Advanced Materials - 2023 - Song - Colorful Triplet Excitons in Carbon Nanodots For Time Delay Lighting

Research Article
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Colorful Triplet Excitons in Carbon Nanodots for Time

Delay Lighting
Shi-Yu Song, Kai-Kai Liu,* Xin Mao, Qing Cao, Na Li, Wen-Bo Zhao, Yong Wang,
Ya-Chuang Liang, Jin-Hao Zang, Xing Li, Qing Lou, Lin Dong, and Chong-Xin Shan*
transient blindness because of the abrupt

Time delay lighting offers an added period of buffer illumination for human darkness of switching off. However, time
eyes upon switching off the light. Long-lifetime emission from triplet exci- delay LEDs based on CNDs have rarely
tons has outstanding potential, but the forbidden transition property due to been investigated, due to the challenging
the Pauli exclusion principle makes them dark, and it stays challenging to phosphorescence wavelength regulation
and limited emission lifetimes.
develop full-color and bright triplet excitons. Herein, triplet excitons emission
The observation of radiative recombina
from ultraviolet (UV) to near infrared (NIR) in carbon nanodots (CNDs) is tion from triplet excitons in CNDs,
achieved by confining multicolor CNDs emitters in NaCNO crystal. NaCNO the easy-preparation, low-cost and eco-
crystal can isolate the CNDs, triplet excitons quenching caused by the friendly features make them a worldwide
excited state electrons aggregation induced energy transfer is suppressed, upsurge of research.[16–18] Generally, the
triplet electrons are populated through
and the confinement crystal can furthermore promote phosphorescence of
the intersystem crossing (ISC) process of
the CNDs by inhibiting the dissipation of the triplet excitons due to non- singlet electrons.[19] In short, electrons are
radiative transition. The phosphorescence from radiative recombination of pumped-up from the ground state to the
triplet excitons in the CNDs covers the spectral region from 300 nm (UV) to singlet excited state after incident photons
800 nm (NIR), the corresponding lifetimes can reach 15.8, 818.0, 239.7, 168.4, are absorbed by CNDs. The electrons spin
426.4, and 127.6 ms. Furthermore, the eco-friendly luminescent lampshades flips under spin-orbit coupling (SOC), and
triplet excitons are formed by combining
are designed based on the multicolor phosphorescent CNDs, time delay
with the holes through coulomb inter
light-emitting diodes are thus demonstrated. The findings will motivate new action.[20,21] These excitons can recombine
opportunities for the development of UV to NIR phosphorescent CNDs and via the radiation transition channel accom
time delay lighting applications. panied by emitting photons slowly, which
is called phosphorescence, featuring a long
emission lifetime. The spin-forbidden
1. Introduction transition feature of triplet excitons makes them hard to be
emissive, and the long residence time makes them easy to be
Carbon nanodots (CNDs) have drawn broad attention as new quenched by surrounding oxygen, energy transfer, and internal
rising efficient emitters,[1,2] which offer intriguing potential vibration/rotation induced non-radiative recombination.[22,23] To
applications in optoelectronic devices,[3–5] displaying, informa obtain efficient phosphorescence in CNDs, it is an effective way
tion encryption,[6–9] time-resolved bio-imaging,[10–12] etc. by introducing heavy atoms, heteroatoms, or other substituents
Especially, light-emitting diodes (LEDs) based on emissive during the formation process of CNDs to enhance SOC
CNDs have been receiving enormous attention as light sources strength.[24,25] The stronger SOC can further accelerate the ISC
because of their eco-friendly feature and easily tunable fluores rate from the singlet excited to triplet excited states and enhance
cence wavelength.[13–15] Time delay LEDs can stay lit for other the triplet excitons population in turn. In addition, suppressing
illumination time, which can give eyes a buffer time to reduce the dissipation channel of triplet excitons by restricting the
vibration/rotation of the CNDs can be achieved through
S.-Y. Song, K.-K. Liu, X. Mao, Q. Cao, N. Li, W.-B. Zhao, Y. Wang, “aggregation,”[26] “crystallization,”[27–29] “confined-domain cross
Y.-C. Liang, J.-H. Zang, X. Li, Q. Lou, L. Dong, C.-X. Shan link-enhanced emission”[30] and “matrix confinement,”[31–34]
Henan Key Laboratory of Diamond Optoelectronic Material and Devices
as well as many other ways. With the consistent efforts of
Key Laboratory of Material Physics
Ministry of Education researchers, enormous strides in phosphorescent CNDs have
School of Physics and Microelectronics been made. However, most observed phosphorescence from
Zhengzhou University radiative triplet excitons in CNDs show single emission in
Zhengzhou 450001, China visible regions, it is difficult to realize full-spectrum phospho
E-mail: liukaikai@zzu.edu.cn; cxshan@zzu.edu.cn
rescence in CNDs due to a lack of uniform guiding principles.
