An all-in-one nanoprinting approach for the synthesis of a nanofilm library for unclonable anti-counterfeiting applications.
Journal
Nature nanotechnology
ISSN: 1748-3395
Titre abrégé: Nat Nanotechnol
Pays: England
ID NLM: 101283273
Informations de publication
Date de publication:
Sep 2023
Sep 2023
Historique:
received:
14
04
2022
accepted:
13
04
2023
medline:
6
6
2023
pubmed:
6
6
2023
entrez:
5
6
2023
Statut:
ppublish
Résumé
In addition to causing trillion-dollar economic losses every year, counterfeiting threatens human health, social equity and national security. Current materials for anti-counterfeiting labelling typically contain toxic inorganic quantum dots and the techniques to produce unclonable patterns require tedious fabrication or complex readout methods. Here we present a nanoprinting-assisted flash synthesis approach that generates fluorescent nanofilms with physical unclonable function micropatterns in milliseconds. This all-in-one approach yields quenching-resistant carbon dots in solid films, directly from simple monosaccharides. Moreover, we establish a nanofilm library comprising 1,920 experiments, offering conditions for various optical properties and microstructures. We produce 100 individual physical unclonable function patterns exhibiting near-ideal bit uniformity (0.492 ± 0.018), high uniqueness (0.498 ± 0.021) and excellent reliability (>93%). These unclonable patterns can be quickly and independently read out by fluorescence and topography scanning, greatly improving their security. An open-source deep-learning model guarantees precise authentication, even if patterns are challenged with different resolutions or devices.
Identifiants
pubmed: 37277535
doi: 10.1038/s41565-023-01405-3
pii: 10.1038/s41565-023-01405-3
pmc: PMC10501905
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
1027-1035Subventions
Organisme : Bundesministerium für Bildung und Forschung (Federal Ministry of Education and Research)
ID : 13XP5050A
Informations de copyright
© 2023. The Author(s).
Références
Estimating the Global Economic and Social Impacts of Counterfeiting and Piracy. A Report Commissioned by Business Action to Stop Counterfeiting and Piracy (BASCAP) (Frontier Economics, 2011).
Aldhous, P. Murder by medicine. Nature 434, 132–134 (2005).
doi: 10.1038/434132a
Ma, T. et al. Dynamic wrinkling pattern exhibiting tunable fluorescence for anticounterfeiting applications. Nat. Commun. 11, 1811 (2020).
doi: 10.1038/s41467-020-15600-6
Pecht, M. & Tiku, S. Bogus: electronic manufacturing and consumers confront a rising tide of counterfeit electronics. IEEE Spectr. 43, 37–46 (2006).
doi: 10.1109/MSPEC.2006.1628506
Lehtonen, M., Oertel, N., & Vogt, H. Features, identity, tracing, and cryptography in product authentication. In 2007 IEEE International Technology Management Conference (ICE), 1–8 (IEEE, 2007).
Liu, Y. et al. Inkjet-printed unclonable quantum dot fluorescent anti-counterfeiting labels with artificial intelligence authentication. Nat. Commun. 10, 2409 (2019).
doi: 10.1038/s41467-019-10406-7
Gao, Z., Han, Y. & Wang, F. Cooperative supramolecular polymers with anthracene‒endoperoxide photo-switching for fluorescent anti-counterfeiting. Nat. Commun. 9, 3977 (2018).
doi: 10.1038/s41467-018-06392-x
Yang, H. et al. Hydrophobic carbon dots with blue dispersed emission and red aggregation-induced emission. Nat. Commun. 10, 1789 (2019).
doi: 10.1038/s41467-019-09830-6
Ðorđević, L., Arcudi, F., Cacioppo, M. & Prato, M. A multifunctional chemical toolbox to engineer carbon dots for biomedical and energy applications. Nat. Nanotechnol. 17, 112–130 (2022).
doi: 10.1038/s41565-021-01051-7
Chen, Y. et al. A self-quenching-resistant carbon-dot powder with tunable solid-state fluorescence and construction of dual-fluorescence morphologies for white light-emission. Adv. Mater. 28, 312–318 (2016).
doi: 10.1002/adma.201503380
Mosconi, D. et al. Synthesis and photochemical applications of processable polymers enclosing photoluminescent carbon quantum dots. ACS Nano 9, 4156–4164 (2015).
