Letter

pubs.acs.org/JPCL

Elucidating Quantum Confinement in Graphene Oxide Dots Based

On Excitation-Wavelength-Independent Photoluminescence
Te-Fu Yeh,† Wei-Lun Huang,‡ Chung-Jen Chung,§ I-Ting Chiang,‡ Liang-Che Chen,† Hsin-Yu Chang,∥
Wu-Chou Su,‡ Ching Cheng,⊥ Shean-Jen Chen,§,∥ and Hsisheng Teng*,†,§
†
Department of Chemical Engineering and Research Center for Energy Technology and Strategy, National Cheng Kung University,
Tainan 70101, Taiwan
‡
Department of Internal Medicine, College of Medicine and Hospital, National Cheng Kung University, Tainan 70101, Taiwan
§
Center for Micro/Nano Science and Technology, National Cheng Kung University, Tainan 70101, Taiwan
∥
Department of Engineering Science, National Cheng Kung University, Tainan 70101, Taiwan
⊥
Department of Physics, National Cheng Kung University, Tainan 70101, Taiwan
*
S Supporting Information

ABSTRACT: Investigating quantum confinement in graphene under

ambient conditions remains a challenge. In this study, we present graphene
oxide quantum dots (GOQDs) that show excitation-wavelength-independ-
ent photoluminescence. The luminescence color varies from orange-red to
blue as the GOQD size is reduced from 8 to 1 nm. The photoluminescence
of each GOQD specimen is associated with electron transitions from the
antibonding π (π*) to oxygen nonbonding (n-state) orbitals. The observed
quantum confinement is ascribed to a size change in the sp2 domains, which
leads to a change in the π*−π gap; the n-state levels remain unaffected by
the size change. The electronic properties and mechanisms involved in
quantum-confined photoluminescence can serve as the foundation for the
application of oxygenated graphene in electronics, photonics, and biology.

fluorescence.3,8,9 The oxidized sp3 sites can be regarded as

T he zero-mass-electron feature for graphene indicates that
finite-sized graphene can exhibit a quantum-confined
energy gap.1 The quantum-confined energy gaps of graphene
quantum dots carved from graphene were determined using a
single-electron transistor with quantum point contacts.2
Because graphene is an environmentally sensitive material, its
intrinsic electronic properties can be determined only under
ultraclean and strictly regulated conditions, which restricts its
practical applications. Graphene oxide (GO)3 and graphene
quantum dots bearing oxygen functionalities4 provide an
opportunity to explore the electronic structures of graphene
under ambient conditions. Despite considerable efforts, study-
ing the optical properties of GO to elucidate the quantum size
effect has been difficult because the presence of defect states
results in excitation-wavelength-dependent photoluminescence
(PL) emissions,5−7 and the inhomogeneous distribution of
oxygenated sites prevents the optical properties from being
strongly dependent on the size.8,9 The synthesis of homoge-
neously oxygenated graphene quantum dots is the key to
deciphering the electronic structure of GO with quantum
confinement.
GO contains sp2 domains and sp3-hybridized carbon atoms
covalently bound to oxygen functional groups.10−13 The CO
bonds disrupt the extended sp2 conjugated network and isolate
the sp2 domains, where the π electrons are confined;
consequently, the band gap becomes finite, giving rise to
fluorophores, and they contribute to long-wavelength fluo-
rescence.14,15 Exploring the size-dependent properties of GO is
essential for elucidating the quantum-confinement fundamen-
tals underlying the optical design of GO.
Numerous methods have been developed for synthesizing
graphene oxide dots (GODs), which exhibit PL emissions of
various wavelengths.4,5,16−20 To obtain size-dependent PL, we
should consider the three major origins of luminescence
emissions in GODs: (I) sp2 domains,3,5,20−22 (II) zigzag edge
sites,4,5 and (III) surface defect sites.20−23 For investigating
quantum confinements in the sp2 domains (origin I), previous
studies have regulated the sp2-domain size by removing the
oxygen groups from GODs; however, these GODs did not
show sp2-domain-dependent PL emissions,3 and this observa-
tion is attributable to uneven oxidation in the sp2 domains.
Peng et al. reported luminescence in three colors in the GODs
of three sizes. The size-dependent luminescence was attributed
to emissions from the zigzag edge structure (origin II) that
shows a controllable energy difference between the σ and π
states in a carbene-like triplet ground state.5 However, the PL
emissions were dependent on the excitation wavelength,6,7
Received: April 7, 2016
Accepted: May 18, 2016

