nanomaterials

Article
SERS-Active Cu Nanoparticles on Carbon Nitride
Support Fabricated Using Pulsed Laser Ablation
Hossein Dizajghorbani-Aghdam 1 , Thomas S. Miller 2 , Rasoul Malekfar 1, * and
Paul F. McMillan 3, *
1 Atomic and Molecular Group, Physics Department, Faculty of Basic Sciences, Tarbiat Modares University,
Tehran 14115-175, Iran
2 Electrochemical Innovation Lab, Department of Chemical Engineering, University College London,
Torrington Place, London WC1E 7JE, UK
3 Department of Chemistry, Christopher Ingold Laboratories, University College London, 20 Gordon Street,
London WC1H 0AJ, UK
* Correspondence: [email protected] (R.M.); [email protected] (P.F.M)




Received: 17 July 2019; Accepted: 23 August 2019; Published: 29 August 2019


Abstract: We report a single-step route to co-deposit Cu nanoparticles with a graphitic carbon nitride
(gCN) support using nanosecond Ce:Nd:YAG pulsed laser ablation from a Cu metal target coated
using acetonitrile (CH3 CN). The resulting Cu/gCN hybrids showed strong optical absorption in the
visible to near-IR range and exhibited surface-enhanced Raman or resonance Raman scattering (SERS
or SERRS) enhancement for crystal violet (CV), methylene blue (MB), and rhodamine 6G (R6G) used
as probe analyte molecules adsorbed on the surface. We have characterized the Cu nanoparticles and
the nature of the gCN support materials using a range of spectroscopic, structural, and compositional
analysis techniques.

Keywords: pulsed laser ablation; acetonitrile (CH3 CN); Cu/gCN hybrids; localized surface plasmon
resonance (LSPR); surface enhanced Raman scattering (SERS); surface enhanced resonance Raman
scattering (SERRS)

1. Introduction
Surface-enhanced Raman spectroscopy (SERS) is a highly sensitive spectroscopic technique used
to detect and study vibrational modes of molecules adsorbed on metal or semiconducting surfaces or
nanoparticles (NP) [1–7]. SERS intensity enhancement factors (EFs) by up to 14 orders of magnitude arise
from a combination of electromagnetic (EM) and chemical (CM) mechanisms [8,9]. EM enhancement
factors (~107 –108 ) are dominant for metallic materials [10,11] compared with the CM enhancement
(~103 ) operating mainly among semiconductors [12–15]. Typical SERS active supports include noble
metals (Au, Ag, Cu) that develop localized surface plasmon resonances (SPR) in the visible range,
giving rise to the photon-vibrational coupling effects leading to SERS with EM enhancement [11,16].
In addition, if the adsorbed analyte contains a chromophore with a UV-visible absorption close to
the SPR wavelength, additional enhancement can be observed due to resonance Raman (SERRS)
effects [17].
Ag and Au NPs have been mainly investigated as the most highly active SERS substrates [11,18–21].
Cu NPs exhibit similar SPR properties but can show lower chemical stability toward adsorbate
species [16,22–25]. Cu NPs are readily produced using solution chemistry techniques, but these
approaches can lead to surface contamination due to atmospheric oxidation, as well as from the
addition of surfactants such as polyethylene glycol, sodium dodecyl sulfate, etc. [26–28], thus hindering
their use for SERS, as well as for biomedical and catalytic applications [29,30]. Laser ablation from

Nanomaterials 2019, 9, 1223; doi:10.3390/nano9091223 www.mdpi.com/journal/nanomaterials

