Electronic Supplementary Material (ESI) for Nanoscale.

This journal is © The Royal Society of Chemistry 2017

Electronic Supplementary Information

Roles of Nitrogen Functionalities in Enhancing the

Excitation-Independent Green-Color Photoluminescence of

Graphene Oxide Dots

Chiao-Yi Teng,a Ba-Son Nguyen,a Te-Fu Yeh,a Yuh-Lang Lee,a Shean-Jen Chen,b and

Hsisheng Teng*a

a
Department of Chemical Engineering and Research Center for Energy Technology and

Strategy, National Cheng Kung University, Tainan 70101, Taiwan

b
College of Photonics, National Chiao Tung University, Tainan 71150, Taiwan

*To whom correspondenec should be addressed. E-mail: hteng@mail.ncku.edu.tw, Tel:

886-6-2385371, Fax:886-6-2344496

Supporting Information for:

(1) Color and quantum yield of graphene oxide dots

(2) Color and quantum yield of carbon dots

(3) TEM images of GODs

(4) XPS analysis of NGODs and GODs

(5) Raman spectra of the GO-based dots

(6) FTIR spectra of the GO-based dots

(7) PL quantum yield measurements

(8) The Mott-Schottky equation for the conductivity-type determination

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(9) UPS analysis for valence band maxima of the GO-based dots

(10) Application of A-GODs as a phosphor for white-light emission

2
1. Color and quantum yield of graphene oxide dots

Table S1 Summary of the color/wavelength (λ) and quantum yield (QY) of

photoluminescence emissions from graphene oxide dots synthesized through top-down and
bottom-up routes.

color/λ (nm) QY (%) heteroatom precursor Ref.

(source) (synthesis)
top-down
ultraviolet/360 28 nitrogen GO 1
(poly(ethylene glycol)) (hydrothermal)
violet/407* 3.4 − GO 2
(ultrasonic)
violet/413 35 nitrogen GO 3
(ammonia) (hydrothermal)
violet/423 7.1 − graphite flask, CNT 4
(electrochemical)
violet/425 8.6 nitrogen GO 5
(ammonia) (hydrothermal)
violet/430 46 nitrogen GO 6
(ammonia) (hydrothermal)
violet/430 6.9 − GO 7
(hydrothermal)
violet/430 12 nitrogen GO 8
(dimethylformamide) (solvothermal)
blue/450 23 − GO 9
(microwave)
blue/450 7.4 nitrogen GO 10
(poly(ethylene glycol) diamine) (chemical-oxidation)
blue/450 9.7 nitrogen graphite nano-particles 11
(dimethylformamide) (solvothermal)
blue/460 21 nitrogen GO 12
(poly(ethylenimine)) (hydrothermal)
cyan/490* 13 boron graphite rod 13
(borax) (electrochemical)
cyan/500 74 nitrogen GO 14
(dimethylformamide) (solvothermal)
cyan/500 12 − GO 9
(microwave)
green/515 11 nitrogen GO 15
(dimethylformamide) (solvothermal)
green/516 12 nitrogen GO 16
(dimethylformamide) (solvothermal)
green/520 31 nitrogen GO 17
(dimethylformamide) (solvothermal)
green/520 14 nitrogen carbon black 18
(insulin) (acidic-refluxing)
3
green/520 18 nitrogen graphite nano-particles 11
(dimethylformamide) (solvothermal)
green/540* 14 − graphite rod 19
(electrochemical)
yellow/570 6.9 nitrogen graphite nano-particles 11
(dimethylformamide) (solvothermal)
yellow/570 2.3 − carbon black 20
(acidic-refluxing)
red/640 15 nitrogen graphite nano-particles 11
(dimethylformamide) (solvothermal)
bottom-up
violet/402* 84 nitrogen melamine 21
(melamine) (pyrolysis)
violet/425* 40 nitrogen citric acid 22
(ammonia) (hydrothermal)
violet/435* 78 nitrogen/sulfur citric acid 23
(urea/thiourea) (hydrothermal)
violet/436* 79 nitrogen melamine 21
(melamine) (pyrolysis)
blue/440 54 − L-glutamic acid 24
(pyrolysis)
blue/450* 94 nitrogen citric acid 25
(ethylene diamine) (hydrothermal)
blue/452 37 nitrogen citric acid 26
(dicyandiamide) (hydrothermal)
blue/470 21 nitrogen pyrene 27
(hydrazine) (hydrothermal)
blue/473 11 − glucose 28
(microwave)
blue/474 12 − glucose 29
(microwave)
cyan/490 45 nitrogen pyrene 27
(hydrazine) (hydrothermal)
cyan/495* 76 nitrogen melamine 21
(melamine) (pyrolysis)
cyan/510 3.8 − hexabenzocoronene 30
(pyrolysis)
green/524* 44 nitrogen/chlorine glucose 31
(ethylenediamine/HCl) (hydrothermal)
green/530 23 nitrogen pyrene 27
(hydrazine) (hydrothermal)
green/535* 12 sulfur pyrene 32
(Na2S) (hydrothermal)
green/560* 71 nitrogen o-phenylenediamine 33
(precursor) (electrochemical)
yellow/570 70 nitrogen pyrene 27
(hydrazine) (hydrothermal)
yellow/570 75 nitrogen glucose 34
(ammonia) (basic-mixing)
4
 orange/587* 72 nitrogen melamine 21
(precursor ) (pyrolysis)