The ORCID identification number(s) for the author(s) of this article
To achieve full-spectrum phosphorescence from ultraviolet
can be found under https://doi.org/10.1002/adma.202212286.
(UV) to near-infrared (NIR) in CNDs, it is necessary to make
DOI: 10.1002/adma.202212286 the triplet excitons with different energies bright. Designing
Adv. Mater. 2023, 35, 2212286 2212286 (1 of 10) © 2023 Wiley-VCH GmbH
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efficient multicolor emitters within CNDs, enhancing the For achieving colorful triplet excitons emission of CNDs,
corresponding density of triplet excitons, and minimizing multicolor singlet excitons emission is necessary. Generally, the
the dissipation channels of triplet excitons by constructing a typical structure of the CNDs is that the atoms of the carbon
reasonable matrix can achieve colorful triplet excitons. skeleton are linked with other carbon atoms or hetero atoms
In this work, a series of multicolor efficient CND emitters through p-π bonding.[39,40] The more atomic orbits contributing
were designed and constructed through regulating amounts to the conjugate π-bonds, the narrower gap can be generated
of conjugate atoms. Introducing multiple hetero atoms (N, O) in this system based on the Hückel theory.[41] For the cyclic
with a lone pair of electrons, improve the SOC strength and conjugated CNDs, the orbital energies are given according to
rate of ISC . Moreover, the formation of multiple ionic bonds the following equation:
and a rigid network confined CNDs in the NaCNO matrix,
the long-lived triplet excitons were stabilized greatly, and high  2π k 
E = α + 2β cos  (1)
UV-visible (VIS) -NIR phosphorescence with long lifetime was  n 
thus demonstrated. The phosphorescence wavelength can be
where α is the energy of an electron in the corresponding
tuned from 300 to 800 nm, which covers the entire UV-VIS-NIR
atomic orbital, β is the strength of bonding interaction caused
spectrum region. The multicolor phosphorescence mechanism
by the atomic orbitals overlap, n is the total number of atoms
of the confined isolation CDs was investigated seriously. Finally,
in the conjugated chain, k is the quantum number (k = 0, ±1,
time delay LEDs were demonstrated based on the multicolor
n n −1
phosphorescent CNDs with long emission time after switching ±2……±( ) for even n, while k = 0, ±1, ±2……±( )). For
off, offering buffer time for eyes to reduce transient blindness 2 2
example, consider n = 10, the express for E is the next equation:
in case of abrupt darkness.
