Time-dependent physical unclonable functions by long-lived triplet excitons in carbon dots

Yan-Wei Hu; Qing Cao; Shi-Yu Song; Yuan Sun; Ya-Chuan Liang; Wen-Bo Zhao; Chao-Fan Lv; Chong-Xin Shan; Kai-Kai Liu

doi:10.1038/s41377-025-01940-9

Your Location：

Home >

Browse articles >

Time-dependent physical unclonable functions by long-lived triplet excitons in carbon dots

Original Articles

- Time-dependent physical unclonable functions by long-lived triplet excitons in carbon dots
- Light: Science & Applications Vol. 14, Issue 10, Pages: 3022-3034(2025)
- Affiliations：
  
  1.Henan Key Laboratory of Diamond Optoelectronic Materials and Devices, School of Physics and Laboratory of Zhongyuan Light, Zhengzhou University, Zhengzhou, China
  2.School of Electronics and Information, Zhengzhou University of Light Industry, Zhengzhou, China
  3.Institute of Quantum Materials and Physics Henan Academy of Sciences, Zhengzhou 450046, China
- Author bio：
  
  Chong-Xin Shan (cxshan@zzu.edu.cn)
  Kai-Kai Liu (liukaikai@zzu.edu.cn)
- Funds：
- DOI：10.1038/s41377-025-01940-9
  CLC：
- Received：13 February 2025，
  
  Revised：2025-05-30，
  
  Accepted：26 June 2025，
  
  Published Online：20 August 2025，
  
  Published：31 October 2025
- Accepted：
Scan QR Code
Hu, Y. W. et al. Time-dependent physical unclonable functions by long-lived triplet excitons in carbon dots. Light: Science & Applications, 14, 3022-3034 (2025).
DOI：

Hu, Y. W. et al. Time-dependent physical unclonable functions by long-lived triplet excitons in carbon dots. Light: Science & Applications, 14, 3022-3034 (2025). DOI： 10.1038/s41377-025-01940-9.

摘要

Abstract

Physical unclonable functions (PUFs)

relying extensively on the random spatial distribution of block elements

are promising technology for generating unclonable cryptograph. Herein

we demonstrate time-dependent PUFs (TD-PUFs) by introducing carbon dots (CDs) with bright and long-lived triplet excitons as block elements. The constructed TD-PUFs evolve into multiple unclonable PUFs over time

effectively breaking the spatial limitation of transitional PUFs and increasing the complexity

making them much more difficult to be attacked. This temporal evolution introduces an additional layer of security

as the dynamic nature of TD-PUFs makes it increasingly c

hallenging for adversaries to predict or replicate their states. We have developed pixel matrix function (PMF) to describe the evolution process of the TD-PUFs

enabling a detailed analysis of the dynamic behavior and unique security features. In addition

we exhibit a TD-PUFs painting (30 × 40 cm

) by an etching technology where the primary structures of the panting undergo a transformation over time

driven by the varying triplet exciton lifetimes of the CDs. The proposed concept of TD-PUFs overcome their spatial limitations and increase the complexity

making the PUF labels more difficulty to be cracked.

关键词

Keywords

references

Kim, J. H. et al. Nanoscale physical unclonable function labels based on block copolymer self-assembly. Nat. Electron. 5 , 433–442 (2022)..

Scholz, A. et al. Hybrid low-voltage physical unclonable function based on inkjet-printed metal-oxide transistors. Nat. Commun. 11 , 5543 (2020)..

Pappu, R. et al. Physical one-way functions. Science 297 , 2026–2030 (2002)..

Gassend, G. et al. Silicon physical random functions. Proc. 9th ACM Conference on Computer and Communications Security (ACM, 2002)

Chen, H. M. et al. Highly secure physically unclonable cryptographic primitives based on interfacial magnetic anisotropy. Nano Lett. 18 , 7211–7216 (2018)..

Das, J. et al. MRAM PUF: a novel geometry based magnetic PUF with integrated CMOS. IEEE Trans. Nanotechnol. 14 , 436–443 (2015)..

Leem, J. W. et al. Edible unclonable functions. Nat. Commun. 11 , 328 (2020)..

