Optical Properties of Carbon Dots: A Review

Mengli Liu
Department of Chemistry and Laboratory of Advanced Materials, Fudan University, Shanghai 200433, P. R. China.
E-mail: [email protected]

Abstract: Fluorescent carbon dots (CDs) have attracted increasing attention in recent years owing to their most significant
advantages in terms of low toxicity, resistance to photobleaching, small size, easy functionalization, eco-friendly synthesis
and diverse imaging capabilities. However, the unclear optical mechanism of CDs greatly limits their further application.
Understanding the optical property of CDs is of great significance for controllable development of top-designed CDs with
functional purposes. In this review, we firstly summarize that light absorption properties of CDs, and demonstrate the
relationship between the absorption spectrum and electron transition of both the core and shell of CDs. Furthermore, we
summarize the common fluorescent mechanisms of CDs, including surface state, quantum confinement effect, conjugated
structures, self-trapped excitons, edge defects, free zigzag sites, and multi-emissive centers. Finally, we also discuss the
phosphorescence properties of CDs. This review gives new insights into how to tune the fluorescence and phosphorescence
of the CDs.
Key words: Carbon dots, Optical properties, Fluorescent mechanism, Light absorption assignments, Phosphorescence

1. Introduction
Fluorescent carbon dots (CDs) consisting of graphene quantum dots (GQDs), carbon nanodots (CNDs) and carbon
quantum dots (CQDs)[1, 2], as an emerging kind of zero-dimensional carbon nanomaterial have attracted intensive attention
from researchers in the fields of bio- and chemo-sensing, cellular imaging, photocatalysis, drug delivery and cancer therapy
due to their ultrasmall size, excellent biocompatibility, high loading capacity, tunable fluorescence, and low cost.[3-5] Some
review papers about CDs have been published and presented the latest research progress of CDs. Our group[6] summarized
the latest progress of CDs in synthesis, fluorescence and chemiluminescence sensing. Furthermore, we summarized the
functionalization strategies of CDs including heteroatom doping and surface modification.[2] Baker’s group[7] provided a
detailed overview of the current state-of-the-art CDs-incorporated devices and their limitations. Guo’s group[8] summarized
recent research progress of CDs in bioimaging, sensing, catalytic and photoelectronic applications.
Currently, there have been some successful reports of CDs with tunable fluorescence from blue to near-infrared. For
example, Lin et al.[9] synthesized the three types of CDs with bright red, green and blue color of fluorescence by varying
the carbon sources. Pang et al.[10] prepared a series of CDs with different fluorescence by modifying the reaction conditions.
Recently, Huang’s group[11] developed a one-pot hydrothermal synthesis route and separated by silica gel column for
preparing a fluorescence ladder from blue to near-infrared of CQDs with the absolute quantum yields higher than 70%.
Therefore, we can obtain the CDs with different emission by controlling the reaction precursors, temperature, or time.
The tunable fluorescent properties make CDs be a powerful tool for chemo- and biosensing. To make better use
of CDs and to tune their optical properties, a full understanding of CDs emission is essential. Unfortunately, a common
fluorescent origin of CDs has not yet been proposed even though some breakthroughs have been obtained in recent years.
Currently, there are two main opinions for fluorescence origin of CDs: the core state, which is induced by perfect carbon
crystals with few defects and modified groups, and the surface state, which is determined by the hybridization of the
carbon backbone and connected chemical groups.[5] Very recently, Mandal et al.[12] proposed the whole CDs is fluorescing
by rotational anisotropy decay dynamics and resonance energy transfer dynamics. Instead, the fluorescing moiety is either
embedded inside the CDs or attached to the surface of the CDs or linked to the CDs through covalent bonds. On the
contrary, Ferrante’s group[13] revealed the emission properties of CDs, neither based on those cores nor molecular species
linked to them but on free molecules, although the presence of carbon core. Therefore, the fluorescent mechanism of CDs
is no unified conclusion until now.
Copyright ©2020 Mengli Liu.
DOI: https://doi.org/10.37256/nat.112020124.1-12
This is an open-access article distributed under a CC BY license
(Creative Commons Attribution 4.0 International License)
https://creativecommons.org/licenses/by/4.0/

Nanoarchitectonics 1| Mengli Liu

 In this review, we summarize the optical properties of CDs, including light absorption assignments, down- and up-
conversion fluorescence, and phosphorescence, illustrating factors that are important and critical to the guiding significance
for controllable synthesis of CDs with specific emission wavelengths. This review will give new insights into how to use
different strategies for tuning the optical properties of CDs, understanding the correlation between the absorption spectrum
and electron transition of CDs.