 2π k 
E = α + 2β cos  (2)
 10 
2. Results and Discussion
where k = 0 ± 1, ± 2, ± 3, ± 4, 5, and the corresponding E are
The emission from singlet (fluorescence) and triplet (phospho α + 2β, α + 1.618β, α + 0.618β, α − 0.618, α − 1.618β, and α − 2β
rescence) excitons in CNDs are depicted by a simplified energy as illustrated in the left of Figure 2a. In addition, the solutions of
diagram, as indicated in Figure 1. Phosphorescence from triplet the secular determinant have the same basic form, whatever the
excitons has a longer lifetime compared to fluorescence due to ring size. As n increases, the highest occupied molecular orbital
the spin-forbidden transition-induced slow radiative rate. Thus, (HOMO) and lowest unoccupied molecular orbital (LUMO)
the phosphorescent CNDs are suitable for time delay lighting separation decrease. Consequently, the photon energy required
that can supply an effective buffer to reduce transient blindness to excite an electron from the HOMO to LUMO also decreases,
because of abrupt darkness, which has a positive influence as shown in the right of Figure 2a. Thus, CNDs with extended
on the human eyes. ISC, radiative, and non- radiative decay conjugated systems are colored from the UV (for small n) to the
rates are of nearly the same importance, in terms of efficient NIR (large n). Based on this theory, the multicolor CND emitters
phosphorescence. High ISC rate caused by strong SOC plays a are designed and demonstrated by regulating precursors and the
key role in the population of triplet excitons.[35,36] For instance, degree of carbonization. These multicolor CND emitters con
ISC can occur in transitions from 1(n, π*) to 3(π, π*) and tain heteroatoms with lone-pair electrons, to meet the required
1(π, π*) to 3(n, π*), in which the transition orbitals p and
x angular momentum of the electron spin-flip (from −1/2 to 1/2;
py effectively overlap under SOC operator. By contrast, the or 1/2 to −1/2), which is necessary for the triplet excitons produc
ISC from 1(π, π*) to 3(π, π*) or from 1(n, π*) to 3(n, π*) is not tion of the CNDs. The LUMO-HOMO energy gaps of the cor
favorable due to minimal orbital overlapping, which results in responding configurations derived from first-density functional
inefficient SOC (Figure S1, Supporting Information). From theory (DFT) calculations are shown in Figure 2b. The calcula
El-Sayed’s rule, introducing hetero atoms with lone-pair elec tion result indicates energy gaps at 3.80, 3.77, 3.54, 3.28, 3.21, and
trons into the CNDs can make the initial and final states have 2.86 eV for configurations 1–6 (Figure 2c). As a proof of concept,
different electronic compositions, which is efficient to increase six types of phosphorescent CNDs (UV-CNDs, B-CNDs, G-CNDs,
the rate of ISC, as well as the population of triplet excitons.[37,38] Y-CNDs, R-CNDs, and NIR-CNDs) were synthesized through a
As a result, the reasonable structures of the CNDs containing NaOH-assisted heating method. The optical properties of CNDs
different conjugate atoms and hetero atoms are designed, and were characterized by photoluminescence (PL) spectra and
the generated multicolor CNDs emitters with an effective popu UV–vis absorption spectra, as shown in Figure 2d. The
lation of triplet excitons were confined within a NaCNO matrix. normalized absorption spectra demonstrate that the peaks have an
The corresponding spin-orbit coefficients (ξ) were also calculated obvious red shift from high energy to low energy region owing to
in Figure S2 (Supporting Information), and all the structures the enlargement of the conjugate area. The corresponding absorp
have effective ξ (S1, Tn), indicating the effective transition of elec tion spectra clearly show the change of the CND gaps, which has
trons from singlet excited state to triplet excited state through a similar tendency to the calculation results. Notably, the range of
ISC, then completing the triplet excitons population through gap variation was extended from UV to visible area, indicating the
Coulomb interaction,. The plots of the multicolor phosphores different conjugate areas were generated in the CNDs. Moreover,
cence spectra of the CNDs are shown in Figure 1b. The phos the fluorescence spectra of the CNDs exhibit tunable emission
phorescence spectra show a wide range from 300 to 800 nm, peaks (345, 413, 518, 538, 605, and 665 nm), providing the possi
which is the first report of UV-VIS-NIR phosphorescent CNDs. bility for the design of UV-VIS-NIR phosphorescent CNDs.
Figure 1. a) Schematic illustration of the phosphorescence and fluorescence transition processes. b) Full-color Room temperature phosphorescent
CNDs.
The corresponding morphology of the CNDs was charac nanocomposites also present the characteristic peaks of
terized by transmission electron microscopy (TEM) to investi NaCNO, indicating that the incorporation of the CNDs into
gate their structure-function relationship. The UV-CNDs and NaCNO may not disturb the crystalline structure of the matrix.
