen evolving complex provides a bio-inspired complex that promotes catalytic H ₂ O oxidation at neutral pH value.