2. Light absorption assignments

Fluorescent CDs display strong optical absorption in the UV region with a long tail extending into the visible range
even to the the NIR region.[14, 15] Fig. 1 shows the relationship between the absorption spectrum and the electron transition
of both the core and shell of CDs. The shell refers to the surrounded functional groups. The short wavelength bands below
300 nm (Fig. 1, Band I) correspond to a p → p* transition involving aromatic sp2 carbons (aromatic C=C bonds), and the
tail starting from 300 nm to 400 nm (Fig. 1, Band II) can be assigned to the intrinsic absorption of n → p* transition of the
C=O bond in carbon cores.[16-22] The absorption bands above 400 nm (Fig. 1, Band III-V) are originated from the surface
state transition with electron lone pairs.[18-20] It worth noting that the n → p* transition and the broad

Figure 1. A schematic illustration of the relationship between the absorption spectrum and electron transition of CDs

surface-state absorption bands are usually overlapped, rather than isolated or separated. Therefore, there is no great
interruption in the emission tuning, yielding a smooth color gradient as the variation of excitation wavelength. [19] Also
note that the low-energy absorption band at about 300 nm results from n → p* and p → p* charge transfer transitions
or interlayer charge transfer with a strong p → p* component.[17] In addition, other factors including structural/energetic
disorder, medium environment, deprotonation, and excitonic coupling only have a weakly influence on the spectra.[17]
The red-shifted UV-vis absorption spectrum from ca. 420 nm (Fig. 1, Band III) to NIR spectral region (Fig. 1, Band V)
is directly attributed to the addition of graphitic nitrogen into the carbon sp2 lattice because the graphitic nitrogen centers
can inject excess electron into the unoccupied π* orbitals and markedly reduce the HOMO−LUMO gap and the energies of
the corresponding optical transitions.[23, 24] Meanwhile, O-containing functional group (hydroxyl, carboxyl, and epoxy) on
CDs surface can narrow the energy levels, resulting in red-shifted absorption.[10, 17, 25]

3. Fluorescent properties
3.1 Down-conversion fluorescence
Many efforts have been made to explain the luminescent mechanism of CDs, but there is no unified conclusion
until now. Currently, the fluorescent origins of CDs have mainly surface state[10, 25-31], quantum confinement effect[9, 32, 33],
conjugated structures[34, 35], self-trapped excitons[36, 37], edge defects[38-41], free zigzag sites[42-44], multi-emissive centers[45-47].

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 Figure 2. Illustration of the tunable fluorescence emission from CDs containing different O-related surface groups

3.1.1 Surface state

The surface state mechanism has been widely studied by researchers. The surface state, including the degree of
surface oxidation and surface functional groups, is directly responsible for the fluorescence of CDs.[5, 48]
The surface oxidation, caused by oxygen-related groups, can create the defect.[25] Different defects can lead to various
emission sites on CDs surface, enhancing the CDs fluorescence.[10, 25] Mainly, the more surface defects there are, the more
excitons (i.e. electrons and holes) can be trapped.[25] Therefore, the radiation from the recombination of trapped excitons
leads to the red-shifted emission. The different emissions (blue, green and red fluorescence) of CDs are derived from varied
transitions. The blue emission of CDs arises from the radiative recombination of the excited electrons from the n → p*
transition of C=O (Fig. 2).[49] With the increase of O-containing groups (C-OH and C-O-C) on sp2-hybridized carbons,
numerous epoxide (or hydroxy)-related localized electronic states form below p* state, producing numerous new energy
levels between n → p* gaps (Fig. 2).[49] Therefore, the band gap reduces as oxygen content increases on CDs surface, that
is, fluorescence redshift result from the increase in the degree of surface oxidation.
The surface functional groups such as C=O and C=N groups, also known as the molecular state, can tune the
fluorescence of CDs. The O-related groups (C=O) and N-related groups (C=N) can introduce two new energy levels
(HOMO−nO and HOMO-nN) and further produce new electron transitions (Fig. 3).[20, 50] Consequently, the red-shift
emission will occur when the electrons in C=O or C=N groups related defect states return to the HOMO. Furthermore, the
white fluorescence is owing to the overlap of diverse light emission induced by electron transitions between the energy
levels.[50]

