skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Synthesis of High Refractive Index Polymer Thin Films for Soft, Flexible Optics Through Halomethane Quaternization of Poly(4‐Vinylpyridine)
Abstract Applications in soft, flexible optical, and optoelectronic applications demand polymer thin film coatings that can accommodate substantial physical deformations. The preparation of high refractive index polymers (HRIPs) through the quaternization of poly(4‐vinylpyridine) (P4VP) thin films with (di)halomethanes is presented. P4VP thin films are prepared by initiated chemical vapor deposition (iCVD) and then quaternized through exposure to saturated vapors of iodomethane (CH3I), dibromomethane (CH2Br2), and diiodomethane (CH2I2), resulting in refractive indices (RI) as high as 1.67, 1.71, and 2.07, respectively (at 632.8 nm). Fourier‐transform infrared (FTIR) spectroscopy and X‐ray photoelectron spectroscopy (XPS) confirmed the quaternization of pyridine pendant groups on the polymer chain to n‐methylpyridinium with primarily an iodide or bromide counterion, though a minor fraction of polyiodides are also detected. Additionally, these films demonstrate superior thermal stability, retaining their refractive index and thickness after thermal excursions to 200 °C. The halogenated P4VP films exhibit superior mechanical flexibility relative to conventional inorganic coatings (Al2O3and Ta2O5) and do not fracture at uniaxial tensile strains as high as 10%. This new material chemistry and fabrication approach method may enable advanced optical designs and functionality in a wide range of substrates and device architectures.  more » « less
Award ID(s):
1845805
PAR ID:
10486869
Author(s) / Creator(s):
 ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Optical Materials
ISSN:
2195-1071
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Flexible optics and optoelectronic devices require stretchable and compliant antireflection coatings (ARC). Conventional optical coatings, typically inorganic thin films, are brittle and crack under strain, while porous or patterned surfaces often lack environmental endurance and/or involve complex processing. Polymeric optical thin films prepared by initiated chemical vapor deposition (iCVD) comprise a promising alternative class of materials. With iCVD, multilayered, uniform thin film coatings can be synthesized conformally on the surface of a temperature-sensitive substrate near room temperature with precise compositional and thickness control. In this study, a model two-layer coating design consisting of poly(1 H ,1 H ,6 H ,6 H -perfluorohexyl diacrylate) (pPFHDA) with a refractive index at 633 nm of n 633 = 1.426 was deposited atop poly(4-vinylpyridine) (p4VP, n 633 = 1.587). Broadband antireflection over the visible wavelength range (400–750 nm) was conferred to a transparent, flexible thermoplastic polyurethane (TPU) substrate ( n 633 ∼ 1.51), reducing the front-surface reflectance from ∼4% to ∼2%. The superior mechanical compliance of polymer ARCs over conventional inorganic coatings (MgF 2 , SiO 2 , and Al 2 O 3 ) on the TPU substrate was thoroughly investigated by monitoring the evolution of film morphology and tensile fracture with applied equibiaxial strain. The polymer ARC withstood at least ε = 1.64% equibiaxial strain without fracture, while all inorganic coatings cracked. Through a repeated application of strain over hundreds of cycles, the antireflection by the polymer film was shown to possess excellent stability and fatigue resilience. Finally, simulations of established iCVD polymer chemistries possessing larger index contrast revealed that reflectance can be further reduced to <1% or better. 
