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Yuan, M. He, G. Hu, J. Jiang, T. Xu, L. Zhou, W. Chen, W. Xiang and X. Liang, Nanoscale, 2017, DOI:
10.1039/C7NR05363K.

Volume 8 Number 1 7 January 2016 Pages 1–660 This is an Accepted Manuscript, which has been through the
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 Page 1 of 21 Nanoscale

Multicolour nitrogen-doped carbon: tuneable photoluminescence and View Article Online

DOI: 10.1039/C7NR05363K

sandwich fluorescent glass-based light-emitting diodes

Yijun Zhang, Rongrong Yuan, Meiling He, Guangcai Hu, Jutao Jiang, Tao Xu, Lei Zhou, Wei Chen,
Weidong Xiang*, Xiaojuan Liang*
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, China.
Abstract:

The first use of the combination of ammonium citrate (AC) and ethylenediamine tetraacetic acid (EDTA) as
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Nanoscale Accepted Manuscript

coordinating precursors for the synthesis of highly fluorescent (quantum yield=67%) multicolour nitrogen-doped

carbon dots (CDs) is reported. Under UV light, these CDs emitted outstanding luminescence in colours from dark

blue to red. Interestingly, a single component white-light CDs point with high fluorescence efficiency was

obtained by surface control. Alterations of the photoluminescence (PL) emission of these full-colour CDs were

tentatively proposed to benefit from surface functional groups, such as C=O and C=N. An energy-level model was

proposed to explain the continuously adjustable full-colour emissions. The white light may be attributed to the

overlap of diverse light emissions induced by the electron transitions between the energy levels. Subsequently, to

avoid aggregation-induced solid-state fluorescence quenching, multicolour CD-based sandwich glasses with

various colour emissions were fabricated, which are anticipated to be compatible with the all-optical

light-emitting diodes (LEDs). The facile preparation and outstanding optical features are believed to provide an

alternative synthesis route and inspire more research into applications and CD-based materials of multicolour

CDs.

Keywords: carbon dots; multicolour emission; white emission CDs; sandwich glass; LED

1. Introduction

Luminescent carbon quantum dots (CDs) have attracted tremendous attention since their first serendipitous

discovery owing to their unique properties, such as high chemical stability, excellent biocompatibility, facile

preparation, low cost and low toxicity 1-4, that make these materials promising candidates for use in bioimaging, 4,5

*College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang , 325035,
China. E-mail: xiangweidong001@126.com ; Fax: +86 577-86689644 Tel: +86 577-86596013
 Nanoscale Page 2 of 21

6,7
fluorescent probes and sensors, optoelectronic devices, 8,9 full-colour displays and white-light emitting
Viewdiodes
Article Online
DOI: 10.1039/C7NR05363K

(WLEDs). 8,10 Owing to their outstanding advantages, CDs have been regarded as new-generation fluorescent

materials. Currently, both top-down and bottom-up routes have been adopted for the synthesis of CDs.11-22

However, the fabricated CDs suffer from the difficulty in exhibiting broadband luminescence with maxima in the

blue-yellow region and multicolour (capable of single wavelength excitation) emissions, which together with their
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low-emission quantum yields (QY) and complicated preparation procedures has hampered their practical

Nanoscale Accepted Manuscript

applications. 23-27 Importantly, the realization of white and multicolour fluorescent CDs is an essential requirement

for many fields. 28-33 Hence, a study of CDs with visible spectrum emission is highly desirable. To date, there have

been only a few reports of multicolour emission CDs under single excitation wavelength that are different from

29-35
the CDs described in the traditional reports with excitation-dependent behaviour Despite the great efforts

devoted to the study of multicolour CDs including long wavelength emission (orange and red) carbon materials

and materials high QYs, solid-state fluorescence quenching would still be considered a great breakthrough.