Figure 3. Possible absorption and emission mechanisms for the N-CDs

3.1.2 Quantum confinement effect

The GQDs is a zero-dimensional quantum confined system, and its fluorescence has been ascribed to the
recombination of electron-hole pairs in quantum-confined GQDs.[42, 51, 52] In detail, the size of GQDs determines their
energy gap, and the gap decreases gradually as the increase of GQDs size.[52, 53] In other words, the red-shifted emission
of GQDs arises from the increase in size. Li’s group[52] demonstrated that the gap decreases gradually as the size of GQDs
increases. Therefore, different particle-sized GQDs have different excitation and emission spectra. Furthermore, Choi

Nanoarchitectonics 3| Mengli Liu

et al.[33] demonstrated that the anomalous fluorescent behaviors of GQDs in the 5−35 nm size range are arising from the
size-dependent shape and corresponding edge-state variations of GQDs. Lin’s group[9] prepared three CDs with red, green
and blue fluorescence through a one-pot solvothermal method. The difference in the fluorescent emission for the CDs are
attributed to the differences in particle size and nitrogen content. Huang et al.[11] prepared the CDs emitted in full-color
from blue to near infrared via a one-pot hydrothermal synthesis route. The fluorescence properties can be coarsely adjusted
by tuning the size of the crystalline carbon core due to quantum confinement effects because the sizes of the CDs play a
more important role in adjusting the band gap of CDs. With the increase of core size, the extent of π-electron system gets
enlarged, correspondingly, reducing the energy gap between valence band (VB) and conduction band (CB).
3.1.3 Conjugated structure
The conjugation system plays an indispensable role in the fluorescence emission of CDs. The large sp2 domain brings
about a decrease in the band gap. As a result, the gradually red-shifted fluorescence of CDs is owing to the decreased band-
gap energy of CDs as the increasing conjugated structure.[32, 35, 54, 55] Furthermore, Pang’s group[10] demonstrated that the
energy levels of the electronic states are strict relevant to the intrinsic electronic structure of CDs. The p-electron domain
can strongly couple with surface electronic states created by the surface oxidation, thus influence the entirely electronic
structure of the CDs. With the increase in the extent of the p-electron domain, the energy gap of p → p* transitions
decreases and a small energy gap is further caused by the surface states. That is, the red-shifted emission of CDs is derived
from the enlarged p-electron domain or the increase of CDs size.
3.1.4 Self-trapped excitons
Self-trapped excitons usually existed both in molecular crystals and in molecular dimers, such as alkali halide crystals,
SiO2 and C60.[56-58] In general, a photoexcited exciton can induce a distortion or reorientation in the molecular geometry. The
exciton and the distortion can bind together to create a polaron. The exciton becomes localized and stabilized after forming
a self-trapped exciton (Fig. 4).[37] The localized bond distortion will produce a strong local potential field, resulting in the
self-trapping of the hot carriers.
The emission of CDs is a kind of hot carrier luminescence, which takes place in excited states during the relaxation
process, producing a unique feature: the system is not fully degraded and the information (momentum, spin, energy, etc.)
of the electronic system induced by the excitation photons is partially/totally conserved.[36] Urban’s group[37] demonstrated
that the broad Stokes shift in CDs is due to the self-trapping of an exciton in the polycyclic aromatic hydrocarbon (PAH)
network. The width and the excitation dependence of the emission come from a selective excitation of PAHs with slightly
different energy gaps and from energy transfer between them. Furthermore, Sun’s group[36] proved the existence of self-
trapped excitons in CDs by using polarization anisotropy spectroscopy and electric-field modulation spectroscopy. The CDs
emission originates from radiative recombination of self-trapped excitons, where the mobilization of the carriers is largely
impeded due to the existence of a strong local potential field, and thus the relaxation of the hot carriers is considerably
suppressed. As compared to itinerant hot free carriers, photo-generated localized exciton excited states in CDs result in a
reduced relaxation and degradation process, which explains that the emission tends to shift to longer wavelength/lower
energy as time increases.
3.1.5 Special edge defects
The fluorescence of CDs can be tuned by defects, which were caused by O-related functional groups at the edge in
CDs or originate from two overlapped spectral bands with intrinsic and extrinsic states. The higher the oxygen content on
the surface is, the larger the defect is, and the more obvious red shift of the fluorescence will are.