Nanomaterials 2019, 9, 1223 2 of 16

a pure metal target in the presence of a liquid medium has been shown to provide a useful alternative
to obtain SERS-active NPs [24,25,31]. Using liquids such as H2 O or acetone results in the formation of
Cu oxides [32–34] that reduce the SERS activity and affect the chemical stability [35]. Here, we explored
the use of the oxygen-free liquids toluene (C7 H8 ) and acetonitrile (CH3 CN) for the Cu laser ablation
experiments. The aromatic hydrocarbon toluene produced Cu NPs surrounded by an amorphous
carbon matrix that resulted in quenching of the SPR. Similar results have been reported for Au
NPs [36,37]. These effects could be reduced by incorporating N atoms in the ablation medium and the
resulting solid matrix surrounding and supporting the Cu NPs. Previous studies have described the
laser ablation of Cu and other transition metal elements using acetonitrile to obtain metal NPs deposited
along with a carbon nitride support, but the nature of the support material obtained has not yet been
fully established [38–42]. Here, we characterized the Cu NPs and the carbon nitride matrix, that we
established to have a polymeric to graphitic character based on mainly sp2 -bonded C and N species
(labelled gCN for convenience), using a range of spectroscopic, diffraction, and imaging techniques.
We evaluated the performance of the Cu/gCN hybrid nanomaterials for their surface-enhanced Raman
or resonance Raman scattering (SERS or SERRS) performance using crystal violet (CV), methylene blue
(MB), and rhodamine 6G (R6G) as probe analyte molecules adsorbed on the NP surface.
Different classes of carbon nitride materials are currently being investigated for applications
including catalysis, photocatalysis, electrochemical energy storage, and conversion, and as supports
for catalytically active metal NPs [43–46]. Most work to date is focused on semiconducting compounds
with Cx Ny Hz compositions and polymeric to layered (“graphitic”) structures are being developed.
Although these materials are often cited as graphitic (g-) C3 N4 , this particular stoichiometry and layered
structure have only been characterized in a single study that described a triazine-based graphitic
carbon nitride (TGCN), produced using the polymerization of dicyandiamide (DCDA: C2 N4 H4 )
in a LiCl:KCl molten salt medium [47]. That process normally results in crystalline polytriazine
imide (PTI) solids containing intercalated Li+ and Cl− ions [48]; the TGCN material consisted of
dark-colored flakes formed at the molten surface or deposited on the walls of the reaction vessel.
However, related studies have found that the layered gCN materials deposited from above the
DCDA/molten salt mixture under analogous reaction conditions had significantly greater C:N ratios,
close to 1.3 [49,50]. That composition is similar to the gCN supports formed in our laser ablation
study, described below. The wide range of materials described as carbon nitrides include N-doped
graphite and graphene produced by chemical or physical vapor deposition exhibit semi-metallic to
semiconducting behavior, with optoelectronic properties determined by the relative C:N ratio and their
distribution within the sp2 -bonded structures [51–53]. Such materials have been formed via the laser
ablation of graphite targets in N2 or NH3 atmospheres, or by the laser-assisted reactions of precursors
in gas and liquid media, giving rise to materials containing up to ≈20 at% nitrogen in the resulting
amorphous to nanocrystalline films [54–60]. There have been reports of embedding Cu NPs in carbon
nitride materials for functional applications. Hydrothermal processing in Cu-containing ionic liquids
produced a Cu/gCN electrocatalyst that showed catalytic activity for the oxygen reduction reaction
(ORR) critical for fuel cell operations [61], while reacting CuCl2 with melamine in methanol formed
supramolecular networks and carbon nitride nanosheets and nanorods with coordinated Cu2+ ions
resulting in enhanced catalytic and visible light photocatalysis properties [62–66].
These last investigations indicate that electronic interactions between Cu NPs and supporting
carbon nitride matrices can lead to the cooperative enhancement of catalytic and photocatalytic effects.
Such interactions could be harnessed to develop other optical properties, including SERS enhancement
of the vibrational signatures of molecular species adsorbed on the surface. Studies have reported
combining semiconductor NPs (such as TiO2 ) with plasmonically active NPs to stabilize and enhance
the performance of SERS substrates [67–69]. Jiang et al. described a hybrid Ag/gCN material with
a stable high-performance SERS activity, demonstrating strong optoelectronic interactions that promote
the SERS enhancement along with charge transfer effects that protect the Ag NPs from oxidation [70,71].
Here we applied pulsed laser ablation of a Cu target coated with acetonitrile (CH3 CN) to create Cu/gCN
Nanomaterials 2019, 9, 1223 3 of 16

hybrid nanomaterials that were characterized using a range of spectroscopic, diffraction, and imaging
techniques, and we studied their SERS/SERRS activity for the probe analyte molecules crystal violet
(CV), methylene blue (MB), and rhodamine 6G (R6G).