Incidentally, Lin’s group have synthesized only three multicolour CDs with blue (435 nm, QY=17.6%), green

(535 nm, QY=4.8%) and red (604 nm, QY=26.1%) emissions using a solvothermal method. Flexible full-colour

emissive PVA films were achieved under UV-light irradiation using these three as-prepared CDs. The mechanism

of the different emission colours was attributed to the quantum size effect and the nitrogen content of the CDs.29

Hu et al. prepared a series of multicolour colors CDs from blue to red (400-710 nm, QY=6-20%) excited by white

light. The tuneable emissions results were ascribed to the CD’s chemical composition, primarily to the epoxides or

34
hydroxyls on the CD surface. William et al. synthesized one type of red emission CDs from

p-phenylenediamine dispersed in different solvents in order to realize various light colours (green to red,

35
QY=10-35%). The QY of the red emission CDs was 9.2%. Zhang et al. reported colourful carbon-dot based

light-emitting diodes (LEDs) from the driving current exciting the blue carbon dots (QY=40%). As is well know,

36,37
semiconductor QDs pioneered the development of multi-coloured LEDs. However, the realization of

2
 Page 3 of 21 Nanoscale

multi-coloured LEDs based on CDs is still being researched. To obtain multicolour emission LEDs, multideck
View Article Online
DOI: 10.1039/C7NR05363K

38
layers were fabricated. Chen’s group claimed that three colours emissions of nitrogen-doped carbon dots (blue

to red, 30.3-49.2%) were realized by controlling the reaction time. Moreover, CD-based white-light-emitting

diodes (WLEDs) were developed by combining the hybrids of a red fluorescent CD film and yellow emitting

phosphor-in-glass (PiG) plate with an InGaN chip. 39 Although they provided multicolour CDs, white-light carbon
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dots were not achieved. Additionally, the adjustable luminescent colours and the continuous regulation of

Nanoscale Accepted Manuscript

luminescence wavelength have not been implemented. Additionally, the luminous efficiency of the device was

relatively low. Therefore, emphasis has been given to the significant work in this area for the realization of white

carbon dots and the multicolour carbon dots with high QYs and continuously adjusted wavelengths. Moreover,

high efficiency devices with solid-state stability still must be developed. Incidentally, there are several examples

40-44
for pure white fluorescent CDs with low-emission QYs which impede their commercial applications in

WLEDs. It is noteworthy that Chen’s group produced blue, orange and white emitting CDs (QY=47%) by a

single-step pyrolysis method in 2012. Unfortunately, only three types of carbon dots were studied. However, to the

best of our knowledge, multicolour fluorescent carbon dots (including those with white emission) have not been

reported. Therefore, emphasis has been given to the significant work in this area for obtaining both multicolour

emission and white emission CDs with excellent PL intensity and high QYs.

Herein, we report an alternative facile and inexpensive strategy for the synthesis of seven colours of

nitrogen-doped CDs with emission wavelengths varying from 467 to 658 nm via pyrolysis of organic matter and

inorganic matter. Impressively, the white emission CDs with high performances were achieved. The QY of the

long wavelength CDs was as high as 32.8%. The mechanism of full-colour emission could be explained by an

energy-level model. More importantly, to avoid solid-state quenching, the multicolor CD films were fabricated by

incorporating the multicolour CDs into Polyamideresin-650 (P-650). Finally, flexible full-color CD-based

3
 Nanoscale Page 4 of 21

sandwich glasses were successfully constructed through a facile spin-coating technology. This demonstrates thatOnline
View Article
DOI: 10.1039/C7NR05363K

these materials are promising for applications in LEDs and full-colour displays.

2. Experimental section

2.1 Raw Materials

All raw materials, including ammonium citrate (AC), ethylenediamine tetraacetic acid (EDTA),
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N,N-dimethylformamide dimethyl acetal (DMF) and ethanol were purchased from Aladdin Ltd. (Shanghai, P. R.

Nanoscale Accepted Manuscript

China). Polyamideresin-650 (P-650) was acquired from the Sinopharm Chemical Reagent Co. (China). All the

materials were used as received without further refinement. Deionized water was used throughout this

investigation.