Figure 4. Scheme of the exciton self-trapping process in a pyrene molecule pair: a free exciton (blue spot) may be self-trapped on a
molecule pair as a self-trapped exciton (red spot), causing the reduction of energy and mobility

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 Seo et al.[39] demonstrated that the blue emission and the robust absorption peak on the higher energy side of GQDs
were associated with the formation of the central state in GQDs. However, the green fluorescence of graphene oxide
quantum dots (GOQDs), which have more oxygen content than GQDs, was resulted from their abundant oxygenous
groups, i.e. defect states. Furthermore, their group[40] proposed that the fluorescence of GQDs is due to the optically excited
carriers in GQDs transferred from intrinsic to extrinsic states. The much slower recombination times at short excitation
wavelengths than at long excitation wavelengths are because of the carrier transfer, because the carrier transfer increased
the relaxation time. In addition, the red-shift behavior of GQDs is related to different numbers of oxygen functional groups
of the basal plane and/or the edge. That is, the degree of oxygen content can tune the fluorescence of GQDs.
3.1.6 Free zigzag sites
The edge structure of GQDs can significantly affect their electronic structure.[44] Therefore, the free zigzag sites on the
edge of GQDs can influence the fluorescence of GQDs.[59] Wu’s group[42] proposed that the fluorescence arises from free
zigzag sites with a carbene-like triplet ground state. The great edge effect of GQDs introduced a new UV-vis absorption
band at 320 nm. Furthermore, the two electronic transitions of 320 nm (3.86 eV) and 257 nm (4.82 eV) obtained in the
excitation spectrum of GQDs can be taken as transitions from the s and p orbitals (HOMOs) to LUMO. Because the two
transitions directly contributed to the blue fluorescence, therefore, the blue emission was the irradiation decay of activated
electrons from the LUMO to the HOMO.
3.1.7 Multi-emissive centers
The tunable fluorescence of CDs arises from various fluorescent centers, this is the hybridization of multiple small
emissive molecules on the emissive carbon cores.[47] In general, the blue-green emission mainly results from the graphitic
core, while the long-wavelength emission is related to different C=O and C=N surface functional groups existing in the
molecular residues. Besides, the various N and O containing conjugated molecular residues can act as different emission
centers.

Figure 5. Ternary fluorescent centers-induced fluorescence

The CDs are composed of carbon core and surface state. The carbon core domain is characterized by a sp2 carbon
structure, while the surface state contains various functional groups. Lin et al.[45] for the firstly reported the multi-
emissive states fluorescent behaviors of CDs. The authors demonstrated that the short-wavelength fluorescence (below
400 nm) arises from the radiative recombination of electron-hole pairs from the carbon core, whereas the long-wavelength
fluorescence (above 400 nm) is a result of the radiative relaxation from the excited state to ground state due to the presence
of different oxygen-containing groups on CDs surface. Especially, the red-shifted emission initiate from the surface
modification with amine groups. The increase of electron density through the addition of lone pair electrons in a nitrogen
of amine groups reduces the energy gap, and consequently the emission moves to the longer wavelength.
In addition, Lin et al.[46] proposed that the fluorescence of CDs resulted from ternary fluorescent centers which
contained core states, edge states and N-related surface states (Fig. 5). The unique edge states refer to the atoms at the edge
of carbon backbone, whereas the surface states are some functional groups adherence on the edge. The core state from
π-π* transitions in CDs contributes to the blue fluorescence, while the edge state from n-π* transitions produces the green
fluorescence. The existence of N-related surface states narrowed the energy levels, resulting in a red fluorescent emission
center. Therefore, the multi-emissions of CDs arise from various fluorescent centers, corresponding to different parts within
one single carbon dot particle.