B-CNDs have a classical shape of quasi-spherical particles with The matrix can form multiple ionic bonds and ultimately a rigid
the size of 3.6 and 3.8 nm (Figure S3a, Supporting Informa network in Figure S5, Supporting Information, suppressing
tion and Figure 3a). In Figure S3b, Supporting Information, the CNDs vibration/rotation-induced non-radiative transition, effi
G-CNDs show the aggregation state, and the size is 4.2 nm. The ciently. To understand the chemical functional group structures
average size of the Y-CNDs and R-CNDs are 4.8 and 5.2 nm as of the CNDs powders, Fourier transforms infrared (FTIR and
shown in Figure 3b,c. The X-ray diffraction (XRD) patterns of X-ray photoelectron spectroscopy (XPS) spectra were recorded.
the CNDs show a typical amorphous peak at 26° in Figure S4, In Figure S6, Supporting Information, the FTIR spectra
Supporting Information. In addition, the XRD patterns of the display characteristic absorption bands at 3451 cm−1 and
multicolor CNDs including B-CNDs, Y-CNDs, and R-CNDs 3274 cm−1, resulting from the stretching vibrations of OH and
Figure 2. a) Schematic illustration of the Hückel theory. b) The six configurations and c) the corresponding HOMO and LUMO of the CNDs.
d) The absorption (left) and fluorescence (right) spectra of the UV-CNDs (purple line), B-CNDs (blue line), G-CNDs (green line), Y-CNDs (yellow line),
R-CNDs (red line), and NIR-CNDs (dark red line).
NH2 groups.[42] The peak located at 1652 cm−1 corresponds to C, N, and O, with the three characteristic peaks C 1s (285 eV),
the stretching vibration of CN/CO and the absorption peak N 1s (400 eV), and O 1s (532 eV), respectively. For the B-CNDs,
at 1457 cm−1 originated from CC stretching vibrations.[43] The the C 1s spectra can be fitted with sp2 C (CC/CC) at 284.5 eV
above results indicate that the CNDs mainly contain some and CN (287.9 eV) in Figure S7b, Supporting Information.
functional groups with a pair of lone electronics (CN/CO, For the Y-CNDs, the C 1s band contained peaks at 284.6 and
OH, NH2). Figure S7a, Supporting Information shows the 288.2 eV for the CC/CC and CN/CO. For the NIR-CNDs,
full XPS, also indicating that the CNDs comprised the elements three peaks at (CC/CC) 284.6 eV, (CN/CO) 285.7 eV,
Figure 3. TEM images of a) B-CNDs, b) Y-CNDs, and c) R-CNDs. Excitation-phosphorescence contour plots of d) B-CNDs, e) Y-CNDs, and f) R-CNDs
at room temperature. g) The photographs of visible RTP CNDs under a 365 nm UV lamp and after removal of the UV lamp. h) Phosphorescence lifetime
decay curves of the corresponding CNDs at room temperature.
CN/CO (288.2 eV) were deconvoluted from the C 1s spectra, peaks centered at 530 nm (G-CNDs), 560 nm (Y-CNDs), and
respectively.[44] It is said that the CNDs with lone electronics of 605 nm (R-CNDs) regardless of excitation wavelengths, indi
heteroatoms were successfully synthesized. cating that CNDs have excitation independent emission
As predicted, long-lifetime multicolor phosphorescence (Figure 3e–f). More excitingly, the NIR-CNDs also show a
was observed from the CNDs powder under ambient condi decent phosphorescence band around 620 to 800 nm, and the
tions after the removal of excitation source. The excitation- main peak at 685 nm, which covers the entire red region and
phosphorescence contour plots of the CNDs powder were extends to the NIR-I region in Figure S8c, Supporting Informa
investigated to get an underlying photoluminescence mecha tion. The phosphorescence with wavelength peak centers from
nism. In Figure S8a, Supporting Information, the phospho UV to NIR region indicates that the multicolor triplet excitons
rescence of UV-CNDs is located mainly from 330 to 390 nm were formed. The strong coupling between the CNDs and the
within the excitation wavelength from 295 to 315 nm, and the matrix NaCNO can restrict the vibration/rotation of the CNDs
maximum UV phosphorescent emission peak at ≈350 nm, (confinement effect), thus further protecting the triplet exci
excitation-independent emission property shows the single tons from non-radiative recombination. In Figure 3g, bright
emission center. For B-CNDs, the phosphorescence spectra multicolor phosphorescence was observed for several seconds
show dominant emission bands at ≈445 nm under excitation by the naked eye after cessation of excitation illumination.
