High Aspect Ratio Nanoscale Pores through BCP-Based Metal Oxide Masks and Advanced Dry Etching.

The reliable and regular modification of the surface properties of substrates plays a crucial role in material research and the development of functional surfaces. A key aspect of this is the development of the surface pores and topographies. These can confer specific advantages such as high surface area as well as specific functions such as hydrophobic properties. Here, we introduce a combination of nanoscale self-assembled block-copolymer-based metal oxide masks with optimized deep reactive ion etching (DRIE) of silicon to permit the fabrication of porous topographies with aspect ratios of up to 50. Following the evaluation of our procedure and involved parameters using various techniques, such as AFM or SEM, the suitability of our features for applications relying on high light absorption as well as efficient thermal management is explored and discussed in further detail.

Highly Ordered Porous Inorganic Structures via Block Copolymer Lithography: An Application of the Versatile and Selective Infiltration of the "Inverse" P2VP-b-PS System.

A facile and versatile strategy was developed to produce highly ordered porous metal oxide structures via block copolymer (BCP) lithography. Phase separation of poly(2-vinylpyridine)-b-polystyrene (P2VP-b-PS) was induced by solvent vapor annealing in a nonselective solvent environment to fabricate cylindrical arrays. In this work, we thoroughly analyzed the effects of the film thickness, solvent annealing time, and temperature on the ordering of a P2VP-majority system for the first time, resulting in "inverse" structures. Reflectometry, atomic force microscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy were used to characterize the formation of the highly ordered BCP morphology and the subsequently produced metal oxide film. At 40 min solvent annealing time, hexagonally close packed structures were produced with cylinder diameters ∼40 nm. Subsequently, the BCP films were infiltrated with different metal cations. Metal ions (Cr, Fe, Ni, and Ga) selectively infiltrated the P2VP domain, while the PS did not retain any detectable amount of metal precursor. This gave rise to a metal oxide porous structure after a UV/ozone (UVO) treatment. The results showed that the metal oxide structures demonstrated high fidelity compared to the BCP template and cylindrical domains presented a similar size to the previous PS structure. Moreover, XPS analyses revealed the complete elimination of the BCP template and confirmed the presence of the metal oxides. These metal oxides were used as hard masks for pattern transfer via dry etching as a further application. Silicon nanopores were fabricated mimicking the BCP template and demonstrated a pore depth of ∼50 nm. Ultimately, this strategy can be applied to create different inorganic nanostructures for a diverse range of applications, for example, solar cells, diodes, and integrated circuits. Furthermore, by optimizing the etching parameters, deeper structures can be obtained via ICP/RIE processes, leading to many potential applications.

Optimization and Control of Large Block Copolymer Self-Assembly via Precision Solvent Vapor Annealing.

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 (ϕs). Phase separation on timescales of ∼10 min is demonstrated once a thickness-dependent threshold ϕs value of ∼0.80-0.86 is achieved, resulting in lamellar feature spacings of over 190 nm. The threshold ϕs value was found to be greater for films with higher dry thickness (D 0) values. Tunability of the domain morphology is achieved through controlled variation of both D 0 and ϕs, with the kinetically unstable hexagonal perforated lamellar (HPL) phase observed at ϕs values of ∼0.67 and D 0 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 ϕs 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 ϕs up to a maximum value at which the films transition to a disordered state. Thicker films are shown to possess a higher maximum ϕs 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 ϕs 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.