Nanoarchitectonics 5| Mengli Liu

 Figure 6. Electron transition diagrams of CDs, and illustration of the integration of multiple surface emission centers on the fluorescent
carbon core

Furthermore, the multi-emission behavior of CDs at single particle level were analyzed by a single particle
fluorescence imaging technique by Zhang et al.[60], which concretely proved that full-color emissions are single-particle
behavior. The authors demonstrated that the functional groups (–C=O and –C=N) can efficiently introduce new energy
levels for electron transitions and result in continuously adjustable full-color emissions. Their group[47] further studied
the emission behavior of single-particle by total internal reflection fluorescence microscopy. The authors demonstrated
that a single carbon dot has multiple emission centers and features of excitation-dependent multi-color emission. Thus,
the full-color emission of CDs originated from the hybridization of multiple small fluorescent molecules on the surface
and emissive graphitic fragments in the core. Both direct electron transitions of the multi-emission centers separately
and energy transfer between different emission-centers all happened in the CDs, resulting in the complicated full-color
emission behavior (Fig. 6).
3.2 Up-conversion fluorescence
The up-conversion fluorescence is an anti-Stokes emission. The CDs can emit the light with higher energy than
the excitation wavelength, that is, the emission wavelength is shorter than the excitation wavelength. [61] Compared with
down-conversion fluorescence, the up-conversion fluorescence of CDs has numerous merits for biological applications by
the virtue of enhanced tissue penetration depth under NIR and a high signal-to-noise ratio because the long-wavelength
fluorescence produced by NIR excitation can avoid the interference of the weak auto-fluorescence background.
The up-conversion fluorescence of CDs is usually considered as a two-photon or multi-photon processes. Sun’s
group[62] first proposed a two-photon mechanism to explain the up-conversion fluorescence. Liu’s group[61] prepared the
green-emissive CDs with excellent upconversion fluorescence of high yield of 34% and a quantum yield (QY) of 16.5%,
which attributed to a multi-photon active process. Rogach’s group[15] reported the surface functionalization could endow
CDs with NIR absorption band and enhanced NIR emission. The introduction of sulfoxide/carbonyl groups in the outer
layers and the edges of the CDs increased surface oxidation, causing a reduction in the LUMO level and producing the red-
shifted absorption band. Meanwhile, the LUMO levels of the outer layers were lower than those of the inner layers because
of the increased surface oxidation, thus producing the NIR absorption band and NIR emission. Moreover, the charge
transfers from the inner layers to the outer layers may also contribute to the NIR emission. Given these unique properties,
the CDs can simultaneously emit two-photon-induced NIR emission and three-photon-induced red emission when excited
at 1400 nm. Kuo’s group[63] obtained N-GQDs modified with the polyethylenimine (PEI) and polystyrene sulfonate (PSS)
which can act as an active two-photon contrast agent in two-photon bioimaging. The strong electron donation and large
π-conjugated systems, which were arising from the polymers containing N and S atoms on the N-GQDs surface, influenced
the charge transfer efficiency. The interaction between the N-GQDs and polymers produced oscillating dipoles, therefore,
the two-photon emission of polymers modified N-GQDs can cause sharp increases or significant changes.

Volume 1 Issue 1|2020| 6 Nanoarchitectonics

 Figure 7. A schematic illustration of various typical electronic transitions processes of GQDs. Normal fluorescence mechanisms in GQDs
for small size (a) and large size (b); Upconverted fluorescence mechanisms in GQDs for large size (c) and small size (d)