2. Materials and Methods

A high-purity copper plate (Cu 99.98%) with a 2-mm thickness coated with acetonitrile served as
the target for the laser ablation experiments. High-purity, methylene blue (MB), crystal violet (CV)
(99.5%), and rhodamine 6G (R6G) (≥95%) were purchased from Sigma Aldrich (Darmstadt, Germany)
and used as SERS probe analytes. Bulk elemental analysis was carried out using an Elementar-Vario
EL III system (Hanau, Germany) and X-ray photoelectron spectroscopy (XPS) was carried out using
a Thermo Scientific K-Alpha instrument (Waltham Massachusetts, U.S.A) with a monochromated Al
Kα source (1486.6 eV). Transmission electron microscopy (TEM) was carried out using Zeiss-EM10C-80
kV (Germany) and JEOL JEM2010-200 kV (Tokyo, Japan) instruments. The micrographs were analyzed
using ImageJ software (Version 6, California, U.S.A) [72] and by manual counting to determine the
mean size of NPs in the TEM images. The average Cu NP sizes were determined to be ≈6 nm, slightly
lower than those estimated from Scherrer broadening of the X-ray powder diffraction data. X-ray
diffraction (XRD) patterns were recorded using an X-Pert MPD (Philips, Eindhoven, Netherlands)
X-ray diffractometer with Co Kα-radiation (λ = 1.79026 Å). Ultraviolet–visible (UV/vis) absorption
spectra were obtained using a PG T80+ spectrophotometer (PG Instruments, Coventry, UK), Fourier
Transform infrared (FTIR) spectra with a Thermo Nicolet NEXUS 670 FTIR (Waltham Massachusetts,
U.S.A), and Raman spectroscopy including SERS or SERRS effects were recorded using a Thermo
Nicolet Almega spectrometer (Waltham Massachusetts, U.S.A) with a 532-nm excitation provided by
a Nd:YLF laser.
Pulsed laser deposition was carried out using a Ce:Nd:YAG laser (λ = 1064 nm) with a 10-ns
pulse width and a 10-Hz repetition rate. The beam was focused on the Cu plate target using a 10-cm
working distance lens. The target was fixed to the bottom of a glass cell and mounted on a rotator in
order to avoid deep ablation. The laser pulse energy was held constant at 100 mJ/pulse. The typical
diameter of the laser spot at the target was 2 mm and the acetonitrile level on the target surface was
2 mm. The pulsed laser was directed on the rotating target surface for 10 min to obtain a colloidal
suspension of ablated nanomaterial particles. The suspension was then dried at 25 ◦ C in air to provide
solid powdered materials for further investigation.
To prepare SERS substrates, 1 mg of the synthesized support materials (Cu/gCN) were suspended
in 5 mL of the different analyte solutions (CV, MB, and R6G) prepared with concentrations ranging
between 10−3 –10−8 mol/L in acetonitrile and stirred for 3 h to allow binding between the analyte
and substrate. The analyte-decorated Cu/gCN solutions were centrifuged and washed multiple
times with absolute acetonitrile to remove any unabsorbed analyte molecules and then the resulting
powders were dispersed into 1 mL acetonitrile. SERS substrates were prepared by dropping aliquots
of analyte-decorated Cu/gCN solutions (10 µL) onto a glass slide and the volatile liquid phase was
left to evaporate at 25 ◦ C in air to form a uniform coating. All Raman and SERS/SERRS experiments
were carried out with the incident laser power maintained at 10 mW for a 60 µm (spot diameter) laser
beam focused at different points on the sample surface maintaining a constant integration time of 100 s
at a spectral resolution of 4 cm−1 . All spectra were measured using 532-nm excitation delivered by
the second harmonic of a Nd:YLF laser and were collected in the range of 400−4000 cm−1 . All data
processing and statistical analysis were carried out using the OMNIC™ software (Version 6) supplied by
Thermo Nicolet (Waltham Massachusetts, U.S.A) and intensity values of the spectra were normalized
according to the integration time within each data set.
Nanomaterials 2019, 9, 1223 4 of 16