from 285 to 315 nm (Figure 3d). In the cases of other multi To our knowledge, this is the first report of the full spectrum
color visible emission CNDs, there are long-lived emission phosphorescent CNDs that can cover the range from UV to
NIR region. The UV-CNDs powder has long phosphorescence they were stored in ambient conditions for 30 days (Figure S15,
lifetimes of 15.2 ms under the following excitation at 310 nm Supporting Information), indicating they can keep working for
at ambient conditions. The multiple phosphorescence lifetimes a long time at ambient conditions . In Figure S16, Supporting
of the B-CNDs, G-CNDs, Y-CNDs, R-CNDs, and NIR-CNDs Information, the phosphorescence intensities of the CNDs
were monitored at 450, 533, 560, 615, 685 nm, and the corre are almost unchanged under continuous light excitation. To
sponding lifetimes can reach 0.82, 0.17, 0.21, 0.23, and 0.13 s, as ensure reproducibility, the visible long-lived luminescence can
shown in Figure 3h and Figure S9, Supporting Information. In be repeatedly activated with no loss in phosphorescence inten
view of the oxygen-quenched property of phosphorescence, the sity for 20 consecutive cycles (Figure S17, Supporting Informa
UV-VIS-NIR phosphorescence performance of the CNDs was tion), suggesting the high stability and signal consistency of
further evaluated at an oxygen-rich environment, as shown in the CNDs. Additionally, time delay LEDs were fabricated based
Figure S10, Supporting Information. The CND powders exhibit on B-CNDs, Y-CNDs, and R-CNDs composites and a UV chip
the nearly same phosphorescence features under oxygen and with 365 nm emission, in view of their multicolor emission and
nitrogen, indicating oxygen-immunity of the triplet excitons in long lifetime (Figure 4f). The integrated LEDs displayed blue,
CNDs with the protection of the matrix. yellow, and red time delay lighting for about 5 s after switching
A transition model of the UV-VIS-NIR phosphorescent CNDs off, verifying the application of time delay lighting based on the
with different radiative and non-radiative rates is shown in designed multicolor phosphorescence CNDs. The optical prop
Figure 4a based on the above results. The triplet electrons of the erties including phosphorescence, fluorescence, and excitation
CNDs were populated through ISC of singlet electrons under properties of the CNDs have been summarized in Table S2,
SOC, and the formed triplet excitons in CNDs were stabilized Supporting Information.
by the NaCNO matrix, leading to the decreased non-radiative White light plays a key role in indoor lighting, and visual
decay rate. Multicolor phosphorescence is thus achieved from impairment will appear when the eyes encounter sudden light-
the CNDs. To get a deeper understanding on the luminescence to-dark transitions.[46,47] Thus, white-light excited LEDs have a
dynamic process of the multicolor phosphorescent CNDs, bigger and more wide application prospect in terms of prac
the time-resolved phosphorescence spectra were measured. The tical applications. The obtained phosphorescent CNDs with a
UV- CNDs powder exhibited a luminescence peak at 350 nm significant excitation peak at the visible area, ensuring that the
with a lifetime of 15.2 ms under the excitation of 310 nm light CNDs can be effectively actived by white light and designed as a
(Figure. S11a, Supporting Information). As seen in Figures 4b–d, time delay lampshade for time delay lighting. As a proof of con
the multiple time-resolved phosphorescence spectra of the cept, the CNDs-based functional wood lampshades were fabri
B-CNDs, Y-CNDs, and R-CNDs were monitored at a wide range cated by assembling the blue, green, and red phosphorescent
of emission wavelengths from 450 to 600 nm, which have a CNDs with wood, in terms of eco-friendly lighting materials, as