© XXXX American Chemical Society 2087 DOI: 10.1021/acs.jpclett.6b00752

J. Phys. Chem. Lett. 2016, 7, 2087−2092
The Journal of Physical Chemistry Letters
indicating that surface defect states might be involved in the PL
process, and the size effect was not strong. The surface defect
sites on GODs (origin III), such as oxygen functionalities,20−23
can provide intermediate states (i.e., the nonbonding states (n-
states) in oxygen atoms) within the π−π* energy gap, which is
reflected by red shifts in both light absorption (n → π*
transition) and PL emissions. Quantum confinement in GODs
is difficult to detect because the reported synthesis processes
generally cause inhomogeneous oxygen distribution and
vacancy defects.24−26
Previous studies reported quantum confinement in graphene
and carbon dots synthesized using amidative cutting27 and
ultrafiltration,28 respectively. However, these studies neglected
the influence of heterogeneities in oxygen functionalities on PL
emissions. In the present study, we develop a method for
synthesizing high-crystallinity, high-uniformity GODs emitting
excitation-wavelength-independent PL and devise a strategy for
particle sieving to elucidate how quantum confinement affect
PL emissions from GODs. We demonstrate that the PL is
associated with the π* → n transition of electrons. The
observed quantum confinement is ascribed to the change in the
size of the sp2 domains, which leads to a change in the π−π*
energy gap; the n-state levels remain unaffected by the change
in size. The results make a meaningful contribution to existing
fundamental understanding of quantum-confined photonics of
graphene.
The preparation of the graphene oxide quantum dots
(GOQDs) used in this study is described in the Supporting
Information. In brief, we first prepared GODs from mild
oxidation of GO sheets that were derived from graphite
oxidation and then sieved the GODs through poly(ether
sulfone) membranes to obtain GOQDs. Here, we report the
direct observation of the quantum size effect in GOQDs
obtained by sieving high-quality GODs by using centrifugation
tubes filled with the polyethersulfone membranes of different
pore sizes. Figure S1 presents high-resolution transmission
electron microscopy (HRTEM) images of GOQD specimens
and Fourier transform (FFT) patterns of two GOQD
specimens. All the particles have high crystallinity and the
graphene {11̅00} planes with a d-spacing of 0.213 nm.
However, aggregation of some particles was inevitable in
TEM analysis (Figure S1i) because the GOQDs were not
protected by capping reagents. We used Raman spectroscopic
analysis to determine the mean sp2-domain size of the GOQD
specimens according to the intensity ratio between the D and G
bands in the Raman spectra (Figure S2).29−32 The sizes
estimated by Raman spectroscopy were consistent with those
approximately determined using HRTEM, although the former
values were slightly smaller because the oxygenated regions
were ignored in the Raman estimation. The GOQD specimens
are denoted using the acronym QD followed by their mean sp2-
domain sizes (in angstrom), as determined by Raman analysis.
For example, QD26 presented in Figure S1 has a mean size of
2.6 nm.
Figure 1a shows the GOQD dispersions (in water at 400 mg
L−1) under daylight lamp irradiation. The color of the
dispersions varied slightly with the GOQD size. Under
ultraviolet light irradiation at 365 nm, the GOQD specimens
exhibited multiple PL colors, varying from orange-red for
QD79 to blue for QD10 (Figure 1b). The size dependence of
the PL color resulted from quantum confinements in the sp2
domain, which is elucidated in the following discussion.
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Figure 1. Photographs of aqueous dispersions of GOQDs of different
sizes. (a) GOQD dispersions under daylight lamp irradiation. (b)
GOQD dispersions under UV lamp irradiation (365 nm center
wavelength).
Considering the probable influence of the thickness of the
GOQD discs on PL emissions,33 we analyzed the topography of
GOQDs on mica substrates by using atomic force microscopy
(AFM). The AFM images (Figure S3) show that the
topographic heights of the GOQDs range from 1 to 2 nm
and are monodisperse at approximately 1.5 nm, indicating that
the GOQDs are principally 1−2 layers. We used X-ray
photoelectron spectroscopy (XPS) to analyze the chemical
composition of each GOQD specimen (Figure S4). The full-
range XPS spectra revealed that the O/C atomic ratios of the
GOQDs with sizes exceeding 2 nm were approximately 0.4−0.5
(Table S1), indicating the similar degree of surface oxidation of
the GOQDs. For the GOQDs with sizes smaller than 2 nm, the
O/C ratios were slightly higher, suggesting that the number of
oxygen groups at the periphery of the GOQDs began
influencing the overall oxygen content.
The composition of oxygen functionalities was obtained by
deconvoluting the C 1s spectra (Figure S5). For sizes larger
than 2 nm (Table S1), the GOQDs showed similar CO