3. Results and Discussion

3.1. Formation and Characterization of Cu/g-CN Materials Produced by Pulsed Laser Ablation in Acetonitrile
The interaction of high-power laser beams with a Cu target can result in several phenomena
including heating, melting, and even vaporization of the surface, leading to the formation of plasma.
A complex process involving adiabatic plasma expansion combined with shockwaves and the formation
of cavitation bubbles result in ablation of Cu NPs that become suspended within the overlying
liquid medium. The high temperatures generated by laser beam absorption using the Cu target
result in bond-breaking and polymerization reactions occurring within the acetonitrile liquid phase
surrounding the ablated metal NPs. Also, radiation from the laser-ablated Cu vapor plume leads
to UV absorption and photolysis reactions within the acetonitrile liquid. The combination of these
thermal and photolytic reaction effects, accompanied by new C–C/C–N bond formation, results in the
formation of a polymerized gCN matrix that then surrounds and supports the Cu NPs formed during
laser ablation treatment [38].
We first characterized the chemical composition of the Cu/gCN hybrid materials using bulk
elemental (CNH) analysis that revealed a C:N ratio of 1.3, which was larger than those expected for g-C3 N4
or polymeric to graphitic gCN materials prepared via the thermolysis of organic precursors [43,44].
However, it only slightly exceeded the C:N ratio found for layered gCN materials produced using
vapor deposition above a molten salt bath from precursors such as DCDA [49,50]. Examination of the
survey C1s and N1s spectra obtained from XPS measurements confirms this observation (Figure 1a–c).
The C1s spectra could be fit using three mixed Gaussian–Lorentzian (GL) peaks at 284.3, 286.0, and 288.2
eV. The peak at 288.2 eV appears at a position that is characteristic of sp2 C atoms bonded within
a cyclic triazine or heptazine systems [44], although this constituted only a minor (5.5%) component of
the overall C contribution. The peak at 286.0 eV (18.55% of the C contribution) was assigned to C–N
bonded species, although it might also contain a contribution from C–O bonded species that are often
recorded for gCN materials due to surface oxidation [44,50]. It is probable that the remainder of the
C–N bonding was represented by a significant, but unresolvable, contribution to the peak at 284.3 eV,
along with a component from adventitious carbon [50,53]. The presence of the C1s peak at 286.0 eV,
as well as a significant proportion of that observed at 284.3 eV, confirmed the presence of significant
C–N interactions within the sample. The N1s spectrum (Figure 1c) was best fit with two GL peaks,
one at 398.4 eV, and a second contribution at 399.5 eV. The smaller peak resembles that observed for
melamine and is usually interpreted to be indicative of C–N–H uncondensed amino (–NH2 ) groups [44].
We note that the IR spectra discussed below indicate the presence of N–H bonded species. The peak
at the higher binding energy (BE) resulted from the remaining C–N species, which included C–N=C
bonded units indicated by the peak in the C1s spectrum. The IR and Raman data also indicated the
presence of terminal nitrile (–C≡N) units that contributed to the N1s signal. The C1s:N1s peak ratio
found from the XPS data was 4.76. This was significantly larger than the value determined using bulk
elemental analysis (1.33), but it was certainly affected by a significant contribution from adventitious
carbon. However, the fact that the C:N ratio was substantially greater than 1 clearly indicates that both
C–C and C–N species were present within the gCN materials. The Cu 2p3/2 peak (Figure 1d) exhibits
a single sharp feature that could be fitted using a GL peak at 933.3 eV. The shape and position of this
feature, as well as the absence of higher BE satellites, rule out the presence of Cu(II), but Cu(I) and
Cu(0) species both have similar XPS signatures, and it is possible that either or both of these species
might be present within the sample [73].
target result in bond-breaking and polymerization reactions occurring within the acetonitrile liquid
phase surrounding the ablated metal NPs. Also, radiation from the laser-ablated Cu vapor plume
leads to UV absorption and photolysis reactions within the acetonitrile liquid. The combination of
these thermal and photolytic reaction effects, accompanied by new C–C/C–N bond formation, results
in the formation of a polymerized gCN matrix that then surrounds and supports the Cu NPs formed
Nanomaterials 2019, 9, 1223 5 of 16
during laser ablation treatment [38].