*excitation independent

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2. Color and quantum yield of carbon dots

Table S2 Summary of the color/wavelength (λ) and quantum yield (QY) of

photoluminescence emissions from carbon dots synthesized from the bottom-up route.

heteroatom precursor
color/λ (nm) QY (%) Ref.
(source) (synthesis)
bottom-up
violet/390 42 nitrogen citric acid 35
(melamine) (hydrothermal)
violet/415 73 nitrogen/sulfur citric acid 36
(L-cysteine) (hydrothermal)
violet/420 99 nitrogen citric acid 37
(2-aminoethanol) (microwave)
violet/430 30 nitrogen/phosphorous glucose 38
(ammonia/phosphoric acid) (hydrothermal)
blue/450 83 nitrogen/magnesium citric acid 39
(ethylenediamine/Mg(OH)2) (hydrothermal)
blue/450 28 nitrogen poly(saccharide) 40
(ethylenediamine) (hydrothermal)
blue/450* 80 nitrogen/boron citric acid 41
(ethylenediamine/boric acid) (hydrothermal)
blue/450* 85 nitrogen citric acid 42
(ethylenediamine) (hydrothermal)
yellow/568* 33 nitrogen triaminobenzene 43
(precursor) (solvotherml)
yellow/573* 38 nitrogen o-phenylenediamine 44
(precursor) (microwave)
red/620* 47 nitrogen/sulfur/copper HEDTAa 45
(L-cysteine/CuCl) (microwave)

*Excitation independent
aN-(hydroxyethyl)-ethylenediaminetriacetic acid

6
3. TEM images of GODs

Fig. S1 Morphology and crystal structure of GODs. (a) TEM image with the inset showing

the histogram of size distribution. (b) HRTEM image of a GOD particle, showing graphene

{ 1 100 } lattice planes with a d-spacing of 0.213 nm.

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4. XPS analysis of NGODs and GODs

Fig. S2 XPS spectra of NGODs and GODs. (a) Full-range spectrum of NGODs. (b)

Full-range spectrum of GODs. (c) C 1s spectrum of NGODs. (d) C 1s spectrum of GODs. (e)

N 1s spectrum of NGODs. C 1s and N 1s spectra are decomposed into several peaks

(indicated by dashed lines) and fitted using a Gaussian function.

8
5. Raman spectra of the GO-based dots

Fig. S3 Raman spectra of GODs, NGODs, A-GODs, and A-NGODs. The dash lines

indicate the positions of the D, G, D’, and 2D bands of GODs.

9
6. FTIR spectra of the GO-based dots

Fig. S4 FTIR spectra of GODs, NGODs, A-GODs, and A-NGODs.

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7. PL quantum yield measurements

A highly reliable method for evaluating the PL quantum yield (QY) is the

comparative method of Williams et al.,48 which involves the use of well characterized

standard samples with known QY values. Plot a graph of integrated fluorescence intensity

from fluorescence spectrum vs. absorbance from UV-vis absorbance spectrum. Repeat above

steps for five solutions with increasing concentrations of the standards and samples. The PL

QY of the samples were calculated in accordance with the following cross-calibration

equation,49

 Grad x  ηx2 
QYx =   2 QYst (3)
 Grad st  ηst 

where Grad is the gradient of the plot of fluorescence intensity vs. absorbance and η is the

reflective index of the solvent. Note that “x” refers to the sample and subscript “st” refers to a

standard with known quantum yield (the values of QYst here for a fluorescein-ethanol solution

and a rhodamine 6G-ethanol solution are 0.79 and 0.95, respectively50,51). In order to

minimize re-absorption, absorbance in the 10×10 mm fluorescence cuvette was kept below

0.1 at an excitation wavelength 470 nm. For each test sample, two QYx values were obtained,

one relative to standard A, the other to standard B. The QY of the sample was then taken as

the average of the two values. Fig. S5 presents the typical fluorescence and absorbance

measurements for an A-GOD dispersion and a fluorescein-ethanol standard solution. Fig. S6

shows the determination of the gradients in the plots of fluorescence intensity vs. absorbance

for the two standards and the A-GODs. Table S3 presents the gradients and PL QY of the

GO-based dots determined using the data of Figs. S5 and S6 in compliance with Eq. (3).

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Fig. S5 PL spectra of (a) the A-GODs dispersion (0.1 mg mL-1) and (b) the

fluorescein-ethanol standard solution (0.03 mg mL-1). Absorption spectra of (c) the A-GODs

dispersion and (d) the fluorescein-ethanol standard solution.

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Fig. S6 Plots of PL intensity vs. absorbance for Rhodamine 6G (black line), fluorescene

(red line), and A-GODs (blue line). Note that the gradient of the lines is proportional to the

QY of the corresponding sample.

