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org Research Article

Modulating Triplet Excited-State Energy in Phosphorescent Carbon

Dots for Information Encryption and Anti-Counterfeiting
Cheng Zhang,∥ Taotao Li,∥ Yu Zheng, Man Zhang, Meilin Liu, Zhengjie Liu, Kui Zhang,*
and Hengwei Lin*
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ABSTRACT: Room-temperature phosphorescent carbon dots (RTP-CDs) may be

Downloaded via NATL CHENG KUNG UNIV on November 11, 2021 at 06:32:02 (UTC).

used in anti-counterfeiting, information encryption, and optoelectronic devices, but

modulating their triplet-state energy is still challenging. Here, a type of RTP-CDs was
developed via hydrothermal polymerization−carbonization of azamacrocycle and
poly(acrylic acid). The introduction of nitrogen heterocycle promotes the intersystem
crossing from the singlet state to the triplet state, and the functional groups of CDs can
form interdot hydrogen bonds to protect the triplet state. In addition, the uncarbonized
heterocycle groups in the CDs provide coordination sites for metal ions. In this case, the
excited triplet-state energy of CDs is quenched by paramagnetic ions (Co2+ and Cu2+)
or transfers to luminescent ions (Tb3+ and Eu3+). Furthermore, the modulation of the
triplet state by metal ion binding was demonstrated in information encryption and anti-
counterfeiting applications.
KEYWORDS: carbon dots, phosphorescence, triplet state, intersystem crossing, coordination

1. INTRODUCTION realize RTP emissions in CDs, a key factor is to promote the

Fluorescent carbon dots (CDs), as a new class of nanomateri- population of excited triplet states. Fortunately, introducing
als with superior luminescence properties, have been widely heteroatoms could significantly enhance the spin−orbit
coupling, leading to the effective transition from the excited
used in many fields, including chemical sensors, biological
singlet state to the triplet state by the intersystem crossing
imaging, and optoelectronic devices.1−4 As a significant
(ISC) process. Inspired by this, doping N, P, or other elements
advantage, the synthetic strategies of CDs are featured by
in CDs greatly facilitated the RTP emission.24−26
simple operation, large-scale preparation, and low cost.5,6
In addition to the effective ISC process, the stability of the
Compared with the “top-down” method of cutting bulk form
excited triplet state is another important factor to obtain RTP
carbon materials, the “bottom-up” method for the synthesis of
emissions.27,28 Based on this, immobilization of CDs in various
CDs involves polymerization and carbonization of small
matrices (e.g., poly(vinyl alcohol), silica, or zeolites) through
organic molecules, which gives CDs more clear structural
hydrogen or covalent bonding is a commonly used method to
information and more fantastic advantages.7−9 On the one
achieve long-lifetime RTP luminescence.29−31 Another valid
hand, through the reasonable selection of precursors, the
way is utilizing rigid environments through intramolecular
optical properties of CDs can be regulated methodically, so
interactions (typically, hydrogen bonding).32,33 It is worth
that the emission wavelength, lifetime, and quantum yields of
noting that the chemical groups for hydrogen bonding (e.g.,
CDs were obtained with desired performance.10,11 On the
−COOH, −OH, −NH2) exhibit effective coordination ability
other hand, by utilizing special functional groups in precursors,
to metal ions as well. In this work, we constructed a kind of
the specific surface environment of CDs is realized, which lays nitrogen heterocycle functional phosphorescent CD to reveal
a foundation for its practical applications.12,13 the influence of the metal ion coordination on excited triplet
Recently, room-temperature phosphorescent (RTP) CDs states. Incorporating nitrogen heterocycles into the CDs
have attracted widespread attention due to the continuous merged the effect of the ISC process, hydrogen bonding
observation of light emission even after turning off the
excitation source.14−17 The feature of phosphorescence
phenomenon originates from the process of light emission Received: June 13, 2021
from the triplet excited state to the singlet ground state.18,19 Published: September 3, 2021
Dominated by the nature of spin-forbidden transitions, the
phosphorescence lasts from several hundred milliseconds to
several seconds, which finds many potential applications such
as anti-counterfeiting, optical device, and catalysis.20−23 To

© 2021 American Chemical Society https://doi.org/10.1021/acsami.1c11029

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Scheme 1. Schematic Illustration of the Hydrothermal Synthesis of Nitrogen Heterocycle Functional RTP-CDsa

a
The chemical structures in the lower left corner showed different nitrogen heterocycles for the preparation of CDs. The photographs in the lower
right corner were taken using CDs as security ink through screen printing.