contents, indicating that the GOQDs had similar concen-
trations of basal-plane oxygen functionalities (mainly the epoxy
group). The concentration of periphery functionalities (CO
and OCO) slightly increased with a decrease in the
particle size because of the increasing contribution of edge sites
to the overall oxygen functionalities. For the size further
decreased to less than 2 nm, the CO content increased at the
expense of the CO/OCO loss, indicating that the
formation of hydroxyl groups at the periphery was favorable for
small GOQDs. Theoretical calculations will reveal that OH is
stable functionalities at the periphery of small-size graphene.
The above XPS analysis reflects the uniform concentrations of
the epoxy CO bonding on the basal plane for all the
GOQDs, which indicates the homogeneous distribution of
oxidized sp3 sites on the basal plane. Fourier transform infrared
(FTIR) spectroscopic measurements of the GOQDs (Figure
S6) also reveal similar epoxy intensities for all the GOQDs.
Figure 2a presents optical absorption spectra. The pro-
gressive shift of the absorption band edge to short wavelengths
with a decrease in the size of the GOQDs is apparent. The
maximal absorbance of each GOQD spectrum can be ascribed
to the π → π* transition in the sp2 domains,3 which dominate
the GOQD structures. The absorption edge may correspond to
the n → π* transitions of nonbonding electrons of oxygen
atoms involved in CO or CO bonds.23 We used ultraviolet
photoelectron spectroscopy (UPS) to determine the highest
occupied orbital level (i.e., the n-state level) of the GOQD
DOI: 10.1021/acs.jpclett.6b00752
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Figure 2. Optical spectroscopic analysis of GOQD suspensions. (a)
Normalized optical absorption spectra of the GOQDs. (b) Normalized
PL spectra of GOQDs excited by 350 nm monochromatic radiation
grated from a xenon lamp.
specimens and found that their n-state levels were almost
identical, irrespective of the GOQD size (Figure S7).
Figure 2b shows the normalized PL spectra of the GOQD
specimens excited at a wavelength of 350 nm. The specimens
exhibited single PL peaks at 580 nm (QD79), 560 nm (QD61),
540 nm (QD54), 520 nm (QD26), 490 nm (QD16), and 460
nm (QD10). The PL emissions encompass the orange-red to
blue region of the visible spectrum. Comparison of the
absorption and PL spectra revealed that the wavelength of
the PL peak was close to that of the absorption edge for each
GOQD specimen (although the absorption edge could not be
precisely positioned in the spectra). Therefore, we assigned the
single-peak PL emissions to radiative π* → n transitions.9 The
energy values or wavelengths of the radiative transitions are
governed by the particle size (i.e., by the degree of quantum
confinement). All the GOQD dispersions showed excitation-
wavelength-independent PL emissions (Figure S8), indicating a
scarcity of trap states between the π* and n-state energy levels.
The trap-free characteristics enable the precise identification of
the discrete energy levels of the orbitals or states in the
electronic structures of the GOQDs.
Figure 3 presents normalized PL excitation (PLE) spectra,
which reveal the excitation wavelengths for local maximum PL
emissions at the peak wavelengths depicted in the PL spectra
(Figure 2b). The deconvolution of the PLE spectra revealed
that each GOQD specimen exhibited three absorptive
transition peaks. The long-wavelength peak is ascribed to the
n → π* transition because this peak has an energy value slightly
larger than that of PL emissions. The intermediate-wavelength
peak has an energy value close to that of the absorbance
maximum and is assigned to the π → π* transition. The short-
wavelength peak with high energy is believed to result from the
n → σ* transition. Such peaks have been reported for GO, in
the sp3 domains associated with hydroxyls, amines, and
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Figure 3. PLE spectra of the aqueous GOQD dispersions. (a) QD79,
(b) QD61, (c) QD54, (d) QD26, (e) QD16, and (f) QD10. The PLE
spectra were monitored at the wavelengths for the maximal PL
emissions from the GOQDs shown in Figure 2b. Each PLE spectrum
can be deconvoluted into three peaks that correspond to electron
transitions: n → σ* (blue), π → π* (green), and n → π* (red).
ethers.34,35 As examples, the PL quantum yields of QD10 and
QD54 were measured to be 6% and 16%, respectively (see the
Supporting Information). The moderate quantum yields
exhibited by the GOQDs can be explained by the fact that
the present work does not cap the GOQDs using any reagents
or specific functionalities.
Figure 4 presents a schematic of the energy levels associated
with the absorption and PL of the GOQDs. We located the n-
state level (i.e., the highest occupied orbital level) of each
GOQD specimen on the basis of the UPS analysis. The n-state
levels of the specimens were located at similar energetic
positions. The energy values required for the n → π*, π → π*,
