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.
Attention:The NSF Public Access Repository (NSF-PAR) system and access will be unavailable from 7:00 AM ET to 7:30 AM ET on Friday, April 24 due to maintenance. We apologize for the inconvenience.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: pH Tunable Patterning of Quantum Dots
Abstract Patterning of quantum dots (QDs) is essential for many, especially high‐tech, applications. Here, pH tunable assembly of QDs over functional patterns prepared by electrohydrodynamic jet printing of poly(2‐vinylpyridine) is presented. The selective adsorption of QDs from water dispersions is mediated by the electrostatic interaction between the ligand composed of 3‐mercaptopropionic acid and patterned poly(2‐vinylpyridine). The pH of the dispersion provides tunability at two levels. First, the adsorption density of QDs and fluorescence from the patterns can be modulated for pH > ≈4. Second, patterned features show unique type of disintegration resulting in randomly positioned features within areas defined by the printing for pH ≤ ≈4. The first capability is useful for deterministic patterning of QDs, whereas the second one enables hierarchically structured encoding of information by generating stochastic features of QDs within areas defined by the printing. This second capability is exploited for generating addressable security labels based on unclonable features. Through image analysis and feature matching algorithms, it is demonstrated that such patterns are unclonable in nature and provide a suitable platform for anti‐counterfeiting applications. Collectively, the presented approach not only enables effective patterning of QDs, but also establishes key guidelines for addressable assembly of colloidal nanomaterials.  more » « less
Award ID(s):
2132538
PAR ID:
10554518
Author(s) / Creator(s):
; ; ; ;
Publisher / Repository:
Wiley
Date Published:
Journal Name:
Small
Volume:
20
Issue:
2
ISSN:
1613-6810
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; ; (, ACS Energy Letters)
    Direct optical lithography presents a promising patterning method for colloidal quantum dots (QDs). However, additional care needs to be taken to prevent deterioration of the optical properties of QDs upon patterning, especially for InP-based QDs. This study proposes an efficient method for high-resolution patterning of InP-based QDs using a photoacid generator while preserving their optical properties. Specifically, our solid-state ligand exchange strategy, replacing chloride ligands with long-chain amine/carboxylate pair ligands, successfully recovered the photoluminescence quantum yield (PLQY) of the patterned InP-based QD films to ∼67% of the original PLQY. Upon examination of the origins of the PLQY reduction during patterning, we concluded that the formation of deep traps caused by the exchanged chloride ligands was the primary cause. Finally, we fabricated high-resolution (feature size: 1 μm), multicolored patterns of InP-based QDs, thereby demonstrating the potential of the proposed patterning method for next-generation high-resolution displays and optoelectronic devices. 
    more » « less
  2. ; ; ; ; ; ; ; (, Advanced Materials)
    Patterning biomolecules in synthetic hydrogels offers routes to visualize and learn how spatially‐encoded cues modulate cell behavior (e.g., proliferation, differentiation, migration, and apoptosis). However, investigating the role of multiple, spatially defined biochemical cues within a single hydrogel matrix remains challenging because of the limited number of orthogonal bioconjugation reactions available for patterning. Herein, a method to pattern multiple oligonucleotide sequences in hydrogels using thiol‐yne photochemistry is introduced. Rapid hydrogel photopatterning of hydrogels with micron resolution DNA features (≈1.5 µm) and control over DNA density are achieved over centimeter‐scale areas using mask‐free digital photolithography. Sequence‐specific DNA interactions are then used to reversibly tether biomolecules to patterned regions, demonstrating chemical control over individual patterned domains. Last, localized cell signaling is shown using patterned protein–DNA conjugates to selectively activate cells on patterned areas. Overall, this work introduces a synthetic method to achieve multiplexed micron resolution patterns of biomolecules onto hydrogel scaffolds, providing a platform to study complex spatially‐encoded cellular signaling environments. 
    more » « less
  3. ; ; (, Soft Matter)
    null (Ed.)
    The effect of static silica particles on the dynamics of quantum dot (QD) nanoparticles grafted with a poly(ethylene glycol) (PEG) brush in hydrogel nanocomposites is investigated using single particle tracking (SPT). At a low volume fraction of homogeneously dispersed silica ( Φ = 0.005), two distinct populations of PEG-QDs are observed, localized and mobile, whereas almost all PEG-QDs are mobile in neat hydrogel ( Φ = 0.0). Increasing the silica particle concentration ( Φ = 0.01, 0.1) results in an apparent change in the network structure, confounding the impact of silica on PEG-QD dynamics. The localized behavior of PEG-QDs is attributed to pH-mediated attraction between the PEG brush on the probe and surface silanol groups of silica. Using quartz crystal microbalance with dissipation (QCM-D), the extent of this interaction is investigated as a function of pH. At pH 5.8, the PEG brush on the probe can hydrogen bond with the silanol groups on silica, leading to adsorption of PEG-QDs. In contrast, at pH 9.2, silanol groups are deprotonated and PEG-QD is unable to hydrogen bond with silica leading to negligible adsorption. To test the effect of pH, PEG-QD dynamics are further investigated in hydrogel nanocomposites at Φ = 0.005. SPT agrees with the QCM-D results; at pH 5.8, PEG-QDs are localized whereas at pH 9.2 the PEG-QDs are mobile. This study provides insight into controlling probe transport through hydrogel nanocomposites using pH-mediated interactions, with implications for tuning transport of nanoparticles underlying drug delivery and nanofiltration. 
    more » « less
  4. ; ; (, Soft Matter)
    Shape changes in electron-beam patterned poly(acrylic acid) can be controlled by the many patterning parameters to create gel-based ribbons with both in-plane and out-of-plane pH-dependent swelling anisotropies. 
    more » « less
  5. ; ; ; ; ; (, Science Advances)
    Scalable fabrication of two-dimensional (2D) arrays of quantum dots (QDs) and quantum rods (QRs) with nanoscale precision is required for numerous device applications. However, self-assembly–based fabrication of such arrays using DNA origami typically suffers from low yield due to inefficient QD and QR DNA functionalization. In addition, it is challenging to organize solution-assembled DNA origami arrays on 2D device substrates while maintaining their structural fidelity. Here, we reduced manufacturing time from a few days to a few minutes by preparing high-density DNA-conjugated QDs/QRs from organic solution using a dehydration and rehydration process. We used a surface-assisted large-scale assembly (SALSA) method to construct 2D origami lattices directly on solid substrates to template QD and QR 2D arrays with orientational control, with overall loading yields exceeding 90%. Our fabrication approach enables the scalable, high fidelity manufacturing of 2D addressable QDs and QRs with nanoscale orientational and spacing control for functional 2D photonic devices. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Text Encoded Conversion
  • XML
  • Save / Share this Record
  • Send to Email