long phosphoresce signal than 1s. In addition, it is revealed illutrated in Figure 5a. The phosphorescent CNDs water solu
that the long-lived luminescence in the red and NIR range from tion was infiltrated into the compound middle lamella of the
600 to 800 nm range can be efficiently excited and the lifetimes delignified wood templates through strong capillary forces, as
of the emission bands at around 685 nm for the NIR-CNDs shown in Figure S18, Supporting Information. The B-CNDs,
reached 0.13 s in Figure S11c, Supporting Information. Further Y-CNDs, and R-CNDs were decorated onto the aligned cellu
more, the temperature-dependent phosphorescence lifetime lose nanofibrils, and multicolor long-lived blue, green, and red
decay curves of B-CNDs, Y-CNDs, and R-CNDs were recorded phosphorescent woods were obtained after drying (Figure 5e),
from 77 to 297 K to further study the influencing factor of the which show significant afterglow and slowly faded away after
phosphorescence lifetime, as shown in Figure 4e. The phospho the removal of excitation light. Interestingly, the CNDs with
rescence lifetimes of B-CNDs, Y-CNDs, and R-CNDs were 2.4, white light excitation can be prepared as functional wood lamp
0.4, and 0.48 s at 77 K. The phosphorescence lifetime increases shades. There is an effective overlap between the CNDs excita
gradually as the temperature decreases, showing a strong tion spectra (from 300 to 500 nm) with that of the indoor white
temperature-dependent phosphorescence property due to the light LEDs (from 400 to 700 nm), as shown in Figure 5b. More
limited vibration under low temperatures (Figure S12, Supporting over, the CNDs show a broadband phosphorescence ranging
Information). The energy difference ∆EST between the fluores from 480 to 630 nm as the excitation wavelength changed from
cence and phosphorescence of B-CNDs, Y-CNDs, and R-CNDs 300 to 500 nm, as shown in Figure 5c. The corresponding lumi
are 0.11, 0.13, and 0.45 eV (Figure S13, Supporting Information). nescence images of the CNDs after white light illumination
The phosphorescence QYs and lifetimes are related to the rates are shown in Figure 5d, bright phosphorescence lasting for 5 s
of the corresponding radiative recombination and non-radiative can be observed. In addition, the photo, temporal and ambient
recombination,[45] which can be depicted by the equations, as stabilities of the CNDs were evaluated (Figure S19, Supporting
shown in Table S1, Supporting Information. The absolute Information), and there was no significant loss in phospho
phosphorescence QYs of the B-CNDs, Y-CNDs, and R-CNDs rescence intensity under continuous excitation. A time delay
are 8.1%, 6.0%, 3.9% (Figure S14, Supporting Information), lighting warm white LED was demonstrated by covering the
and the nonradiative recombination rate knr of B-CNDs is time delay lampshade on a commercial white LED, as shown
1.12 s−1 at 297 K, which is smaller than that of both Y-CNDs in Figure 5f. Warm white afterglow (CIE coordinate: (0.36,0.40)
(4.56 s−1) and R-CNDs (4.25 s−1). The decreased knr of the can last for 2 s, which can protect against transient blindness
B-CNDs compared to both Y-CNDs and R-CNDs may be due of eyes from abrupt darkness. This opens up opportunities to
to the smaller conjugate area. Moreover, no obvious decrease utilize full carbon-based phosphorescence materials for eco-
in phosphorescence intensity can be observed even though friendly time delay lighting.
Figure 4. a) A transition model schematic diagram of the multicolor phosphorescent CNDs. Time-resolved phosphorescence spectra of the b) B-CNDs,
c) Y-CNDs, and d) R-CNDs. e) Temperature-dependent phosphorescence decay plots of the B-CNDs, Y-CNDs, and R-CNDs. f) Photographs of the
time delay LEDs with switch on and switch off.