Hu, Y. W. et al. Flexible and biocompatible physical unclonable function anti-counterfeiting label. Adv. Funct. Mater. 31 , 2102108 (2021)..

John, R. A. et al. Halide perovskite memristors as flexible and reconfigurable physical unclonable functions. Nat. Commun. 12 , 3681 (2021)..

Kuribara, K. et al. Organic physically unclonable function on flexible substrate operable at 2 V for IoT/IoE security applications. Org. Electron. 51 , 137–141 (2017)..

Zhang, J. F. et al. An all-in-one nanoprinting approach for the synthesis of a nanofilm library for unclonable anti-counterfeiting applications. Nat. Nanotechnol. 18 , 1027–1035 (2023)..

Ahn, J. et al. Nanoseed-based physically unclonable function for on-demand encryption. Sci. Adv. 11 , eadt7527 (2025)..

Liu, Y. et al. Inkjet-printed unclonable quantum dot fluorescent anti-counterfeiting labels with artificial intelligence authentication. Nat. Commun. 10 , 2409 (2019)..

Carro-Temboury, M. R. An optical authentication system based on imaging of excitation-selected lanthanide luminescence. Sci. Adv. 4 , e1701384 (2018)..

Im, H. et al. Four-dimensional physical unclonable functions and cryptographic applications based on time-varying chaotic phosphorescent patterns. ACS Nano 18 , 11703–11716 (2024)..

Im, H. et al. Chaotic organic crystal phosphorescent patterns for physical unclonable functions. Adv. Mater. 33 , 2102542 (2021)..

Nocentini, S. et al. All-optical multilevel physical unclonable functions. Nat. Mater. 23 , 369–376 (2024)..

Becker, M. A. et al. Bright triplet excitons in caesium lead halide perovskites. Nature 553 , 189–193 (2018)..

Bowen, E. J. Fluorescence AND phosphorescence. Nature 165 , 659–660 (1950)..

Forster, C. F. & Rickard,E. F. Phosphorescence in plastics. Nature 197 , 1199–1200 (1963)..

Mahato, P. et al. Fast and long-range triplet exciton diffusion in metal–organic frameworks for photon upconversion at ultralow excitation power. Nat. Mater. 14 , 924–930 (2015)..

Cao, Q. et al. Brighten triplet excitons of carbon nanodots for multicolor phosphorescence films. Nano Lett. 22 , 4097–4105 (2022)..

Song, S. Y. et al. Self-exothermic reaction driven large-scale synthesis of phosphorescent carbon nanodots. Nano Res. 14 , 2231–2240 (2021)..

Song, S. Y. et al. Ultraviolet phosphorescent carbon nanodots. Light Sci. Appl. 11 , 146 (2022)..

Liang, Y. C. et al. Thermally enhanced phosphorescent carbon nanodots for monitoring cold-chain logistics. Small 20 , 2312218 (2024)..

Jiang, L. Y. et al. Time division colorful multiplexing based on carbon nanodots with modifiable colors and lifetimes. Nano Lett. 24 , 8418–8426 (2024)..

Zhou, R. et al. Multiphoton excited singlet/triplet mixed self-trapped exciton emission. Nat. Commun. 14 , 1310 (2023)..

Gu, Q. Y. et al. Fast transfer of triplet to doublet excitons from organometallic host to organic radical semiconductors. Adv. Mater. 36 , 2402790 (2024)..

Han, S. Y. et al. Lanthanide-doped inorganic nanoparticles turn molecular triplet excitons bright. Nature 587 , 594–599 (2020)..

Jeon, S. O. et al. High-efficiency, long-lifetime deep-blue organic light-emitting diodes. Nat. Photonics 15 , 208–215 (2021)..

Liang, Y. C. et al. Lifetime-engineered carbon nanodots for time division duplexing. Adv. Sci. 8 , 2003433 (2021)..

Liang, Y. C. et al. Phosphorescent carbon-nanodots-assisted förster resonant energy transfer for achieving red afterglow in an aqueous solution. ACS Nano 15 , 16242–16254 (2021)..