However, Li’s group[52] argued that the multi-photon excitation is inadequate to account for the up-conversion
fluorescence of CDs. The authors prepared GQDs with frequency upconverted emission by a facile hydrazine hydrate
reduction of graphene oxide. Given constant energy difference of ca. 1.1 eV between the excitation light and emission
light, an energy level structural model for the up-conversion fluorescence properties were constructed as shown in Fig.
7. The up-conversion fluorescence originates from the relaxation of electrons from a higher energy state of the p orbital
(LUMO) to the s orbital since some electrons would inevitably transit to the LUMO when many low energy photons excite
the electrons in the p orbital. Although the electrons of the s orbital can also be transitioned, it only can emit conventional
down-conversion light.
3.3 Temperature-dependent emission
Temperature-dependent fluorescence property has rarely been reported, but it can provide a unique insight into the
understanding of the luminescence mechanism of CDs.[64-66] Generally speaking, the fluorescent intensity of CDs exhibits
a monotonous decrease with increasing temperature, the relaxation dynamics become faster at higher temperatures in the
meantime, which could be mainly owing to the occurrence of non-radiative decay processes.[64] The thermal activation
of non-radiative trapping may be responsible for non-radiative relaxation.[64] Tang et al.[64] demonstrated that the dual
fluorescence bands of CDs arise from core and surface state emission but the energy transfer between core and surface
state is ineffective. The very broad fluorescence band is due to the strong electron-electron interactions and weak electron-
phonon interactions. Liu et al.[65] declared that the thermo-dependent properties of N, S co-doped CQDs are attributed to
the temperature enhanced population of non-radiative channels of surface (trap/defect) states. More non-radiative channels
would be activated at a higher temperature, and more excited electrons returned to the ground state via a non-radiative
process, resulting decreased fluorescence intensity.
3.4 Concentration-dependent emission
Concentration-dependent fluorescence behavior has been widely concerned by researchers due to its close relationship
with surface state emission. A long-wavelength-emitting fluorescent occurs gradually with the increasing of CDs
concentration. On the other hand, because of the re-absorption effect at high concentration, the luminescent efficiency
decreases as the concentration increasing. [67]
Hu et al.[68] clarified that the red-shifted emission as the increase of CDs concentration is ascribed to that the radiative
recombination of electrons results in the transformation into two or more centers. Furthermore, Lin et al.[46] proposed that
the concentration-dependent fluorescent properties are due to the existence of multi-emissive centers in CDs. The much-
closed distance between the emissive centers on particle surface in CDs solution with high concentration can provide
a pathway for the non-radiative recombination of charge carriers. The low concentration CDs increases the distance of
particle, which weaken the non-radiative relaxation, leading to the enhancement of luminescent efficiency. As for the
emission wavelength, the decreased concentration can cause a blue-shift emission owing to the inductive effect and
preservation effect.
Nanda et al.[69] elucidated that the tunable fluorescence of the CDs can be controlled by the interparticle distance. At
low concentration of CDs, the increase of interpartical distance decreases the interaction among the particles, resulting
in the blue-shift with increase of fluorescent intensity due to the radiative process. At higher concentration of CDs, the
interparticle distance decreases and the interaction between particles increases, resulting in the red-shift and decrease of
fluorescent intensity due to the self-absorption.
3.5 pH-Dependent emission

Nanoarchitectonics 7| Mengli Liu

 The pH-dependent behavior is also closely relevant with the surface functional groups of the CDs by protonation-
deprotonation. The deprotonation may lead to electrostatic doping/charging to CDs and shift the Fermi level.[70]
The pH conditions can dramatically modify the nature of the energy levels and consequently influence the type of
electronic transitions involved in CDs. Choudhury et al.[71] demonstrated that red-shifted emission of CDs along with
the increased pH is attributed to the gradual creation of new CDs species in the medium that absorb and emit at longer
wavelengths. In addition, the fluorescence intensity of CDs is strong at acid conditions because the strong vibrational
coupling of the OH functional groups, produced by H-bonding effects, can cause the energy level broadening and improve
the conformational rigidity of CDs. However, the eliminated H-bonding effect upon deprotonation at basic conditions may
lead to the reduced vibrational coupling and more discrete energy levels, which results in the decrease of fluorescence for
CDs.
Moreover, Chang et al.[72] prepared P and N co-doped CDs with dual fluorescent emissions (R1 and R2) through
solvothermal synthesis. Interesting, the CDs show pH-dependent fluorescence behavior, and R1 exhibits continuous
quenching, while the R2 opposites with increasing the pH value. The variant of fluorescence can be easily recognized
from the original background with the naked eyes. The authors further clarified that the N- and P-states are responsible
for the effect of pH variation on R1 and R2 emissions, respectively. When pH value > 7, the density of the P-state can be
enhanced through the combination of P-related groups with OH- radicals, thus promoting R2 emission. When pH value < 7,
the protonation of the amine groups would dismiss the unpaired electrons and reduce the electron density in CDs. Not only
does this influence the yield of radiative recombination but it also incurs a blue shift of the fluorescent peak.
Lin et al.[45] demonstrated that the pH-dependent behavior attributed to the carboxylic (−COOH) and amine (−
NH2) functional groups on CDs surface. The −COOH and −NH2 have electron-withdrawing and -donating properties,
respectively. The –COOH group at acidic pH can withdraw the electrons from the conduction band of the carbon-core and
hold back electron-hole recombination, causing the fluorescence reduction. On the contrary, the –COOH group becomes
deprotonated (−COO−) as the pH increase, thereby reducing the electron-withdrawing capability. As a result, the electron-
hole recombination becomes feasible, causing the fluorescence enhancement. The −NH2 group cannot enhance the
fluorescence under either acidic or basic conditions in comparison to that at pH = 7. The fluorescence is not enhanced at
basic pH which is attributed to the electron transfer, whereas the decreased luminescence efficiency at acidic pH is due to
the protonated form (−NH3+) that may reduce electron-donating efficiency.
However, there are also reports that pH-dependent behavior originates from pH-induced aggregation. Zhang et al.[73]
clarified that the red-shifted emission of CDs is due to the formation of CDs aggregates. The CDs can be a well-dispersed
solution under low pH values, however, the CDs can form the aggregates with increasing the pH value due to noncovalent
molecular interactions, such as hydrogen bonds between the carboxyl groups.