and n → σ* transitions in each GOQD specimen (Figure 3)
were used to determine the levels of the π, π*, and σ* states on
the basis of the identified n-state level. The excitation-
wavelength-independent PL emissions were ascribed to the
π* → n transition. The PLE spectra depict an energy difference
between the absorptive n → π* and radiative π* → n
transitions. This energy difference cannot be attributed to the
relaxation of electrons to shallow trap states below the π* level
because the presence of trap states generally results in
excitation-wavelength-dependent emissions. Instead, the energy
level diagram in Figure 4 shows that the transition of electrons
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Figure 4. Schematic energy level diagram for GOQD specimens. A
schematic of the energy levels associated with size-dependent PL
emissions from the GOQDs. The energy levels are determined on the
basis of UPS (see Figure S7) and PLE (see Figure 3) analysis. The
level of the n-states is not disturbed by a change in the particle size,
whereas the levels of the π, π*, and σ* orbitals vary considerably with
the size. The π* → n recombination, which involves phonon scattering
and an electron transition, is responsible for the excitation-wavelength-
independent PL in the GOQD specimens. The relaxation of electrons
from the σ* orbital to the π* orbital is essential for PL emissions
induced by short-wavelength excitation. The PL color varies from
orange-red (for QD79) to blue (for QD10).
from the π* orbital to the n-state orbital for radiative
recombination involves energy loss through phonon scattering
for achieving momentum alignment, although we cannot rule
out the possibility of other relaxation mechanisms causing the
energy difference. Because the PL emissions were excitation-
wavelength-independent, electrons excited to the σ* orbital
relaxed to the π* orbital for radiative π* → n recombination.
Figure 5a shows the particle size dependence of the π−π*
energy gap. Clearly, the quantum confinements in the sp2
domain led to the widening of the π−π* energy gap with a
decrease in the particle size. For GOQDs smaller than 2 nm,
the gap energy exhibits a sharp increase with a decrease in the
size. The sharp increase can be ascribed to the increased
confinement influence of the peripheral oxygen functionalities
on the enclosed sp2 domains. Chemical analysis by using XPS
revealed higher oxygen content in the GOQDs smaller than 2
nm.
Figure 5b shows a conceptual schematic of quantum
confinements introduced in GOQDs for elucidating the
variation of the energy level with particle size. The basal
plane of the GOQDs comprises an sp2-domain frame decorated
with oxidized sp3 sites or islands. The sp2 region is a continuous
phase, and in small GOQDs, confinements are introduced in
the sp2 domain to regulate the π−π* energy gap. A decrease in
the diameter of the disc-like GOQDs leads to a decrease in the
size of the connected sp2 domain, thereby increasing the π−π*
energy gap. Oxidized sp3 sites introduce n-state levels within
the energy gap, and these levels become the highest occupied
orbitals in the GOQDs. The energy levels of the n-states are
fixed and unrelated to the GOQD size, as shown in Figure 4.
For GOQDs smaller than 2 nm, the peripheral oxygen groups
occupy an appreciable fraction of the GOQD framework to
exert a strong influence on the electronic structure.
To support the interpretation presented in Figure 5, we
performed density functional theory (DFT)-based first-
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Figure 5. Quantum confinements introduced in the sp2 domain. (a)
Variation of the π−π* energy gap with the particle size for GOQDs
(determined from measurements, Figure 4) and for oxidized graphene
quantum dots (O-GQDs, see the structural schematics) as determined
from calculations (see Figures S9−S11). (b) Schematic of the
mechanism underlying the decrease in the size of the continuous sp2
phase, which surrounds the isolated sp3 sites or islands, with a decrease
in the diameter of the GOQDs. The orange areas represent
oxygenated sp3 sites or islands, which are homogeneously distributed
in the basal plane of the GOQDs.
principles calculations by using the Vienna ab initio simulation
package code (Figures S9−S11).36,37 The calculations were
performed to estimate the π−π* energy gap for graphene
quantum dots and oxidized graphene quantum dots (GQDs
and O-GQDs, respectively), in which the graphene layers are
bonded with hydrogen atoms and hydroxyl groups, respectively,
at the periphery (see Figure S9). The calculations also revealed
that small graphene sheets bonded with edge oxygen atoms are
not stable, which explains why the CO bonding was replaced
by the OH for the small GOQDs. The OH or H groups
represent the extremes for attachment at graphene periphery
because OH strongly attracts electrons from graphene,
whereas H donates electrons, and the results for attachments
with carboxyl and carbonyl groups should be within those for