doi: 10.1021/acsnano.5b00319
Wang, L. et al. Full-color fluorescent carbon quantum dots. Sci. Adv. 6, eabb6772 (2020).
doi: 10.1126/sciadv.abb6772
Shao, J. et al. Full-color emission polymer carbon dots with quench-resistant solid-state fluorescence. Adv. Sci. 4, 1700395 (2017).
doi: 10.1002/advs.201700395
Meng, T. et al. Ultrabroad-band, red sufficient, solid white emission from carbon quantum dot aggregation for single component warm white light emitting diodes with a 91 high color rendering index. Chem. Commun. 55, 6531–6534 (2019).
doi: 10.1039/C9CC01794A
Zhou, Z. et al. Hydrogen peroxide-treated carbon dot phosphor with a bathochromic-shifted, aggregation-enhanced emission for light-emitting devices and visible light communication. Adv. Sci. 5, 1800369 (2018).
doi: 10.1002/advs.201800369
Wang, J., Yang, Y. & Liu, X. Solid-state fluorescent carbon dots: quenching resistance strategies, high quantum efficiency control, multicolor tuning, and applications. Mater. Adv. 1, 3122–3142 (2020).
doi: 10.1039/D0MA00632G
Zeng, S. et al. Bio-inspired sensitive and reversible mechanochromisms via strain-dependent cracks and folds. Nat. Commun. 7, 11802 (2016).
doi: 10.1038/ncomms11802
Liu, X. et al. Binary temporal upconversion codes of Mn
doi: 10.1038/s41467-017-00916-7
Qi, Q. et al. Solid-state photoinduced luminescence switch for advanced anticounterfeiting and super-resolution imaging applications. J. Am. Chem. Soc. 139, 16036–16039 (2017).
doi: 10.1021/jacs.7b07738
Carro-Temboury, M. R., Arppe, R., Vosch, T. & Sørensen, T. J. An optical authentication system based on imaging of excitation-selected lanthanide luminescence. Sci. Adv. 4, e1701384 (2018).
doi: 10.1126/sciadv.1701384
Zhang, J.-C. et al. Achieving thermo-mechano-opto-responsive bitemporal colorful luminescence via multiplexing of dual lanthanides in piezoelectric particles and its multidimensional anticounterfeiting. Adv. Mater. 30, 1804644 (2018).
doi: 10.1002/adma.201804644
Wang, Z. et al. Hybrid chloroantimonates(III): thermally induced triple-mode reversible luminescent switching and laser-printable rewritable luminescent paper. Angew. Chem. Int. Ed. 58, 9974–9978 (2019).
doi: 10.1002/anie.201903945
Fighting counterfeiting at the nanoscale. Nat. Nanotechnol. 14, 497–497 (2019).
Dodda, A. et al. Graphene-based physically unclonable functions that are reconfigurable and resilient to machine learning attacks. Nat. Electron. 4, 364–374 (2021).
doi: 10.1038/s41928-021-00569-x
John, R. A. et al. Halide perovskite memristors as flexible and reconfigurable physical unclonable functions. Nat. Commun. 12, 3681 (2021).
doi: 10.1038/s41467-021-24057-0
Leem, J. W. et al. Edible unclonable functions. Nat. Commun. 11, 328 (2020).
doi: 10.1038/s41467-019-14066-5
Kim, M. S. et al. Revisiting silk: a lens-free optical physical unclonable function. Nat. Commun. 13, 247 (2022).
doi: 10.1038/s41467-021-27278-5
Gao, Y., Al-Sarawi, S. F. & Abbott, D. Physical unclonable functions. Nat. Electron. 3, 81–91 (2020).
doi: 10.1038/s41928-020-0372-5
Buchanan, J. D. R. et al. ‘Fingerprinting’ documents and packaging. Nature 436, 475–475 (2005).
doi: 10.1038/436475a
Bae, H. J. et al. Biomimetic microfingerprints for anti-counterfeiting strategies. Adv. Mater. 27, 2083–2089 (2015).
doi: 10.1002/adma.201405483
Zheng, Y. et al. Unclonable plasmonic security labels achieved by shadow-mask-lithography-assisted self-assembly. Adv. Mater. 28, 2330–2336 (2016).
doi: 10.1002/adma.201505022
Smith, A. F., Patton, P. & Skrabalak, S. E. Plasmonic nanoparticles as a physically unclonable function for responsive anti-counterfeit nanofingerprints. Adv. Funct. Mater. 26, 1315–1321 (2016).