3. Conclusion wavelength from UV (300 nm) to NIR (800 nm) region was
demonstrated. The introduced multiple heteroatoms (N, O)
In conclusion, multicolor phosphorescent CNDs were designed within the conjugate area of the CNDs enhance SOC strength
by adjusting conjugate atoms, and their corresponding and increase the ISC rates, and this plays a key role in the
triplet excitons become bright under the confinement of the population of triplet excitons. High-density ionic bonding to
NaCNO matrix. As a result, tunable phosphorescence with the CNDs emitters in the NaCNO matrix suppresses non-radiative
Figure 5. a) Possible applications of the phosphorescent CNDs as optical lighting materials for interior delay reminder illumination. b) The spectra
of sunlight (top) and the excitation spectra of warm white phosphorescent CNDs. c) Excitation-emission contour plots of the daylight excited CNDs.
d) The photographs of the CNDs powders excited by white light. e) The photographs of blue, green, and red wood films under excitation 365 nm UV
lamp on/off. f) Photographs of the CNDs densified wood film after switching off the white light lamp and the correspondng CIE coordinate.
transition and facilitates triplet excitons radiative recombina phosphorescent materials with high performance but also
tion. Luminescent function wood lampshades based on the advance more applications in time delay lighting.
multicolor phosphorescent CNDs were fabricated, and the
time delay warm white LEDs were demonstrated by covering
the lampshade on commercial LEDs, protecting transient 4. Experimental Section
blindness of eyes from abrupt darkness. This work will Unless otherwise noted, all reagents used in the experiments, including
be instrumental not only in the design of UV-VIS-NIR melamine, imidazole, maleic anhydride, protoporphyrin, and sodium
hydroxide (NaOH) were purchased from commercial sources without Fabrication of the LEDs: Multicolor LEDs with delayed lighting were
further purification. Deionized water was used in all experiments. fabricated based on B-CNDs, Y-CNDs, and R-CNDs composites and a
Preparation of UV-CNDs: 0.5 g melamine and 0.5 g NaOH precursors UV-emitting chip. All types of LEDs had a similar preparation process. The
were mixed in a mortar and ground uniformly for 10 min, and then the CNDs (10 mg) were added to 1.6 g of Polyvinyl alcohol (PVA). The mixture
solid mixtures were removed in a corundum boat and heated at 400 °C was stirred for 30 min (100 rpm) and added to the surface of the UV LED
for 10 h. The obtained CNDs sample was slowly cooled down to room chip, respectively. Then, the device was dried in an oven at 40 °C for 30 min.
temperature. Fabrication of the Phosphorescent Wood Films: Natural balsa wood
Preparation of B-CNDs: 0.5 g melamine and 1 g NaOH precursors samples were soaked in NaClO2 solution and treated for 24 h. The
were dissolved in 10 mL deionized water, then transferred into a 50 mL delignified samples were rinsed with deionized water and then used for
beaker and heated at 200 °C for 8 h. the preparation of the phosphorescent wood films. The treated wood
Preparation of G-CNDs, Y-CNDs, R-CNDs: A typical preparation samples were soaked in the CNDs solution. The B-CNDs, G-CNDs, and
involved the addition of 0.4 g of solid, powdered imidazole to 2 g of maleic R-CNDs solution (20 mg mL−1) were prepared for further use. The CNDs
anhydride, and then stirring the mixtures in a mortar until the precursor solution was impregnated into the solvent-exchanged samples by using
was completely black. The obtained black powders were washed with 0.3 bar vacuum filtration for 30 min, and this process was repeated five
deionized water three times to remove impurities, and the remnants times. Then the multicolor phosphorescent wood films were obtained.
were dried in an oven at 60 °C. The obtained black powder as seed
CNDs were used for further experimentation. For G-CNDs, 0.01 g seed
CNDs and 0.6 g NaOH precursors were mixed in a mortar and ground
uniformly. Afterward, the mixed solid was transferred into a 50 mL Teflon- Supporting Information
lined stainless-steel autoclave and heated at 200 °C for 10 h, respectively.
Supporting Information is available from the Wiley Online Library or
When the reaction temperature slow down to room temperature, the
from the author.
resulting solid was dissolved in 30 mL of deionized water, then transferred
into a beaker. Last, the G-CNDs powder could be obtained for further
characterization after drying at 60 °C. Y-CNDs and R-CNDs were prepared
using a procedure like that described above for G-CNDs, except for the Acknowledgements
different ratios between seed CNDs and NaOH with a suitable amount.