OH or H groups shown in Figure S9. The shape of
graphene, in addition to the periphery functionality type,
influences the electronic structure of GQDs;38 however, we
only used a round shape for calculation because the GOQDs
are disc-like.
Figure 5a shows the variation of the π−π* energy gap with
the O-GQD particle size according to the DFT calculations.
Using O-GQDs to simulate the energy gap of the GOQDs is
more realistic relative to the use of GQDs. The measured and
calculated data show similar trends for the variation of the
π−π* energy gap with the particle size (Figure 5a); the
calculated gap values are smaller than the values obtained from
optical measurements by 1.5−2.0 eV. The gap values calculated
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using the Kohn−Sham method are known to be under-
estimated.39−41 The use of the GW approximation39−41 for
quasiparticle calculations, which are nevertheless not employed
in the present study due to the limit in computing resources,
would increase the calculated gap values in Figure 5a by
approximately 1.5−2 eV, considerably reducing the difference
between the absolute values obtained from calculations and the
measurements. The agreement, at least in the trend, between
the measured and calculated gap values lends strong support to
the quantum-confinement model presented in Figure 5b.
Figure S12 presents the time-resolved photoluminescence
(TRPL) decay profiles of the GOQD specimens excited by a
femtosecond pulse laser at 730 nm. The two-photon PL
intensities of the individual GOQD specimens were measured
at the characteristic peak wavelengths presented in Figure 2b.
Figure S12 shows that the average lifetime of the GOQDs
decreases with increasing particle size, from 1.1 ns for QD10 to
0.75 ns for QD79. A previous study reported that large
graphitic domains facilitated delocalization of excited electrons
to result in frequent energy loss at defect states.17 In the
GOQDs of the present study, larger QDs (such as QD79)
imposed less restriction on the delocalization of the excited
electrons in the π* orbital, which resulted in higher probability
of nonradiative recombination at defect sites. By contrast, small
QDs (such as QD10) confined excited electrons in discrete
orbitals, therefore to extend the lifetime of the excitons. The
TRPL results further illustrate the significant influence of
quantum confinements on the performance of the GOQDs.
In summary, we have reported the facile synthesis of high-
crystallinity GOQDs that show excitation-wavelength-inde-
pendent PL emissions because of the introduction of size-
dependent quantum confinement. PL emissions, whose color
changed from orange-red to blue upon reducing the GOQD
size, originated from the π* → n transition and the energy loss
associated with phonon scattering. The quantum confinement
resulted from a change in the particle size, and it led to a
change in the sp2-domain size and thus in the π*−π gap energy.
By contrast, the oxygen n-state orbitals located in the π*−π gap
showed similar energy levels for all the GOQDs, irrespective of
the particle size. The prominent confinement effects of the
GOQDs can be explained by the strong conjugation of
electrons in the sp2 domains in the basal plane, which allowed
the introduction of confinement in the sp2 domain through the
regulation of the particle size. The oxygenated sp3 sites or
islands in the basal plane are isolated by the continuous sp2
phase, and the peripheral oxygen functionalities strongly
influence the electronic structure in GOQDs smaller than 2
nm. This work provides important insights suggesting that
rationally designed GOQDs can be applied in electronic,
photonics, and biology applications. The metal-free feature
makes GOQDs a promising medium for biological cell imaging
and proliferation tracking. Additionally, the multiple-color
emissions suggest the applicability of the GOQDs to cell
labeling.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpclett.6b00752.
Methods, high-resolution TEM images of GOQDs,
Raman spectroscopy for the estimation of the sp2-
domain size of GOQDs, AFM images and height profiles
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of GOQDs, XPS and FTIR analyses of GOQDs, UPS
analysis for the valence band edges of GOQDs, excitation
wavelength-independent PL feature of GOQDs, theoreti-
cal energy gap calculations for GOQDs. (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: hteng@mail.ncku.edu.tw. Fax: 886-6-2344496.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This research was supported by the Ministry of Science and
Technology, Taiwan (104-2221-E-006-231-MY3, 104-2221-E-
006-234-MY3, 104-3113-E-006-005, and 104-3113-E-006-011-
CC2), and by the Ministry of Education, Taiwan, The Aim for
the Top University Project to the National Cheng Kung
University.
■
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2092 DOI: 10.1021/acs.jpclett.6b00752

J. Phys. Chem. Lett. 2016, 7, 2087−2092