Nanomaterials 2019, 9, x FOR PEER REVIEW 5 of 15

presence of N–H bonded species. The peak at the higher binding energy (BE) resulted from the
remaining C–N species, which included C–N=C bonded units indicated by the peak in the C1s
spectrum. The IR and Raman data also indicated the presence of terminal nitrile (–C≡N) units that
contributed to the N1s signal. The C1s:N1s peak ratio found from the XPS data was 4.76. This was
significantly larger than the value determined using bulk elemental analysis (1.33), but it was
certainly affected by a significant contribution from adventitious carbon. However, the fact that the
C:N ratio was substantially greater than 1 clearly indicates that both C–C and C–N species were
present within the gCN materials. The Cu 2p3/2 peak (Figure 1d) exhibits a single sharp feature that
could be fitted using a GL peak at 933.3 eV. The shape and position of this feature, as well as the
absence of higher BE satellites, rule out the presence of Cu(II), but Cu(I) and Cu(0) species both have
Figure
similar XPS1.
Figure (a) XPS
(a) XPS survey
1.signatures, survey spectrum,
and spectrum,
it is possible(b) C1s,
(b) C1s, either
that (c) N1s,
(c) N1s, and
orand
both (d)ofCu 2p3/2
these XPS spectra
3/2species
XPS spectra ofbe
mightof the Cu/gCN
present
the Cu/gCN within
material[73].
the sample
material produced by
produced by laser
laser ablation
ablation under
under acetonitrile.
acetonitrile.
UV-visible absorption spectra of the Cu/gCN nanomaterials obtained in suspension in
UV-visible
We absorption spectra
firstfollowing
characterized of the Cu/gCN
the ablation
chemical nanomaterials
composition obtainedhybrid
of theaCu/gCN in suspension in using
acetonitrile
acetonitrile the laser synthesis exhibited peak at ≈580 nmmaterials
due to the bulk
localized
following
elemental the laser ablation
(CNH) resonance synthesis
analysis that exhibited
revealed a C:N a peak
ratio at ≈580
of (Figure
1.3, whichnm due to the localized surface plasmon
was larger than those expected for
surface plasmon (SPR) band of the Cu NPs 2) [16,24,74].
resonance
g-C (SPR) band of the Cu NPs (Figure 2) [16,24,74].
3N4 or polymeric to graphitic gCN materials prepared via the thermolysis of organic precursors