2.2 Synthesis of the multicolour fluorescent carbon dots (CDs).

Multicolour fluorescent CDs were synthesized by a facile solvothermal route. Briefly, a series of quality (0.1,

0.2, 0.3, 0.5 and 0.7 g) ammonium citrate (AC) were dispersed in 10 ml of DMF. Subsequently, the mixtures were

transferred to a 20 ml Teflon lined stainless-steel autoclave and then heated at 160 °C for 6 h, resulting in a

dark-brown solution, which is the red-emitting CDs (denoted as RCDs-1, RCDs-2, RCDs-3, RCDs-5, and RCDs-7

in the Fig. 1). Different combinations of AC, EDTA and DMF solvent result in diverse luminescence behaviours,

as tabulated in Table S1 (ESI†). Similarly, for the synthesis of the full-colour red, orange, yellow, white, cyan,

blue and dark blue luminescent CDs, the molar ratio between AC and EDTA was set at 1: 0, 4: 1, 3: 2, 1: 4, 1: 9, 2:

3, 0: 1, and the obtained materials were denoted as RCDs, OCDs, YCDs, WCDs, CCDs, BCDs, DCDs,

respectively.

2.3 Construction of the multicolour fluorescent CD-based sandwich glasses and CD-based LEDs

To investigate the possibility of the CDs acting as phosphors in LEDs, a colour converter with a CDs-based

sandwich glass was fabricated. The ultrathin glass plate (commercial glass) with the diameter of 50 mm and

thickness of 0.2 mm was purchased. To realize the stacking configuration, a flexible spin-coating technology was
4
 Page 5 of 21 Nanoscale

adopted to deposit the high-performance CD/P-650 hybrids with the multicolour fluorescent CDs (0.1-0.5 mg)Online
View Article
DOI: 10.1039/C7NR05363K

solution and P-650 (0.5 g) on the upper surface of the glass substrate. Subsequently, another ultrathin glass

substrate was placed on the completed hybrids. Finally, the CD-based sandwich glasses were achieved. A drying

treatment (100 ℃) for 24 h in vacuum was used to eliminate bubbles and solidify the glasses as shown in Fig. S1

(ESI†).
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For the fabrication of LEDs, the full-colour CDs-based sandwich glasses were incised into 3.3×2.8 mm cullet.

Nanoscale Accepted Manuscript

The full-colour LEDs were constructed by integrating the glass with the blue GaN LED chips centred at 460 nm.

2.4 Characterization

UV-vis spectra were recorded with a UV-2450 spectrometer, where the each sample was placed in cuvettes

(1.0 cm path length) to obtain the absorption spectra. To confirm the microstructure and particles size of the CDs,

transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) images were acquired using an FEI

Tecnai F20 operating at 200 kV. Fluorescence spectra and PL QY were obtained using a Horiba Jobin Yvon

Fluromax-4P spectrophotometer equipped with an absolute QY measurement apparatus. Time-resolved PL

lifetime measurements were recorded using a time-correlated single-photon counting (TCSPC) lifetime

spectroscopy system with a picosecond-pulsed diode laser (EPL-360 nm) as the single wavelength excitation light

source. To survey the surface functional chemical groups of the CDs material, the Fourier transform infrared

(FTIR) spectra and X-ray photoelectron spectroscopy (XPS) analysis were performed using a Bruker Equinox 55

FTIR spectrometer in the range of 600-4000 cm-1 and Axi Ultra DLD spectrometer with monochromatic Al Ka as

the excitation source. Optical properties of the constructed LEDs such as the colour rendering index (CRI), colour

coordinates (CIE), correlated colour temperature (CCT) and luminous efficacy (LE) were evaluated using an

integrating sphere (PMS-50, Everfine, China) under the forward current of 20 mA.