Figure 1. Structure and optical properties of RTP-CDs. (a) TEM image of CDs-4; (b) FT-IR spectra of CDs; (c) UV−vis absorption spectra of
CDs; (d) photographs of luminescent CDs; top panel: under 365 nm excitation in dispersion; middle panel: CD powder under 365 nm excitation
on; bottom panel: CD powder under 365 nm excitation off; (e) 3D fluorescence image of CDs-4 dispersion; (f) fluorescence lifetime decay curves
at 380 nm under 320 nm excitation; (g) 3D phosphorescence image of CDs-4 powder; and (h) phosphorescence lifetime decay curves at 525 nm
under 350 nm excitation.

protection, and strong metal ion affinities. By binding with
metal ions, the triplet excited-state energy of phosphorescent
CDs was quenched by paramagnetic ions (Co2+ and Cu2+) or
transferred to luminescent ions (Tb3+ and Eu3+). It is
demonstrated that modulating triplet excited-state energy
through metal ion binding offers the possibilities for
information encryption and anti-counterfeiting.
2. RESULTS AND DISCUSSION
2.1. Design and Synthesis of RTP-CDs. In our
experiments, carboxyl-enriched poly(acrylic acid) (PAA) and
nitrogen-containing heterocycles were selected as precursors to
prepare polymer-like phosphorescent CDs. Four representative
nitrogen heterocycle structures (1,4-diazacyclohexane, 1,4,7-
triazacyclononane, 1,4,7,10-tetraazacyclododecane, and
1,4,8,11-tetraazacyclotetradecane) were employed, and the
obtained products were denoted as “CDs-1”, “CDs-2”, “CDs-
43242
3”, and “CDs-4”, respectively. As shown in Scheme 1, under
hydrothermal conditions (200 °C for 10 h), the secondary
amines in the heterocyclic structure exhibited high reactivity,
which cross-linked with the carboxyl groups on PAA to form
the amide bond. Moreover, these heterocycles contained two
(or more) nitrogen reaction sites, leading to the formation of
coil configuration during the dehydration and polymerization
process. Notably, the heterocycles not only serve as linkers to
obtain polymer-like CDs but also act as heteroatoms to
facilitate the ISC process for the origin of phosphorescence.
By observation of transmission electron microscopy (TEM)
images, we found that the RTP-CDs showed quasi-spherical
shape with the size of ∼4 nm (Figures 1a and S1). Fourier
transform infrared (FT-IR) spectra showed that numerous
chemical groups existed on the surface of CDs (Figure 1b).
The wide absorption from 3800 to 3200 cm−1 corresponded to
the stretching vibration of O−H and N−H bonds, while 2942
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ACS Applied Materials & Interfaces
Figure 2. (a) UV−vis absorption spectra of CDs-3 dispersion (2.5 mg in 1 mL of H2O) in the presence of different amounts of Co2+ ions; (b)
fluorescence and (c) phosphorescence spectra of CDs-3 in the presence of Co2+; (d) UV−vis absorption spectra of CDs-4 dispersion (2.5 mg in 1
mL of H2O) in the presence of different amounts of Cu2+ ions; (e) fluorescence and (f) phosphorescence spectra of CDs-4 in the presence of Cu2+.
All of the inset photos showed the changes of CDs before (left) and after (right) treating with 0.2 μmol of the corresponding metal ions.
cm−1 attributed to the vibration of C−H bonds. It is worth
noting that the stretching vibration of CO at 1640 cm−1, the
bending vibration of N−H at 1550 cm−1, and the C−N
vibration at 1251 cm−1 indicated the formation of amide
bonds.15 The chemical bonding can be further confirmed by
high-resolution XPS spectra (Figure S2). The C 1s revealed
the presence of C−C/CC (284.7 eV), C−N/C−O (285.5
eV), and CO (288.8 eV).10 N 1s was deconvoluted into C−
NC (399.7 eV), N−(C)3 (400.6 eV), and N−H (401.7
eV).24 The O 1s displayed CO (531.6 eV) and C−O (533.1
eV).34 These chemical groups (CC/CN/CO and C−
N/C−O) produced corresponding UV−vis absorption, which
