<p>Stencilling, in which patterns are created by painting over masks, has ubiquitous applications in art, architecture and manufacturing. Modern, top-down microfabrication methods have succeeded in reducing mask sizes to under 10 nm (refs. <sup><CitationRef CitationID="CR1">1</CitationRef>,<CitationRef CitationID="CR2">2</CitationRef></sup>), enabling ever smaller microdevices as today’s fastest computer chips. Meanwhile, bottom-up masking using chemical bonds or physical interactions has remained largely unexplored, despite its advantages of low cost, solution-processability, scalability and high compatibility with complex, curved and three-dimensional (3D) surfaces<sup><CitationRef CitationID="CR3">3</CitationRef>,<CitationRef CitationID="CR4">4</CitationRef></sup>. Here we report atomic stencilling to make patchy nanoparticles (NPs), using surface-adsorbed iodide submonolayers to create the mask and ligand-mediated grafted polymers onto unmasked regions as ‘paint’. We use this approach to synthesize more than 20 different types of&#xa0;NP coated with polymer patches in high yield. Polymer scaling theory and molecular dynamics (MD) simulation show that stencilling, along with the interplay of enthalpic and entropic effects of polymers, generates patchy particle morphologies not reported previously. These polymer-patched NPs self-assemble into extended crystals owing to highly uniform patches, including different non-closely&#xa0;packed superlattices. We propose that atomic stencilling opens new avenues in patterning NPs and other substrates at the nanometre length scale, leading to precise control of their chemistry, reactivity and interactions for a wide range of applications, such as targeted delivery, catalysis, microelectronics, integrated metamaterials and tissue engineering<sup><CitationRef AdditionalCitationIDS="CR6 CR7 CR8 CR9 CR10" CitationID="CR5">5</CitationRef>–<CitationRef CitationID="CR11">11</CitationRef></sup>.</p>

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Patchy nanoparticles by atomic stencilling

  • Ahyoung Kim,
  • Chansong Kim,
  • Tommy Waltmann,
  • Thi Vo,
  • Eun Mi Kim,
  • Junseok Kim,
  • Yu-Tsun Shao,
  • Aaron Michelson,
  • John R. Crockett,
  • Falon C. Kalutantirige,
  • Eric Yang,
  • Lehan Yao,
  • Chu-Yun Hwang,
  • Yugang Zhang,
  • Yu-Shen Liu,
  • Hyosung An,
  • Zirui Gao,
  • Jiyeon Kim,
  • Sohini Mandal,
  • David A. Muller,
  • Kristen A. Fichthorn,
  • Sharon C. Glotzer,
  • Qian Chen

摘要

Stencilling, in which patterns are created by painting over masks, has ubiquitous applications in art, architecture and manufacturing. Modern, top-down microfabrication methods have succeeded in reducing mask sizes to under 10 nm (refs. 1,2), enabling ever smaller microdevices as today’s fastest computer chips. Meanwhile, bottom-up masking using chemical bonds or physical interactions has remained largely unexplored, despite its advantages of low cost, solution-processability, scalability and high compatibility with complex, curved and three-dimensional (3D) surfaces3,4. Here we report atomic stencilling to make patchy nanoparticles (NPs), using surface-adsorbed iodide submonolayers to create the mask and ligand-mediated grafted polymers onto unmasked regions as ‘paint’. We use this approach to synthesize more than 20 different types of NP coated with polymer patches in high yield. Polymer scaling theory and molecular dynamics (MD) simulation show that stencilling, along with the interplay of enthalpic and entropic effects of polymers, generates patchy particle morphologies not reported previously. These polymer-patched NPs self-assemble into extended crystals owing to highly uniform patches, including different non-closely packed superlattices. We propose that atomic stencilling opens new avenues in patterning NPs and other substrates at the nanometre length scale, leading to precise control of their chemistry, reactivity and interactions for a wide range of applications, such as targeted delivery, catalysis, microelectronics, integrated metamaterials and tissue engineering511.