4. Phosphorescence
Phosphorescence properties of CDs, especial long-lifetime room-temperature phosphorescence (RTP), have gained
wide attention recently. In order to achieve RTP, two prerequisites should primarily be considered: one focuses on
enhancing spin–orbit coupling by the introduction of transition metals to promote intersystem crossing efficiency; the other
seeks to restrict vibration and rotation to suppress non-radiative transitions.[74, 75]

Figure 8. Proposed FL and PL emission processes of the RTP CDs powder and aqueous solution

Volume 1 Issue 1|2020| 8 Nanoarchitectonics

 CDs with abundant highly cross-linked structures of non-conjugated groups can provide an alternative, novel, and
promising approach to achieving the RTP. Yang’s group[74] proposed that the polymer CDs can be a new type of RTP
materials. The abundant energy levels in the polymer CDs increase the probability of intersystem crossing, and their
covalently cross-linked framework structures greatly suppress the non-radiative transitions. Furthermore, the authors
demonstrated that the RTP property is directly attributed to a crosslink-enhanced emission effect. Lin’s group[75] further
developed that the CDs with long-lifetime RTP (1.46 s). The doping of N and P elements is critical for the ultra-long
RTP which is considered to be favored by an n → p* transition facilitating intersystem crossing (ISC) for effectively
populating triplet excitons. In addition, possibilities of the formation of hydrogen bonds in the interior of the CDs may play
a significant role in producing RTP. Interesting, the as-prepared CDs emit intense RTP but weak FL in the solid form, the
intense RTP showing the effective ISC and stabilization of the excited triplet species, and the weak fluorescence resulting
from aggregation-induced quenching; while in solution, they exhibit strong FL but no RTP, a result ascribed to the presence
of abundant sub-fluorophores and the disruption of interparticle hydrogen bonds by water in CDs, respectively (Fig. 8).
The RTP in aqueous solution is difficult to achieve because phosphorescence quenching usually occurs in the
presence of water owing to the presence of dissolved oxygen as well as the occurrence of solvent-assisted relaxation.[76]
Very recently, Zhou’ group[77] utilized bound water to construct hydrogen-bonded networks between CDs and cyanuric acid
particles for achieving RTP of CDs in aqueous environments. In the presence of water, the surfaces of the cyanuric acid
particles can strongly absorb a layer of highly ordered water molecules (non-freezing bound water). These bound water
molecules can construct robust bridge-like hydrogen-bonded networks between the CDs and cyanuric acid particles, which
not only effectively rigidifies the C=O bonds of CDs but also greatly enhances the rigidity of the entire system, resulting in
the enhancement of phosphorescence.

5. Conclusions and outlook

This review is intended to introduce the optical properties of CDs, including light absorption assignments, down-
and up-conversion fluorescence, and phosphorescence. Many studies about luminescent mechanisms have been published
in recent years, but, none of them is convincing and can interpret a large amount of reported data. The CDs prepared by
different methods own different size, morphology, or surface state, etc. The fluorescence of CDs is dictated by either the
combination or competition between these factors. In addition, the intrinsic structure of CDs is still unclear, and varies with
the reaction precursor, temperature and time. Therefore, developing new technologies and strategies to explore the intrinsic
structure of CDs is a future research focus. Meanwhile, investigation of the optical properties of CDs includes the different
emission centers, excitation dependence, and pH, concentration and solvent sensitivity, all of which are hot research topics.
Therefore, more theoretical and experimental methods need to be made to reveal the mystery of CDs fluorescence. In
conclusion, the researches on CDs in various fields will continue to increase rapidly in the years to come.

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