is attributed to the π → π* and n → π* transitions at 291 and
336 nm, respectively (Figure 1c). Combining the structural
characterization, we confirm that plentiful functional groups
anchored on the surface of CDs, which provided the possibility
for hydrogen bonding or metal ion coordination.
2.2. Optical Properties of RTP-CDs. The synthesized
CDs showed superior fluorescence properties in aqueous
dispersion. Under the excitation of UV light, all of the CDs
displayed blue light luminescence (Figure 1d, top panel) and
exhibited the excitation-dependent luminescent behavior
(Figures 1e and S3). With quinine sulfate as a reference, we
calculated the fluorescence quantum yields (QYs) of the four
CDs: (19.5 ± 0.6)% for CDs-1, (14.1 ± 0.9)% for CDs-2,
(16.7 ± 0.7)% for CDs-3, and (28.3 ± 1.1)% for CDs-4,
respectively. The fluorescence decay curves could be fitted to
the biexponential function with lifetime ∼5 ns (Figure 1f and
Table S1). The CD powder was obtained by freeze drying. The
powders also presented strong fluorescence, indicating that
there was no aggregation-induced quenching in these CDs
(Figure 1d, middle panel). As shown in Figure S4, the
fluorescence emission shifts to longer wavelengths as the
excitation was turned to higher wavelengths. Interestingly, after
turning off the UV lamp, green light phosphorescence emission
could be observed for about 10 s to naked eyes (Figure 1d,
bottom panel and Figure S5). Slight excitation-dependent
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phosphorescence was observed in the CD powders (Figure
S6). The decay curves of phosphorescence could be fitted by
the triexponential function, and the average lifetimes of CDs-
1−CDs-4 are 389, 389, 382, and 494 ms, respectively (Figure
1h and Table S2). The dependence of excitation wavelength
and multiexponential fitting of lifetimes would be attributed to
the different degree of polymerization and carbonization,
leading to the existence of multiple luminescence centers in
RTP-CDs.14 Finally, we tested the reproducibility of the
synthetic strategy for the phosphorescent CDs (Figure S7).
The CDs from different batches showed intense phosphor-
escence with similar emission wavelengths, which demon-
strated excellent reproducibility of the hydrothermal synthesis.
In principle, to achieve long-lifetime RTP emissions, two key
principles need to be required: (i) intense spin−orbit coupling
to boost ISC from singlet (S) to triplet states (T) and (ii)
stabilization of the excited triplet state for reducing the
nonradiative energy consumption. In our developed RTP-CDs,
the nitrogen heterogeneous atom doping effectively promoted
the ISC process. As a control experiment, we synthesized CDs
using PAA as a sole precursor under the same hydrothermal
conditions. However, upon removal of UV excitation, RTP
emission of PAA-only CDs was not apparent (Figure S8). With
the calculation of energy gap between lowest S1 and T1 states
(ΔEST), the energy gaps of CDs-1, CDs-2, CDs-3, and CDs-4
are 0.56, 0.61, 0.59, and 0.60 eV, respectively (Figure S9). Such
small energy gaps are beneficial for the ISC process.34 On the
other hand, abundant hydrophilic moieties existed on the
surface of RTP-CDs (structure characterization mentioned
above). When the CDs dried to the solid state, a large number
of interdot hydrogen bonds were formed by these hydrophilic
groups. Thus, nonradiative transitions of CD powder were
greatly suppressed to generate RTP emission. Comparatively,
when the CDs were dispersed in water, undetectable RTP
emission was observed in the dispersion due to the breakdown
of the interdot hydrogen bonds (Figure S10). In addition, we
investigated the phosphorescence of CDs-4 in different
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solvents. The results showed that solvents such as acetonitrile