Generally, the 0.02 g seed CNDs were used to react with NaOH (0.8 g) for This work was supported by the National Natural Science Foundation
Y-CNDs. The 0.02 g seed CNDs was used to react with NaOH (0.2 g) for of China (grant nos. 62075198, 11974317, 12274378) and the Outstanding
R-CNDs, respectively. The obtained samples were cooled down to room Youth Foundation of Henan (grant nos. 222300420087).
temperature, mixed with water (50 mL), and dried in air at 60 °C. Note: Marking to indicate Chong-Xin Shan as a second corresponding
Preparation of NIR-CNDs: 0.002 g protoporphyrin and 0.2 g NaOH author was added on May 25, 2023, after initial publication online.
precursors were dissolved in 20 mL aqueous polyvinyl alcohol solution,
then transferred into a 50 mL stainless-steel autoclave and heated at
120 °C for 6 h. The obtained pink solution was cooled down to room
temperature and dried in air at 60 °C. Conflict of Interest
Characterization: TEM images were measured on TEM (Tecnai
G2 F20 S-TWIN) at 200-kV acceleration voltage to characterize the The authors declare no conflict of interest.
microstructures of all the CNDs. FTIR spectra were recognized on an
FTIR (Nicolet 6700) spectrometer. XRD patterns were collected with a
Smartlab X-ray diffractometer (Rigaku, Japan) using Cu Kα radiation. XPS Author Contributions
were obtained using an X-ray photoelectron spectrometer to measure
the bonding state of the CNDs. The cross-section and surface of the K.-K.L. conceived the idea. K.-K.L. and C.-X.S. supervised and coordinated
phosphorescent wood materials were observed by a JSM-6700F (JEOL, all aspects of this project. S.-Y.S. and K.-K.L. wrote the manuscript.
Japan) field emission scanning electron microscope (FESEM). S.-Y.S. carried out the synthesis and characterization. J.-H.Z. and X.L.
First-Principles DFT Calculations: DFT method was used to optimize performed the structural characterizations. X.M. did the theoretical
the ground state geometries of the multicolor phosphorescent CNDs. calculation. Q.C., W.-B.Z., Y.W., Y.-C.L., Q.L., and L.D. commented on the
The identity approximation was carried out using the B3LYP functional paper. All authors discussed the results.
together with the chain of spheres exchange method. Furthermore,
considering the different non-covalent interactions, Grimme’s
dispersion (D3) correction with Becke-Johnson (BJ) damping parameter
was introduced in the calculation. For the rational adsorption spectrum Data Availability Statement
and spin-orbital coupling, the time-dependent DFT was used to calculate
Research data are not shared.
the excitation energies. In addition, the nature of the structure with
minimum energy (resting point) was performed by conducting frequency
analysis. DFT calculations were performed using the Visual Molecular
Dynamics package and Gaussian 09 package.
Optical Measurements: The fluorescence spectra and excitation-
Keywords
emission spectra of the CNDs were measured on a Hitachi F-7000 PC carbon nanodots, triplet excitons, phosphorescence, time delay, lighting
fluorescence spectrophotometer. Ultraviolet-visible (UV–vis) absorption
spectra of the CNDs were obtained using Hitachi UH 4150 UV–vis Received: December 30, 2022
spectrophotometers, respectively. The lifetimes, kinetic measurements, Revised: February 14, 2023
and time-resolved emission spectra were measured using an Edinburgh Published online: March 29, 2023
FLS1000 fluorescence spectrophotometer equipped with a microsecond
flash-lamp (uF2), a xenon arc lamp (Xe2), a nanosecond hydrogen flash-
lamp (nF920) and, respectively. The temperature-dependent spectra
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Advanced Materials - 2023 - Song - Colorful Triplet Excitons in Carbon Nanodots For Time Delay Lighting

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Colorful Triplet Excitons in Carbon Nanodots for Time

transient blindness because of the abrupt

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