13
Table S3 The gradients and PL QY of the GO-based dots determined using the data of

Figs. S5 and S6 in compliance with Eq. (3).

Gradx QYFL QYR6G QYaverage

GODs 526276.4 0.11 0.12 0.12
NGODs 669806.3 0.14 0.15 0.14
A-GODs 2918441.7 0.61 0.65 0.63
A-NGODs 2679225.1 0.56 0.60 0.58

The parameters used in Eq (3):

GradFL = 3614712.3
GradR6G = 4085559.7
ηwater = 1.33
ηethanol = 1.36
QYFL = 0.79
QYR6G = 0.95

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8. The Mott-Schottky equation for the conductivity-type determination

The GODs were deposited on a glassy carbon substrate. The conductivity types and Fermi

level (EF) potentials of the GOD films were then determined via electrochemical impedance

spectroscopic analysis based on the Mott-Schottky equation,46,47 i.e.

1 2 kT
= ( E − EF − ) for n-type conductivity
C 2
eεε 0 N D e
1 2 kT
=− ( − E + EF + ) for p-type conductivity
C 2
eεε 0 N A e
where C represents the capacitance of the space−charge region, ε0 is the vacuum permittivity,

ε is dielectric constant of semiconductors, e is the electron charge, E is applied potential, EF is

the Fermi level potential, k is the Boltzmann constant, T is the absolute temperature, and NA

(ND) is the acceptor (donor) density. Nota that the temperature term is generally small and can

be neglected. The capacitance values of the space−charge region were obtained at various

applied potentials. According to the Mott-Schottky equation, 1/C2 and E are linearly related,

with a negative slope indicating p-type conductivity and a positive slope indicating n-type

conductivity.

Fig. S7 presents the variation of the capacitance in the space-charge region of the GODs

and A-GODs with the applied potential in compliance with the Mott–Schottky equation.

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Fig. S7 Variation of capacitance (C) with applied potential in 2 M H2SO4 presented in the

Mott-Shottky relationship for electrodes deposited with (a) GODs and (b) A-GODs. The

capacitance was determined by electrochemical impedance spectroscopy and the negative and

positive slopes correspond to p- and n-type conductivities, respectively.

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9. UPS analysis for valence band maxima of the GO-based dots

To identify the valence band maxima (i.e., the n-state, denoted as Ev), the GODs were

deposited on the silicon substrate and the value of Ev was determined using UPS with He I

light (21.2 eV) irradiation. The UPS analysis was performed in accordance with:

EB + Ek + ϕ = 21.2 (1)

where EB is the binding energy measured from the Fermi level, Ek is the kinetic energy of

electrons, ϕ is the work function of the GODs, and 21.2 eV is the excitation energy of the He

I light.

Ev was then calculated as:

Ev = 21.2 − (EB2 − EB1) (2)

where EB2 is the secondary cutoff binding energy in the UPS spectra, in which the Ek of the

excited electrons is equal to 0 and the EB1 is the difference between the Fermi edges and the

valence band edges. Fig. S8 shows the UPS spectra of the GODs and A-GODs. Note that EB1

can be determined from the intercepts of the extrapolated straight lines on the abscissa at low

binding energy. Similarly, EB2 can be estimated using the secondary cutoff values (Ek = 0 eV)

in the UPS spectra, which are obtained from the intercepts of the extrapolated straight lines

on the abscissa at high binding energy. The UPS widths is obtained directly as the difference

between EB2 and EB1. Finally, Ev is obtained by subtracting these UPS widths from the

excitation energy (21.2 eV).

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Fig. S8 UPS spectra of the samples: (a) GODs and (b) A-GODs. The VBM levels with

respect to the Fermi levels were determined from the intercepts of the extrapolated straight

lines (blue dashed line) on the abscissa at low binding energy. The intersections of the tangent

(red dashed line) with the abscissa at high binding energy give the secondary electron onset

binding energy. The UPS widths (black lines) can be determined by these two intercept

binding energies, and the VBM levels can be calculated by subtracting these widths from the

excitation energy (21.2 eV).

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10. Application of A-GODs as a phosphor for white-light emission

We mixed aqueous solutions of A-GOD (0.5 g L-1) and poly(vinyl alcohol) (PVA) (10

wt%) to form the precursor mixture of the A-GODs-embedded PVA film. For the fabrication

of white light emitting diode (LED), the mixture was dispensed on a violet (365 nm)-LED

chip and thermally dried at 60 °C for 24 h. The combination of the A-GODs-embedded PVA

film and violet-LED chip provides white light emissions, which are tunable through adjusting

the concentration of A-GODs in the PVA film. The device was characterized in a N2-filled

glove box with oxygen and water contents less than 1 ppm. The Commission International

d’Eclairage color coordinate of the light emission from the device was measured using a

Keithley 2400 source meter and a PR650 colorimeter.

Fig. S9 A-GODs as a phosphor for white-light emission. (a) A device consisting of an

A-GODs-embedded PVA film covering a violet (365 nm)-light emitting diode (LED) chip. (b)

White light emission from the device when the LED turned on. (c) The Commission

International d’Eclairage color coordinate for the white light emission shown in panel (b).

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