doi: 10.1002/adfm.201503989
Hill, S. A. et al. Practical three-minute synthesis of acid-coated fluorescent carbon dots with tuneable core structure. Sci. Rep. 8, 12234 (2018).
doi: 10.1038/s41598-018-29674-2
Luong, D. X. et al. Gram-scale bottom-up flash graphene synthesis. Nature 577, 647–651 (2020).
doi: 10.1038/s41586-020-1938-0
Yao, Y. et al. Carbothermal shock synthesis of high-entropy-alloy nanoparticles. Science 359, 1489–1494 (2018).
doi: 10.1126/science.aan5412
Zhang, J. et al. Laser-driven growth of structurally defined transition metal oxide nanocrystals on carbon nitride photoelectrodes in milliseconds. Nat. Commun. 12, 3224 (2021).
doi: 10.1038/s41467-021-23367-7
Zhang, J. et al. Nanolayer laser absorber for femtoliter chemistry in polymer reactors. Adv. Mater. 34, 2108493 (2022).
doi: 10.1002/adma.202108493
Eickelmann, S., Ronneberger, S., Zhang, J., Paris, G. & Loeffler, F. F. Alkanes as intelligent surface thermometers: a facile approach to characterize short-lived temperature gradients on the micrometer scale. Adv. Mater. Interfaces 8, 2001626 (2021).
doi: 10.1002/admi.202001626
Sun, M., Hong, C.-Y. & Pan, C.-Y. A unique aliphatic tertiary amine chromophore: fluorescence, polymer structure, and application in cell imaging. J. Am. Chem. Soc. 134, 20581–20584 (2012).
doi: 10.1021/ja310236m
Zhu, S., Song, Y., Shao, J., Zhao, X. & Yang, B. Non-conjugated polymer dots with crosslink-enhanced emission in the absence of fluorophore units. Angew. Chem. Int. Ed. 54, 14626–14637 (2015).
doi: 10.1002/anie.201504951
Schindelin, J. et al. Fiji: an open-source platform for biological-image analysis. Nat. Methods 9, 676–682 (2012).
doi: 10.1038/nmeth.2019
Hu, Y.-W. et al. Flexible and biocompatible physical unclonable function anti-counterfeiting label. Adv. Funct. Mater. 31, 2102108 (2021).
doi: 10.1002/adfm.202102108
Arppe, R. & Sørensen, T. J. Physical unclonable functions generated through chemical methods for anti-counterfeiting. Nat. Rev. Chem. 1, 0031 (2017).
doi: 10.1038/s41570-017-0031
Sun, J., Shen, Z., Wang, Y., Bao, H., & Zhou, X. LoFTR: Detector-free local feature matching with transformers. In Proceedings of the IEEE/CVF Conference on Computer Vision and Pattern Recognition (CVPR), 8922–8931 (IEEE/CVF, 2021).
Zhou, B. & Yan, D. Simultaneous long-persistent blue luminescence and high quantum yield within 2D organic–metal halide perovskite micro/nanosheets. Angew. Chem. Int. Ed. 58, 15128–15135 (2019).
doi: 10.1002/anie.201909760
Kim, J. H. et al. Nanoscale physical unclonable function labels based on block copolymer self-assembly. Nat. Electron. 5, 433–442 (2022).
doi: 10.1038/s41928-022-00788-w
Zhang, J. et al. Nanolayer laser absorber for femtoliter chemistry in polymer reactors. Adv. Mater. 34, 2108493 (2022).
doi: 10.1002/adma.202108493
Zhang, J. et al. Laser-driven growth of structurally defined transition metal oxide nanocrystals on carbon nitride photoelectrodes in milliseconds. Nat. Commun. 12, 3224 (2021).
doi: 10.1038/s41467-021-23367-7
Birch, D. J. S. & Geddes, C. D. Sol-gel particle growth studied using fluorescence anisotropy: an alternative to scattering techniques. Phys. Rev. E 62, 2977 (2000).
doi: 10.1103/PhysRevE.62.2977
Kaur, J. & Kant, R. Curvature-induced anomalous enhancement in the work function of nanostructures. J. Phys. Chem. Lett. 6, 918 (2015).
doi: 10.1021/acs.jpclett.5b01197