and cyclohexane do not destroy the hydrogen bonds, and thus
the phosphorescence can still be observed (Figure S11).
Temperature-dependent RTP-emission experiments also illus-
trated the stabilization of the triplet state by hydrogen bonds.
As shown in Figure S12, when the temperature increased, the
fluorescence and phosphorescence intensity of CDs-3
decreased gradually, but the phosphorescence intensity
decreased more significantly (fluorescence quenched 7.6%
and phosphorescence quenched 84.8% with the temperature
increasing to 50 °C) with temperature because of the
quenching of vibrational effects.25
2.3. Coordination Ability for Metal Ions. According to
the structural characterization, the formation of CDs mainly
included intermolecular condensation and carbonization
process. Notably, we assumed that the structures of macro-
cycles remained on the surface of RTP-CDs due to incomplete
carbonization. Previous literature studies reported that these
heterocycles have strong coordination ability for metal ions;
meanwhile, the metal ions have remarkable influence on the
triplet state of phosphorescence.35,36 To this end, the effects of
metal ions on the luminescence of CDs are investigated in
detail. Due to the difference in the coordination ability of the
heterocycles in the CDs, the as-synthesized CDs showed
different affinities to metal ions. We found that CDs-3
exhibited intense binding ability to Co2+ ions, while CDs-4
responded intimately to Cu2+ ions (Figure S13). As shown in
Figure 2a, when Co2+ ions were added to the CDs-3 Figure 3. Fluorescence spectra of CDs-4 dispersion (2.5 mg in 1 mL
dispersion, a new absorption peak generated at 510 nm, of H2O) in the presence of different amounts (0−0.2 μmol) of (a)
leading to the color of CDs-3 dispersion changing from Tb3+ ions and (b) Eu3+ ions; phosphorescence spectra of CDs-4 (2.5
colorless to pale pink. This weak absorption peak could be mg in 1 mL of H2O) in the presence 0.2 μmol of (c) Tb3+ ions and
attributed to the d−d transitions of Co2+ in the CD complex. It (d) Eu3+ ions (insert show the photographs of corresponding
was worth nothing that the intensity of the absorption peak powders); and (e) schematic illustration of the energy transfer from
increased no longer when the amount of Co2+ reached 0.2 the excited triplet state to Tb3+ and Eu3+ ions.
μmol, which indicated the saturation of coordination (Figure
S14). As shown in Figure 2b, the fluorescence intensity showed energy transfer from the excited triplet state of CDs to Tb3+
a negligible decrease with 0.2 μmol of Co2+ ions. Further and Eu3+ ions, the lanthanide ions were effectively excited.
increasing the amount of Co2+ ions (to 1 μmol) did not cause Notably, the green and red emissions were not observed by
obvious fluorescence quenching. However, the addition of naked eyes upon removal of the UV irradiation due to the
Co2+ significantly quenched the phosphorescence of CDs-3 short lifetime of Tb3+ and Eu3+ (inset of Figure 3c,d). The
(Figure 2c). A similar phenomenon was also observed in the decay curves demonstrating the lifetimes of the coordinated
CDs-4-Cu2+ complex. The absorption peak of d−d transitions Tb3+ and Eu3+ are 2.0 and 1.9 ms, respectively (Figure S15).
of Cu2+ generated at 513 nm (Figure 2d) and the fluorescence Taking the advantages of energy transfer from the excited
were slightly quenched by Cu2+ ions (Figure 2e). Meanwhile, triplet state of CDs-4 to lanthanides, the coordinated Tb3+ and
the phosphorescence of CDs-4 was effectively quenched by Eu3+ can be sensitized effectively by phosphorescent CDs
Cu2+ ions (Figure 2f). Phosphorescence quenching was mainly (Figure 3e).
attributed to the following two reasons: (i) metal ion 2.4. CDs for Information Encryption and Anti-
coordination disturbed the hydrogen bonds between the Counterfeiting. The modulation of the triplet state of CDs
interdots, leading to destabilization of the triplet state and by metal ion binding can be used in many fields of application.
(ii) quenching of the excited triplet state due to the As a preliminary instance, we demonstrated the application for
paramagnetic perturbations.37 information encryption and anti-counterfeiting. The nitrogen
In addition, the developed CDs also showed strong binding heterocycle functional CDs were employed as luminescent ink
ability to lanthanide ions. Tb3+ and Eu3+ ions were selected and the desired information or patterns were fabricated by
owing to their ladder-like energy levels and prominent screen printing. As shown in Figure 4a, Morse code was made
