An official website of the United States government
Abstract We present a versatile platform for fabricating two‐photon excitable carbon dot‐based nanocomposite thin films by harnessing the structural versatility of polymer brushes in combination with electron‐beam lithography (EBL). This approach enables the precise spatial organization of carbon dots (CDs) at the nanoscale, facilitating dynamic modulation of their photoluminescent properties in response to environmental stimuli. Three model systems were examined, incorporating pH‐ and thermally responsive polymers, functionalized through covalent and dynamic covalent bonding strategies. By leveraging the spatial control afforded by nanostructured polymer brushes, we achieved precise tuning of optical properties while mitigating aggregation‐induced quenching, a longstanding challenge in solid‐state CD applications. In addition to the advances in controlling optical properties, this work highlights the potential of polymer brush systems to function as optically active, reprogrammable surfaces. The resulting nanoscale‐engineered materials exhibit highly responsive, reconfigurable photonic behavior, offering a scalable pathway for integrating advanced optical interfaces into microchip technologies, biosensing platforms, and multiplexed diagnostic systems. The fusion of polymer brushes, carbon dots, and advanced lithographic techniques marks a substantial advancement in the development of functional materials with nanoscale precision and stimuli‐responsive properties.
more »
« less
This content will become publicly available on March 3, 2026
Bottom‐Up Patterning of Transparent and Conductive Metal–Polymer Composite Hypersurfaces
Abstract The challenge of fabricating transparent and conductive (T/C) films and patterns for applications in flexible electronics, touch screens, solar cells, and smart windows remains largely unsolved. Traditional fabrication techniques are complex, costly, time‐consuming, and struggle to achieve the necessary precision and accuracy over electronic and optical properties. Here, hypersurface photolithography (HP), which integrates microfluidics, a digital micromirror device, and photochemical surface‐initiated polymerizations is used to create polymer brush patterns. The high‐throughput optimization enabled by HP provides conditions to fabricate patterns composed of cross‐linked polymer brushes containing Au‐binding 2‐vinylpyrrolidine (2VP) groups with precise control over the height and the composition at each pixel. Au nanoparticles (AuNPs) are incorporated into the polymer brush patterns through in situ reduction of Au ions, resulting in T/C composite AuNP/polymer brush patterns. The sheet resistance at 100 mA of a 2VP‐AuNP‐functionalized patterns on a glass substrate is 0.42 Ω sq−1with 86% transmittance of visible light. Additional patterns demonstrate multiplexing by copatterning rhodamine B functionalized fluorescent polymer brushes and AuNP/polymer brush conductive domains. This work solves the challenge of creating T/C films by forming metal‐polymer composites from polymer brush patterns, offering a scalable solution for electronic and optical device development and fabrication.
more »
« less
- PAR ID:
- 10577075
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Functional Materials
- Volume:
- 35
- Issue:
- 31
- ISSN:
- 1616-301X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Polymer‐brush‐grafted nanoparticles (PGNPs) that can be covalently crosslinked post‐processing enable the fabrication of mechanically robust and chemically stable polymer nanocomposites with high inorganic filler content. Modifying PGNP brushes to append UV‐activated crosslinkers along the polymer chains would permit a modular crosslinking strategy applicable to a diverse range of nanocomposite compositions. Further, light‐activated crosslinking reactions enable spatial control of crosslink density to program intentionally inhomogeneous mechanical responses. Here, a method of synthesizing composites using UV‐crosslinkable brush‐coated nanoparticles (referred to as UV‐XNPs) is introduced that can be applied to various monomer compositions by incorporating photoinitiators into the polymer brushes. UV crosslinking of processed UV‐XNP structures can increase their tensile modulus up to 15‐fold without any noticeable alteration to their appearance or shape. By using photomasks to alter UV intensity across a sample, intentionally designed inhomogeneities in crosslink density result in predetermined anisotropic shape changes under strain. This unique capability of UV‐XNP materials is applied to stiffness‐patterned flexible electronic substrates that prevent the delamination of rigid components under deformation. The potential of UV‐XNPs as functional, soft device components is further demonstrated by wearable devices that can be modified post‐fabrication to customize their performance, permitting the ability to add functionality to existing device architectures.more » « less