3. Results and discussion

A series of RCDs were successfully fabricated using different AC concentrations through a facile

5
 Nanoscale Page 6 of 21

solvothermal method. All obtained samples were observed under UV light to determine whether theyView
merited
Article Online
DOI: 10.1039/C7NR05363K

further investigation (Fig. 1 (a)). Fig. 1 (b) demonstrates how the PL peak position of the RCDs can be tuned from

583 to 658 nm through the variation of the AC content from 0.1 g to 0.7 g. The optimal RCDs-3 were selected for

further investigation.
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Nanoscale Accepted Manuscript

Fig. 1. (a) Photographs of the RCDs-1, RCDs-2, RCDs-3, RCDs-5 and RCDs-7 solutions under UV light (left). (b) PL emission

spectra of the CDs with various contents of AC. Inset shows a graph of the fluorescence peak position for the different RCDs.

With this motivation in mind, various amounts of EDTA were used. Interestingly, it was found that each

solution displays an emission under UV irradiation. We can precisely tune the chemical composition of the

reaction system to tune the colour, from dark blue to red even the white emission in any region of the visible

spectrum. (Fig. 2)

Fig. 2. Schematic of the synthesis of the RCDs, OCDs, YCDs, WCDs, CCDs, BCDs, DCDs.

To confirm that quantum size effects or surface defects are the origin of this amazing phenomenon, we used TEM

measurements to verify the morphology and structure of the three types of CDs, including the RCDs, WCDs and
6
 Page 7 of 21 Nanoscale

DCDs. As depicted in Fig. 3, these samples were well-dispersed, with average particle sizes of approximately 5.87Online
View Article
DOI: 10.1039/C7NR05363K

nm, 5.55 nm and 5.48 nm for the RCDs, WCDs, and DCDs, respectively (Fig. 3). The obtained HRTEM images

show that all of the CDs exhibited identical well-resolved lattice fringes with interplanar spacings of 0.21 nm and

27,31,35,39
0.32 nm, corresponding to the (100) and (002) diffraction facets of graphene. Furthermore, the particle

size distributions of theses samples remained so broad that their differences in fluorescence could not be clearly
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ascribed to differences in particle sizes. The TEM data clearly demonstrate that the interesting phenomenon

Nanoscale Accepted Manuscript

displayed by these CDs is not due to quantum size effects. 31

Fig. 3. TEM and HRTEM images of (a and d) the RCDs, (b and e) WCDs and (c and f) DCDs.

How do the surface defects influence the fluorescence of the CDs? The Fourier transform infrared (FTIR)

spectra shown in Fig. 4 revealed that all CD samples possessed abundant hydrophilic groups such as O-H (3468

cm-1), N-H (3383-3163 cm-1), C-O (1258 cm−1) and C=O (1628 cm−1), on their surfaces, thereby ensuring their

31, 35
good solubility in water. Moreover, the stretching vibrations of the C-H (2943 cm-1), C=N (1655 cm-1), C-C

(1524 cm−1), and C-N (1388 and 1496 cm-1) bonds were observed for each sample, indicating the formation of

31, 39
polyaromatic structures in the CDs during the reaction process. A comparison of the FTIR spectra of these

samples reveals two important observations. One is the enhancement of the typical stretching vibration of the O-H

bonds at 3468 cm-1 from the RCDs to DCDs. Generally, a broad O-H band indicates multiple structures of

hydroxyl groups on the nanoparticle surfaces, resulting in higher polarity and hydrophilicity of the DCDs

7
 Nanoscale Page 8 of 21

45
compared to the RCDs. The other is the weakening of the C=N vibration bands at approximately 1655 cm-1Online
View Article
DOI: 10.1039/C7NR05363K

from the DCDs to RCDs, indicating that an increase in the nitrogen content accompanies the PL redshift of the

CDs. 29, 39
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Nanoscale Accepted Manuscript

Fig. 4. Infrared spectra of the full-colour CDs.