    more » « less
  2. Abstract Materials with tunable infrared refractive index changes have enabled active metasurfaces for novel control of optical circuits, thermal radiation, and more. Ion‐gel‐gated epitaxial films of the perovskite cobaltite La1−xSrxCoO3−δ(LSCO) with 0.00 ≤x≤ 0.70 offer a new route to significant, voltage‐tuned, nonvolatile refractive index modulation for infrared active metasurfaces, shown here through Kramers–Kronig‐consistent dispersion models, structural and electronic transport characterization, and electromagnetic simulations before and after electrochemical reduction. As‐grown perovskite films are high‐index insulators forx< 0.18 but lossy metals forx> 0.18, due to a percolation insulator‐metal transition. Positive‐voltage gating of LSCO transistors withx> 0.18 reveals a metal‐insulator transition from the metallic perovskite phase to a high‐index (n> 2.5), low‐loss insulating phase, accompanied by a perovskite to oxygen‐vacancy‐ordered brownmillerite transformation at highx. Atx< 0.18, despite nominally insulating character, the LSCO films undergo remarkable refractive index changes to another lower‐index, lower‐loss insulating perovskite state with Δn >0.6. In simulations of plasmonic metasurfaces, these metal‐insulator and insulator‐insulator transitions support significant, varied mid‐infrared reflectance modulation, thus framing electrochemically gated LSCO as a diverse library of room‐temperature phase‐change materials for applications including dynamic thermal imaging, camouflage, and optical memories. 
    more » « less
  3. Dielectric mirrors based on Bragg reflection and photonic crystals have broad application in controlling light reflection with low optical losses. One key parameter in the design of these optical multilayers is the refractive index contrast, which controls the reflector performance. This work reports the demonstration of a high-reflectivity multilayer photonic reflector that consists of alternating layers of TiO2films and nanolattices with low refractive index. The use of nanolattices enables high-index contrast between the high- and low-index layers, allowing high reflectivity with fewer layers. The broadband reflectance of the nanolattice reflectors with one to three layers has been characterized with peak reflectance of 91.9% at 527 nm and agrees well with theoretical optical models. The high-index contrast induced by the nanolattice layer enables a normalize reflectance band of Δλ/λoof 43.6%, the broadest demonstrated to date. The proposed nanolattice reflectors can find applications in nanophotonics, radiative cooling, and thermal insulation. 
    more » « less
  4. Abstract BaTiO3is a technologically relevant material in the perovskite oxide class with above‐room‐temperature ferroelectricity and a very large electro‐optical coefficient, making it highly suitable for emerging electronic and photonic devices. An easy, robust, straightforward, and scalable growth method is required to synthesize epitaxial BaTiO3thin films with sufficient control over the film's stoichiometry to achieve reproducible thin film properties. Here the growth of BaTiO3thin films by hybrid molecular beam epitaxy is reported. A self‐regulated growth window is identified using complementary information obtained from reflection high energy electron diffraction, the intrinsic film lattice parameter, film surface morphology, and scanning transmission electron microscopy. Subsequent optical characterization of the BaTiO3films by spectroscopic ellipsometry revealed refractive index and extinction coefficient values closely resembling those of stoichiometric bulk BaTiO3crystals for films grown inside the growth window. Even in the absence of a lattice parameter change of BaTiO3thin films, degradation of optical properties is observed, accompanied by the appearance of a wide optical absorption peak in the IR spectrum, attributed to optical transitions involving defect states present. Therefore, the optical properties of BaTiO3can be utilized as a much finer and more straightforward probe to determine the stoichiometry level present in BaTiO3films. 
    more » « less
  5. Abstract Iridescent color-shift pigments have been used in some industrial applications, e.g., for cosmetics and packaging. To achieve environmental-friendly and lasting color, thin-film interference is used to generate structural color. By maximizing the refractive index (RI) difference between the thin films (i.e., using an ultralow RI film), super-iridescent structural color can be produced. While the lowest refractive index of a naturally occurring solid dielectric is close to 1.37 (i.e., MgF2), we synthesized highly porous dielectric SiO2aerogel to achieve ultralow-RI (n ~ 1.06) and demonstrated a high-refractive index/low-refractive index/absorber (HLA) trilayer structural color. The achieved structural color is highly iridescent and capable of tracing a near-closed loop in CIE color space. By tuning the refractive index, thickness, and geometry of the aerogel layer, we control the reflection dip’s shape, therefore producing a wide range of vivid and iridescent colors. 
    more » « less