ABSTRACT
High refractive index (RI) thin films are of critical importance for advanced optical devices, and the high refractive index polymers (HRIPs) constitute an interesting class of materials for high RI thin films due to low cost, good processability, light weight, and high flexibility. However, HRIPs have yet to realize their full potential in high RI thin film applications due to their relatively low RI, strong absorption in the blue light region, and limited film formation methods such as rapid vitrification. Herein, we report a development of a new HRIP thin film generated through a one-step vapor-phase process, termed sulfur chemical vapor deposition (sCVD), using elemental sulfur and divinyl benzene. The developed poly(sulfur-co-divinyl benzene) (pSDVB-sCVD) film exhibited RI (measured at 632.8 nm) exceeding 1.97, one of the highest RIs among polymers without metallic elements reported to date. Because the sCVD utilized vaporized sulfur with a unique sulfur-cracking step, formation of long polysulfide chains was suppressed efficiently, while high sulfur content as high as 85 wt % could be achieved with no apparent phase separation. Unlike most of inorganic high RI materials, pSDVB-sCVD was highly transparent in the entire visible range and showed extremely low birefringence of 10 × 10-4. The HRIP thin film with unprecedentedly high RI, together with outstanding transparency and low birefringence, will serve as a key component in a wide range of high-end optical device applications.
ABSTRACT
High refractive index polymers (HRIPs) have recently emerged as an important class of materials for use in a variety of optoelectronic devices including image sensors, lithography, and light-emitting diodes. However, achieving polymers having refractive index exceeding 1.8 while maintaining full transparency in the visible range still remains formidably challenging. Here, we present a unique one-step vapor-phase process, termed sulfur chemical vapor deposition, to generate highly stable, ultrahigh refractive index (n > 1.9) polymers directly from elemental sulfur. The deposition process involved vapor-phase radical polymerization between elemental sulfur and vinyl monomers to provide polymer films with controlled thickness and sulfur content, along with the refractive index as high as 1.91. Notably, the HRIP thin film showed unprecedented optical transparency throughout the visible range, attributed to the absence of long polysulfide segments within the polymer, which will serve as a key component in a wide range of optical devices.
ABSTRACT
Despite their capability, sub-10 nm periodic nano-patterns formed by strongly segregating block copolymer (BCP) thin films cannot be easily oriented perpendicular to the substrate due to the huge surface energy differences of the constituent blocks. To produce perpendicular nano-patterns, the interfacial energies of both the substrate and free interfaces should be controlled precisely to induce non-preferential wetting. Unfortunately, high-performance surface modification layers are challenging to design, and different kinds of surface modification methods must be devised respectively for each neutral layer and top coat. Furthermore, conventional approaches, largely based on spin-coating processes, are highly prone to defect formation and may readily cause dewetting at sub-10 nm thickness. To date, these obstacles have hampered the development of high-fidelity, sub-5 nm BCP patterns. Herein, an all-vapor phase deposition approach initiated chemical vapor deposition is demonstrated to form 9-nm-thick, uniform neutral bottom layer and top coat with exquisite control of composition and thickness. These layers are employed in BCP films to produce perpendicular cylinders with a diameter of ≈4 nm that propagate throughout a BCP thickness of up to ≈60 nm, corresponding to five natural domain spacings of the BCP. Such a robust approach will serve as an advancement for the reliable generation of sub-10 nm nano-patterns.