The surface chemical composition characteristics of these samples were further investigated by XPS. The full

spectra presented in Fig. 5 show three typical peaks: C 1s (285 eV), N 1s (400 eV), and O 1s (531 eV). These

findings indicate that the samples consisted of the same elements. In the high-resolution spectra, the C 1s band can

be resolved into three peaks, corresponding to sp2 carbons (C=C/C-C, 284.5 eV), sp3 carbons (C−N, 285.7 eV),

and carbonyl carbons (C=O, 287.7 eV).45 The N 1s band can be deconvoluted into two peaks at 399.6 eV and

400.2 eV representing amino N and pyrrolic N. The O 1s band contained one peak at 531.4 eV that could be

35
assigned to C=O. Obviously, the XPS intensity at 399 eV gradually decreases from the RCDs to DCDs,

implying a corresponding decrease in the content of amide groups in the CDs (Table 1), consistent with the FTIR

results. According to the previous report by Pang, the nitrogen-containing functional groups are responsible for

the redshift of the CDs, which is caused by narrowed energy levels. 32

8
 Page 9 of 21 Nanoscale

View Article Online

DOI: 10.1039/C7NR05363K
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Nanoscale Accepted Manuscript

Fig. 5. XPS full survey and high-resolution XPS of the C1s, O1s, and N1s spectra of the (a-d) RCDs, (e-h) OCDs, (i–l) YCDs, (m-p)

WCDs, (q-t) CCDs, (u-x) BCDs, (y-β) DCDs.

9
 Nanoscale Page 10 of 21

Table 1. XPS elemental analysis results of the RCDs, OCDs, YCDs, WCDs, CCDs, BCDs, DCDs. View Article Online
DOI: 10.1039/C7NR05363K

Samples C (mol%) O (mol%) N (mol%) O/C (mol%) N/C (mol%)

RCDs 60.88 23.22 15.9 38.1 26.1

OCDs 64.19 21.72 14.09 33.8 22.0

YCDs 66.75 19.87 13.38 29.7 20.0

WCDs 63.79 24.3 11.91 38.1 18.7

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CCDs 64.01 24.46 11.53 38.2 18.0

Nanoscale Accepted Manuscript

BCDs 68.28 22.32 9.4 32.7 13.8

DCDs 76.69 23.03 0.28 30.0 0.37

The UV-vis absorption spectra of the samples are shown in Fig. 6. In the UV region of each curve between

200-300 nm, a single peak is observed at 230 nm, likely corresponding to the π-π* transitions of C=C and C=N

bonds of the sp2 C domain in the sp3 C matrix, while the absorption bands in the region of 300-700 nm are

25
attributed to the n-π* transitions of the C=O and C=N bonds. Consequently, the transitions from the n states to

the defect states on the surfaces of the CDs occur in accordance with the many previous studies of CDs. 27,31,33,39,

46-48
Notably, the absorption spectra of the WCDs with a broad absorption band in the vicinity of 300 nm are

distinctly different from those of the other CDs. This distinction is ascribed to the variety of functional groups,

such as amino and oxygen groups, which caused the trapping of the excited-state energy by the surface states. 33

10
 Page 11 of 21 Nanoscale

View Article Online

DOI: 10.1039/C7NR05363K
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Nanoscale Accepted Manuscript

Fig. 6. UV-vis absorption spectra of the RCDs, OCDs, YCDs, WCDs, CCDs, BCDs, DCDs.

The resulting CDs exhibit interesting optical properties and were thoroughly investigated. As illustrated in

2-4
Fig. 7, unlike many other reported CDs, the dual-band-type CDs examined here, such as the RCDs, OCDs,

YCDs, WCDs and CCDs, emit fluorescence with excitation-independent behaviour, but the BCDs and DCDs

exhibit excitation-dependent behaviour with increasing amounts of EDTA. Impressively, the fluorescence

emission peaks of the prepared CDs samples were clear blueshift from 658 nm, 605 nm, 599 nm, 592 nm, 568 nm

472 nm and 469 nm when the concentration of EDTA increased, showing red, orange, yellow, white, cyan, blue

and dark blue colours (see the inset photos in Figs. 7 (a-g)). Generally, excitation-dependent behaviours of CDs

33
result from the presence of nanoparticles of different sizes and a distribution of different surface states. The

TEM images show that the sizes of the multicolour fluorescent CDs are not very uniform, and in fact, range from

