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: Tunable structural color of bottlebrush block copolymers through direct-write 3D printing from solution
Additive manufacturing of functional materials is limited by control of microstructure and assembly at the nanoscale. In this work, we integrate nonequilibrium self-assembly with direct-write three-dimensional (3D) printing to prepare bottlebrush block copolymer (BBCP) photonic crystals (PCs) with tunable structure color. After varying deposition conditions during printing of a single ink solution, peak reflected wavelength for BBCP PCs span a range of 403 to 626 nm (blue to red), corresponding to an estimated change in d-spacing of >70 nm (Bragg- Snell equation). Physical characterization confirms that these vivid optical effects are underpinned by tuning of lamellar domain spacing, which we attribute to modulation of polymer conformation. Using in situ optical microscopy and solvent-vapor annealing, we identify kinetic trapping of metastable microstructures during printing as the mechanism for domain size control. More generally, we present a robust processing scheme with potential for on-the-fly property tuning of a variety of functional materials.  more » « less
Award ID(s):
1727605 1847828
PAR ID:
10195236
Author(s) / Creator(s):
; ; ; ; ; ;
Date Published:
Journal Name:
Science Advances
Volume:
6
Issue:
24
ISSN:
2375-2548
Page Range / eLocation ID:
eaaz7202
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. In nature, structural and functional materials often form programmed three-dimensional (3D) assembly to perform daily functions, inspiring researchers to engineer multifunctional 3D structures. Despite much progress, a general method to fabricate and assemble a broad range of materials into functional 3D objects remains limited. Herein, to bridge the gap, we demonstrate a freeform multimaterial assembly process (FMAP) by integrating 3D printing (fused filament fabrication (FFF), direct ink writing (DIW)) with freeform laser induction (FLI). 3D printing performs the 3D structural material assembly, while FLI fabricates the functional materials in predesigned 3D space by synergistic, programmed control. This paper showcases the versatility of FMAP in spatially fabricating various types of functional materials (metals, semiconductors) within 3D structures for applications in crossbar circuits for LED display, a strain sensor for multifunctional springs and haptic manipulators, a UV sensor, a 3D electromagnet as a magnetic encoder, capacitive sensors for human machine interface, and an integrated microfluidic reactor with a built-in Joule heater for nanomaterial synthesis. This success underscores the potential of FMAP to redefine 3D printing and FLI for programmed multimaterial assembly. 
    more » « less
  2. Abstract Machine learning can empower the design of cascaded diffractive optical elements (DOEs) at terahertz frequencies enabling the realization of holograms with a tailored multi‐degree‐of‐freedom reconfigurable operation when altering either the number, spacing, rotational alignment, and/or order of the elements. This unprecedented control over the spatial terahertz light distribution can profoundly impact multiple terahertz applications such as signal multiplexing, imaging, and displays. This work demonstrates this multi‐degree‐of‐freedom control in structures fabricated through 3D printing employing low‐loss materials. The designs are validated through 3D finite‐difference time‐domain (FDTD) simulations and experimental measurements, showing that, in all cases, the desired diffraction patterns are generated. 
    more » « less
  3. Abstract Hydrogels hold much promise for 3D printing of functional living materials; however, challenges remain in tailoring mechanical robustness as well as biological performance. In addressing this challenge, the modular synthesis of functional hydrogels from 3‐arm diblock copolypeptide stars composed of an inner poly(l‐glutamate) domain and outer poly(l‐tyrosine) or poly(l‐valine) blocks is described. Physical crosslinking due to ß‐sheet assembly of these star block copolymers gives mechanical stability during extrusion printing and the selective incorporation of methacrylate units allows for subsequent photocrosslinking to occur under biocompatible conditions. This permits direct ink writing (DIW) printing of bacteria‐based mixtures leading to 3D objects with high fidelity and excellent bacterial viability. The tunable stiffness of different copolypeptide networks enables control over proliferation and colony formation for embeddedEscherichia colibacteria as demonstrated via isopropyl ß‐d‐1‐thiogalactopyranoside (IPTG) induction of green fluorescent protein (GFP) expression. This translation of molecular structure to network properties highlights the versatility of these polypeptide hydrogel systems with the combination of writable structures and biological activity illustrating the future potential of these 3D‐printed biocomposites. 
    more » « less
  4. At the intersection of the outwardly disparate fields of nanoparticle science and three-dimensional printing lies the promise of revolutionary new “nanocomposite” materials. Emergent phenomena deriving from the nanoscale constituents pave the way for a new class of transformative materials with encoded functionality amplified by new couplings between electrical, optical, transport, and mechanical properties. We provide an overview of key scientific advances that empower the development of such materials: nanoparticle synthesis and assembly, multiscale assembly and patterning, and mechanical characterization to assess stability. The focus is on recent illustrations of approaches that bridge these fields, facilitate the design of ordered nanocomposites, and offer clear pathways to device integration. We conclude by highlighting the remaining scientific challenges, including the critical need for assembly-compatible particle–fluid systems that ultimately yield mechanically robust materials. The role of domain boundaries and/or defects emerges as an important open question to address, with recent advances in fabrication setting the stage for future work in this area. 
    more » « less
  5. Reconfigurable metasurfaces have been pursued intensively in recent years for the ability to modulate the light after fabrication. However, the optical performances of these devices are limited by the efficiency, actuation response speed and mechanical control for reconfigurability. In this paper, we propose a fast tunable optical absorber based on the critical coupling of resonance mode to absorptive medium and the plasma dispersion effect of free carriers in semiconductor. The tunable absorber structure includes a single-layer or bi-layer silicon photonic crystal slab (PCS) to induce a high-Q optical resonance, a monolayer graphene as the absorption material, and bottom reflector to remove transmission. By modulating the refractive index of PCS via the plasma dispersion of the free carrier, the critical coupling condition is shifted in spectrum, and the device acquires tuning capability between perfect absorption and total reflection of the incident monochromatic light beam. Simulation results show that, with silicon index change of 0.015, the tunable absorption of light can achieve the reflection/absorption switching, and full range of reflection phase control is feasible in the over coupling region. The proposed reconfigurable structure has potential applications in remote sensing, free-space communications, LiDAR, and imaging. 
    more » « less