luminescent performance.38 As shown in Figure 3a,b, when by CDs-3 and interferential dot was made by CDs-3-Co2+
Tb3+ and Eu3+ were mixed with the dispersion of CDs-4, the complex. Under UV light irradiation, wrong information
fluorescence of CDs-4 was quenched, and new emission peaks “RTP” was decrypted using blue fluorescence. Based on the
gradually generated at the characteristic wavelength of Tb3+ phosphorescence quenching of CDs-3-Co2+, the correct
and Eu3+. Phosphorescence spectra of powder samples also information “ATM” was displayed with removing of the UV
showed obvious emission peaks of coordinated lanthanide ions source. In addition, the sensitization of Eu3+ by CDs-4 can be
(5D4 → 7F6, 5D4 → 7F5, 5D4 → 7F4, and 5D4 → 7F3 at 490, 544, used for anti-counterfeiting. When the pattern drawn by CDs-4
585, and 621 nm for Tb3+ in Figure 3c, 5D0 → 7F1 and 5D0 → was sprayed with a solution containing Eu3+ ions, the blue light
7
F2 at 592 and 616 nm for Eu3+ in Figure 3d). With the help of of CDs-4 was transformed to the red light of CDs-4-Eu3+. The
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ACS Appl. Mater. Interfaces 2021, 13, 43241−43246
ACS Applied Materials & Interfaces
Figure 4. (a) Demonstration of information encryption using CDs-3
and CDs-3-Co2+ as security ink for Morse Code printing and (b)
images of anti-counterfeiting pattern using CDs-4 under UV
excitation; left: CDs-4 pattern; right: CDs-4 pattern sprayed with
0.1 M EuCl3 solution.
above results indicate that information encryption and anti-
counterfeiting can be easily achieved through the modulation
of the triplet state by metal ion binding.
3. CONCLUSIONS
In conclusion, a new type of polymer-like CD was synthesized
using nitrogen-containing heterocycles and PAA through the
polymerization−carbonization process. The developed CDs
exhibited an excellent long-lived RTP emission as a result of
the enhanced ISC process by nitrogen doping and interlaced
hydrogen bonds by surface functional groups. Furthermore,
anchored heterocycles provided coordination sites for
transition and lanthanide metal ions. Phosphorescence
quenching or energy transferring could take place with the
formation of the “metal ion−carbon dot” complex. The study
reported here not only provides a convenient method to design
phosphorescent CDs with RTP emission but also opens a
window to expand the applications of CD-based materials for
optical display, information processing, and chemical sensors.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.1c11029.
Experimental, TEM images, high-resolution XPS spectra,
fluorescence emission spectra, photographs of CD
powders, phosphorescence emission spectra, reproduci-
bility, low-temperature (77 K) fluorescence and
phosphorescence emission spectra, lifetime decay curves
of CDs with Eu3+ and Tb3+, and lifetime fitting (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Kui Zhang − School of Chemistry and Chemical Engineering,
Anhui University of Technology, Maanshan 243032, China;
orcid.org/0000-0002-5634-9952; Email: zhangkui@
mail.ustc.edu.cn
Hengwei Lin − School of Chemical and Material Engineering,
Jiangnan University, Wuxi 214122, China; orcid.org/
0000-0002-0589-7035; Email: linhengwei@nimte.ac.cn
43245
www.acsami.org Research Article
Authors
Cheng Zhang − School of Chemistry and Chemical
Engineering, Anhui University of Technology, Maanshan
243032, China
Taotao Li − School of Chemistry and Chemical Engineering,
Anhui University of Technology, Maanshan 243032, China
Yu Zheng − School of Chemistry and Chemical Engineering,
Anhui University of Technology, Maanshan 243032, China
Man Zhang − School of Chemistry and Chemical Engineering,
Anhui University of Technology, Maanshan 243032, China
Meilin Liu − School of Chemistry and Chemical Engineering,
Anhui University of Technology, Maanshan 243032, China
Zhengjie Liu − Institute of Physical Science and Information
Technology, Anhui University, Hefei 230601, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.1c11029
Author Contributions
∥
C.Z. and T.L. contributed equally to this study.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the Natural Science Foundation
of Anhui Province (1908085MB41), the Natural Science
Foundation of Anhui Province for Distinguished Young
Scholars (2008085J11), the Natural Science Foundation of
Education Department of Anhui Province (KJ2019A0011),
and the Innovative Training Program for College Students
(202010360038).
■
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ACS Appl. Mater. Interfaces 2021, 13, 43241−43246