2 to 10 nm. Meanwhile, the emission band shapes of the RCDs, OCDs, YCDs, WCDs and CCDs are asymmetric

with small shoulder peaks in the visible region. These phenomena suggest the PL of these CDs is related to the

diverse surface states. Therefore, the excitation-independent behaviour indicates that the PL properties of the

RCDs, OCDs, YCDs, WCDs and CCDs depend on the surface states rather than on the quantum size effect, and

the surface states of these CDs should be rather uniform. For the BCDs and DCDs, this may be explained by the

distribution of different surface states. Remarkably, the WCDs exhibit excellent fluorescence properties. Although
11
 Nanoscale Page 12 of 21

their fluorescent mechanism is currently unclear, it may be attributed to the nonuniformity of the grain size
View of theOnline
Article
DOI: 10.1039/C7NR05363K

WCDs. Multiple excitation centres are present on every nanoparticle and surface energy traps that are created by

40
surface groups according to previous reports. Moreover, the obtained QYs are listed in Table S2 (ESI†) and

reached 30.4%, 31.6%, 32.8%, 35.9%, 46.1%, 67.4%, and 65.8%. The RCDs exhibited a QY of 30.4% that was

higher than the previously reported values (red). 29,34,35 These results confirm that the as-produced samples possess
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excellent fluorescence properties.

Nanoscale Accepted Manuscript

Furthermore, time-resolved photoluminescence measurements were carried out (Fig. 8). The PL decay

curves are analysed by fitting the following equation：

Y (t )  1exp ( / t1 )   2 exp(  / t 2 ) (1)

Here, α1 and α2 are the constants specifying the effect on the decay with lifetimes τ1 and τ2. The average lifetime

can be evaluated using using the following relation:

    2 2
2 2

 av  1 1 (2)
1 1   2 2
A short-lived component τ1 and a long-lived component τ2 comprised the emission decay and are related to

25,40,48
the electronic transitions in the material, indicating the strong coupling between the core and surface sates.

Compared with these CDs, these modest results of the decay lifetime indicate that semblable radiationless pitfall

and fluorescent perssad are present. The “radiationless pitfall” means that the -COOH and epoxy groups. And

49
“fluorescent perssad” represents that carbonyl, epoxy, and amino moieties. Combining the data of Table S2

(ESI†) and the enlarged decay curves from 5 to 20 ns, the difference in fluorescence decay kinetics among the

different samples can be observed. Compared to the DCDs, the RCDs exhibit a low QY and long lifetime. As is

well known, various fluorophores or energy levels present in the samples are responsible for their multiple

lifetimes. Thus, it can be deduced that multi-state emissions with different fluorophores or energy levels are

generated in multicolour CDs. The mechanism of fluorescence was related to the molecule-like states and a dark

50
intrinsic state, which has been investigated by Wang’s group. They found that the intrinsic state is attributed to
12
 Page 13 of 21 Nanoscale

View τ
the graphene core and its PL occurs with a dominant short time and low PL QY. The two radiative lifetime 1 and
Article Online
DOI: 10.1039/C7NR05363K

τ2 may be assigned to intrinsic recombination of initially populated core states, and surface states, respectively.

40,51
Based on our fit values in Table S2 (ESI†), the τ2 ( long-lived component) have a important role in the radiative

lifetime, which suggest that the fluorescence decay kinetics of these CDs was mainly caused by their surface

states.
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Nanoscale Accepted Manuscript

Fig. 7. Photoluminescence spectra of the RCDs (a), OCDs (b), YCDs (c), WCDs (d), CCDs (e), BCDs (f), and DCDs (g) under

13
 Nanoscale Page 14 of 21

different excitation wavelengths (recorded from 360 nm to 480 nm). (h) Normalized PL emission spectra of all products excited by
View Article Online
DOI: 10.1039/C7NR05363K

460 nm.
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Nanoscale Accepted Manuscript

Fig. 8. Fluorescence decay curves for the RCDs, OCDs, YCDs, WCDs, CCDs, BCDs and DCDs. Inset shows an enlarged view

of the decay curves between 5 and 20 ns.