Song, S. Y. et al. Colorful triplet excitons in carbon nanodots for time delay lighting. Adv. Mater. 35 , 2212286 (2023)..

Shi, W. Y. et al. Defect-stabilized triplet state excitons: toward ultralong organic room-temperature phosphorescence. Adv. Funct. Mater. 28 , 1804961 (2018)..

Liang, Y. C. et al. Water-induced ultralong room temperature phosphorescence by constructing hydrogen-bonded networks. Nano Res. 13 , 875–881 (2020)..

Liang, Y. C. et al. Ultralong and efficient phosphorescence from silica confined carbon nanodots in aqueous solution. Nano Today 34 , 100900 (2020)..

Daugman, J. Information theory and the IrisCode. IEEE Trans. Inf. Forensics Security 11 , 400–409 (2016)..

Daugman, J. The importance of being random: statistical principles of iris recognition. Pattern Recognit. 36 , 279–291 (2003)..

Dodda, A. et al. Graphene-based physic ally unclonable functions that are reconfigurable and resilient to machine learning attacks. Nat. Electron. 4 , 364–374 (2021)..

Li, Q. et al. Physical unclonable anticounterfeiting electrodes enabled by spontaneously formed plasmonic core–shell nanoparticles for traceable electronics. Adv. Funct. Mater. 31 , 2010537 (2021)..

Alkatheiri, M. S., Aseeri, A. O. & Zhuang, Y. A deep learning method for the security vulnerability study of feed-forward physical unclonable functions. Arab. J. Sci. Eng. 49 , 12291–12303 (2024)..

Gu, Y. Q. et al. Gap-enhanced Raman tags for physically unclonable anticounterfeiting labels. Nat. Commun. 11 , 516 (2020)..

Wang, K. et al. All-silicon multidimensionally-encoded optical physical unclonable functions for integrated circuit anti-counterfeiting. Nat. Commun. 15 , 3203 (2024)..

Huang, J. et al. Near-infrared circularly polarized luminescent physical unclonable functions. ACS Nano 18 , 15888–15897 (2024)..

Alharbi, A. et al. Physically unclonable cryptographic primitives by chemica l vapor deposition of layered MoS 2 . ACS Nano 11 , 12772–12779 (2017)..

Gao, Y. S., Al-Sarawi, S. F. & Abbott, D. Physical unclonable functions. Nat. Electron. 3 , 81–91 (2020)..

Zhang, T. T. et al. Multimodal dynamic and unclonable anti-counterfeiting using robust diamond microparticles on heterogeneous substrate. Nat. Commun. 14 , 2507 (2023)..

Han, Y. M. et al. Strengthening multi-factor authentication through physically unclonable functions in PVDF-HFP-phase-dependent a-IGZO thin-film transistors. Adv. Sci. 11 , 2309221 (2024)..

Yang, J. X. et al. Bionic micro-texture duplication and RE 3+ space-selective doping of unclonable silica nanocomposites for multilevel encryption and intelligent authentication. Adv. Mater. 35 , 2306003 (2023)..

Arppe, R. & Sørensen, T. J. Physical unclonable functions generated through chemical methods for anti-counterfeiting. Nat. Rev. Chem. 1 , 0031 (2017)..

Shin, J. et al. Multi-dimensional physically unclonable functions: optoelectronic variation-induced m ulti-key generation from small molecule PN heterostructures. Adv. Funct. Mater. 34 , 2314949 (2024)..

Zhang, J. F. et al. Printed smart devices for anti-counterfeiting allowing precise identification with household equipment. Nat. Commun. 15 , 1040 (2024)..

Lin, X. F. et al. Physical unclonable functions with hyperspectral imaging system for ultrafast storage and authentication enabled by random structural color domains. Adv. Sci. 11 , 2401983 (2024)..

Liu, Y. M. et al. A novel physical unclonable function based on silver nanowire networks. Adv. Funct. Mater. 34 , 2304758 (2024)..

Lin, Y. H. et al. Unclonable micro-texture with clonable micro-shape towards rapid, convenient, and low-cost fluorescent anti-counterfeiting labels. Small 17 , 2100244 (2021)..

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

No data

Related Author

No data

Related Institution

No data

⁰