-
Abstract Durable and conductive interfaces that enable chronic and high‐resolution recording of neural activity are essential for understanding and treating neurodegenerative disorders. These chronic implants require long‐term stability and small contact areas. Consequently, they are often coated with a blend of conductive polymers and are crosslinked to enhance durability despite the potentially deleterious effect of crosslinking on the mechanical and electrical properties. Here the grafting of the poly(3,4 ethylenedioxythiophene) scaffold, poly(styrenesulfonate)‐b‐poly(poly(ethylene glycol) methyl ether methacrylate block copolymer brush to gold, in a controlled and tunable manner, by surface‐initiated atom‐transfer radical polymerization (SI‐ATRP) is described. This “block‐brush” provides high volumetric capacitance (120 F cm─3), strong adhesion to the metal (4 h ultrasonication), improved surface hydrophilicity, and stability against 10 000 charge–discharge voltage sweeps on a multiarray neural electrode. In addition, the block‐brush film showed 33% improved stability against current pulsing. This approach can open numerous avenues for exploring specialized polymer brushes for bioelectronics research and application.more » « less
-
Abstract Conjugated polymer brush (CPB) films are more robust and exhibit more vertically aligned polymer chains than their spun‐cast analogs. We prepare CPB films of poly(3‐hexylthiophene) (P3HT) by coupling an amine‐terminated surface (ATS) formed from (3‐aminopropyl)triethoxysilane (APTES) on Si/SiO2to 4‐bromobenzoic acid using standard, inexpensive peptide coupling reagents. The resulting terminal bromobenzene is reacted with Pd(PtBu3)2and immersed in the monomer solution. X‐ray photoelectron spectroscopy, spectroscopic ellipsometry and static water contact angle measurements confirm the surface chemistry at each stage of P3HT CPB preparation. Atomic force microscopy(AFM) and UV–vis spectrophotometry indicate that the CPB films prepared by this method exhibit similar morphology and optical properties to those produced from other methods of poly(3‐alkylthiophene) CPB film preparation. Variations of the standard approach, such as using a pre‐synthesized silane counterpart or with (11‐aminoundecyl)triethoxysilane, show comparable film morphologies by AFM. This method is used to produce the first CPB film of poly(3‐dodecylthiophene), showing its utility for exploring CPB films of more sterically demanding polymers. Peptide coupling is used to prepare an analogous functionalized thiol for initiating P3HT CPB film growth from Au surfaces, and microcontact printing with this thiol allows preparation of the first patterned CPB film of P3HT.more » « less
-
ABSTRACT The stability of nonpatterned and nanopatterned strong polyelectrolyte brushes (PEBs) is studied as a function of both brush character and the properties of a contacting liquid. High‐molecular‐weight PEBs of poly(4‐methyl vinylpyridinium iodide) (PMeVP) are synthesized using surface‐initiated radical‐chain polymerization. Nanopatterned brushes (NPBs) line with pattern sizes ranging from 50 to 200 nm are generated by patterning the initiator layer using deep‐ultraviolet photolithography followed by brush growth initiated from the patterned layer. Homogeneous PEBs with different degrees of charging and grafting densities are exposed to water and salt solutions with different temperatures for different periods. The degradation is monitored through dry‐state ellipsometry and atomic force microscopy measurements. Enhanced degrafting for more strongly swollen polymer brushes can be observed in agreement with an “entropic spring” model. Based on the results of the nonpatterned brushes, the NPBs are exposed to water at different temperatures and external salt content for varying periods of time. Counterintuitively, the NPBs show increased degrafting for smaller patterns, which is attributed to different polymer chain dynamics for nanobrushes and microbrushes. We investigate the influence of thermodynamic and kinetic parameters on the stability of (nanopatterned) PEBs and discuss the role of entanglements and formation of complexes in such films. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1283–1295more » « less