Based on the precursor materials and experimental results, a possible growth mechanism for the multicolour

property is illustrated in Fig. 2. Urea, EDTA and AC could assemble into a nanostructure through the

intermolecular H-bonding. Under solvothermal conditions, a dehydrolysis process occurred between urea, EDTA

52
and AC to form the multicolour CDs with abundant carboxyl, hydroxyl, and amide groups on the surface. To

further confirm that the tuneable PL originated from the surface defect states, the pH-dependent behaviour of the

RCDs was examined. In Fig. S2 (ESI†), the RCDs are shown to be enhanced in both acidic and alkaline

environments, and the PL peak blueshifts significantly as the pH decreases. The blueshift of the PL with

decreasing pH value (Fig. S2(c)) suggest that the high concentration of H+ causes electronic transition changes of

53
π–π* and n–π* in the RCDs by refilling or depleting their energy levels. This means that H+ forms a charge

transfer complex around the CDs, where the stability is directly related to the energy necessary for the charge
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 Page 15 of 21 Nanoscale

transfer to the adsorbate. Hence, the protonation and deprotonation of the RCDs due to changes in theView
pHArticle
mayOnline
DOI: 10.1039/C7NR05363K

54,55
cause electrostatic doping/charging in the RCDs, thereby shifting the Fermi level. The pH effect can be

ascribed to the basic nature of the emitting states on the surface of the CDs.

Currently, two popular PL mechanisms have been proposed for CDs: with the first mechanism, based on the

band gap transitions in the conjugated π-conjugated. The second mechanism is related to surface defects on the
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CDs. In accordance with the former mechanism, several reports ascribed the PL redshift of the CDs to quantum

Nanoscale Accepted Manuscript

29,32
size effects. However, in our case, we believe the surface states to be the dominant factor controlling the PL

variations because all of our samples exhibited similar and broad size distributions. Obviously, the DCDs show

characteristic absorption peak at 230 nm for the π-π* transitions of the sp2 C domains in Fig. 6, with a tail

extending in the visible range. Additionally, the shoulder peaks are located at 341 nm, which can be ascribed to

the n-π* transitions of C=O. The absorption bands in the region of 350-700 nm are attributed to the n-π*

transitions of C=N. 35,39 The absorption peaks almost disappear with only one remaining peak before 300 nm after

the addition of AC. The redshifts of the CDs may arise from the effects of the C=O and C=N groups on the energy

levels of CDs.39 Notably, these CDs exhibit a double-exponential decay with the lifetime listed in Table S2 (ESI†).

It is well know that the existence of diverse fluorophores or energy levels exist in the samples is beneficial for

their multiple lifetimes. Based on the above studies, an energy-level model for the surface states for the

mechanism is proposed to account for the continuously adjustable full-colour emissions, as illustrated in Fig. 9.

The oxygen-based groups and amine-based groups contribute to the surface states in the CDs, which coincide with

2-4
the previous reports. An electron transition from the highest occupied molecular orbital (HOMO) to the π*

orbital of the lowest unoccupied molecular orbital (LUMO). 49 For the CDs with various surface states, except for

the HOMO-2 (π) energy level, two new HOMO-1 and HOMO energy levels are introduced by the abundant

surface functional groups, such as C=O and C=N. Then, efficient electron transitions can occur from the two new

HOMO-1 and HOMO energy levels to the LUMO (π*). As a result, the PL band in the long wavelength region

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will occur, while the electrons in the N-related defect states return to the HOMO.39 To provide supportView
forArticle
thisOnline
DOI: 10.1039/C7NR05363K

conclusion, CDs with different surface groups were prepared by varying the ratio of AC to EDTA from 1:0 to 0:1.

These CDs feature full-colour emission properties. The variation of the PL peaks is consistent with the change of

contents for the C=O and C=N groups. These results for the multicolour emissions were derived from the

radiation of the excited electrons from the n-π* transitions of the C=O and C=N groups. 49 Thus, the continuously
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adjustable full-colour emissions could be achieved. Last but not least, the WCDs were achieved due to the

Nanoscale Accepted Manuscript

nonuniformity of grain the size, as confirmed by TEM. More importantly, the multiple excitation centres on every

40
nanoparticle and surface energy traps are created by the surface groups. It is believed that the surface states of

the CDs are similar to a molecular state, wherein various surface states correspond to a relatively wide distribution

of different energy levels. The emission band shape of the WCDs is asymmetric with small shoulder peaks in the

visible region. These phenomena suggest the PL of the WCDs is related to the diverse surface states. Similarly, the

absorption spectra of the WCDs exhibit a broad band in the region of 250-500 nm, implying that multiple energy

levels exist in the CDs. The white light may be attributed to the overlap of diverse light emissions induced by the

electron transitions in the multiple levels.

Fig. 9. (a) Structure of the multicolour CDs. (b) Schematic illustration of the proposed energy level and electron transition diagrams

of the multicolour CDs.

4. Applications

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View Article Online

DOI: 10.1039/C7NR05363K
Published on 11 October 2017. Downloaded by University of Newcastle on 11/10/2017 07:44:15.

Nanoscale Accepted Manuscript

Fig. 10. CIE colour coordinates of the multicolour LED fabricated by integrating the 460 nm blue chip with the multicolour

CD-based sandwich glasses. EL of the fabricated multicolour CD-based sandwich glass: RCDs (a), OCDs (b), YCDs (c), WCDs (d),

CCDs (e), BCDs (f), DCDs (g). The inset photograph of the multicolour CD-based sandwich glass LEDs.

Table 2. Photoelectric parameters of the multicolour LEDs

Samples Thickness CIE coordinates LE (lm/W) CCT (K) CRI

X Y
RCDs 0.61 0.32 25.63 1396 74.8
OCDs 0.50 0.32 24.37 2055 50.8
YCDs 0.42 0.33 25.10 3986 75.1
WCDs 0.7 mm 0.32 0.33 32.26 6565 68.4
CCDs 0.27 0.30 28.97 9656 76.2

BCDs 0.23 0.26 21.58 100000 74.0

DCDs 0.19 0.12 17.91 100000 38.9

Considering the outstanding optical properties of the multicolour CDs in solution, preparation of full-colour

emissive LEDs was attempted. Excitingly, the CIE coordinate of all these composite glasses display a linear

distribution, that is, the seven CDs are located at the adjacent flankian locus. We note that full-colour emission

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sandwich glasses could be achieved with the appropriate thickness. These devices showed nice emission colours
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DOI: 10.1039/C7NR05363K
of red, orange, yellow, white, cyan, blue and dark blue. Fortunately, a white-light emission sandwich glass with a

CIE coordinate of (0.32, 0.33) was gained and is very close to the pure white light (0.33, 0.33). Furthermore, the

relevant electroluminescence (EL) spectra of the constructed LEDs are attached to Fig. 10. The related

photoelectric parameters including CCT, CRI, luminous efficacy (LE) and chromaticity coordinates (CIE) are

tabulated in Table 2. Therefore, the CDs have great potential for the preparation of LEDs for various colour

emissions.
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5. Conclusions

Nanoscale Accepted Manuscript

In summary, multicolour nitrogen-doped CDs were synthesized from a precursor comprising AC and EDTA.

Importantly, the mixtures of these CDs in glasses displayed ensemble emissions of their individual components,

thus demonstrating the potential for the preparation of flexible full-colour emissive glasses. To the best of our

knowledge, this is the first time that emissions of the various colours, including white emission CDs excited by

UV light, have been realized. We found that the continuously adjustable full-colour emissions were due to the

energy level and electron transitions of the surface functional groups, such as C=O and C=N. In consideration of

their excellent performances, these CDs can be potentially used in numerous applications, such as flexible

full-colour displays and optoelectronic devices. This work offers an open insight into multicolour CDs from the

viewpoints of synthesis and mechanism, which will be beneficial to the applications of multicolour CDs in the

near future.

Acknowledgments

The work was financially supported by the Zhejiang Province Natural Science Foundation (LQ14E020006)

and National Nature Science Foundation of China (51472183 and 51672192).

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