[43,44]. However, it only slightly exceeded the C:N ratio found for layered gCN materials produced
using vapor deposition above a molten salt bath from precursors such as DCDA [49,50]. Examination
of the survey C1s and N1s spectra obtained from XPS measurements confirms this observation
(Figure 1a–c). The C1s spectra could be fit using three mixed Gaussian–Lorentzian (GL) peaks at
284.3, 286.0, and 288.2 eV. The peak at 288.2 eV appears at a position that is characteristic of sp2 C
atoms bonded within a cyclic triazine or heptazine systems [44], although this constituted only a
minor (5.5%) component of the overall C contribution. The peak at 286.0 eV (18.55% of the C
contribution) was assigned to C–N bonded species, although it might also contain a contribution from
C–O bonded species that are often recorded for gCN materials due to surface oxidation [44,50]. It is
probable that the remainder of the C–N bonding was represented by a significant, but unresolvable,
contribution to the peak at 284.3 eV, along with a component from adventitious carbon [50,53]. The
presence of the C1s peak at 286.0 eV, as well as a significant proportion of that observed at 284.3 eV,
confirmed the presence of significant C–N interactions within the sample. The N1s spectrum (Figure
1c) was best fit with two GL peaks, one at 398.4 eV, and a second contribution at 399.5 eV. The smaller
peak resembles that observed for melamine and is usually interpreted to be indicative of C–N–H
uncondensed
Figure amino (–NH
Figure 2.2. UV–visible
UV–visible 2) groups
absorption
absorption [44]. We
spectrum
spectrum note
of aof that
typical the
Cu/gCN
a typical IR spectra
nanomaterial
Cu/gCN discussed below
synthesized
nanomaterial usingindicate
synthesized using the
pulsed
laser
pulsedablation in acetonitrile.
laser ablation The insetThe
in acetonitrile. shows a vertically
inset shows a expanded region of the
vertically expanded spectrum
region of thearound the
spectrum
position of the surface plasmon resonance for Cu NPs.
around the position of the surface plasmon resonance for Cu NPs.

The
The XRD
XRD pattern
pattern ofof dried
dried powders
powders obtained
obtained using
using Co Co Kα
Kα radiation
radiation showed
showed weakweak sharp
sharp peaks
peaks
that were distinct from the broad and more intense features from the amorphous
that were distinct from the broad and more intense features from the amorphous gCN matrix gCN matrix (Figure 3).
(Figure
The weak
3). The weakpeaks
peaksoccurring at at
occurring 50.7 ◦ and
50.7° and59.2 ◦
59.2°2θ2θ
(λ(λ = =1.79026
1.79026Å)Å)were
wereidentified
identifiedwith
withthe
the {111}
{111} and
and
{200}
{200} reflections of crystalline Cu (2.09 and 1.08 Å, respectively). A very weak feature could just
reflections of crystalline Cu (2.09 and 1.08 Å, respectively). A very weak feature could just be
be
distinguished ◦
distinguished at at 89.1
89.1° 2θ
2θ (1.27
(1.27 Å)
Å) that
that corresponded
corresponded to to the
the {220}
{220} reflection.
reflection. Examining
Examining the the widths
widths ofof
these features indicated an NP size with an average mean diameter ≈32 nm estimated
these features indicated an NP size with an average mean diameter ≈32 nm estimated using Scherrer's using Scherrer’s
formula ◦
formula (Table
(Table1).
1). The
The pattern
pattern was
was dominated
dominated by by aa strong,
strong, broad
broad peak
peak at
at 34.3
34.3° 2θ
2θ (3.03
(3.03 Å),
Å), along
along with
with
a weaker feature at 28.9° 2θ (3.59 Å). These resembled the broad reflections observed for polymeric
to graphitic carbon nitride materials prepared using thermolysis of organic precursors, where they
are commonly interpreted in relation to the {002} and {100} planes of polytriazine to polyheptazine
graphitic layered structures, even though the actual materials are known to be incompletely
polymerized and contain ribbon-like units along with partially formed sheets [44,75–77]. Similar
Nanomaterials 2019, 9, 1223 6 of 16

a weaker feature at 28.9◦ 2θ (3.59 Å). These resembled the broad reflections observed for polymeric to
graphitic carbon nitride materials prepared using thermolysis of organic precursors, where they are
commonly interpreted in relation to the {002} and {100} planes of polytriazine to polyheptazine graphitic
layered structures, even though the actual materials are known to be incompletely polymerized and
contain ribbon-like units along with partially formed sheets [44,75–77]. Similar features were also
found for nanocrystalline layered materials with higher C:N ratios close to those observed for the
gCN supports created in this study [44,49,50]. We note, however, that the main XRD peak occurred at
a value that is ≈11% smaller than the interplanar d002 spacing of crystalline graphite (d002 = 3.28 Å),
or gCN compounds
Nanomaterials with
2019, 9, x FOR both
PEER low (~3.26 Å) and high C:N ratios (~3.24 Å) [44,49,50,75–77].
REVIEW 6 of 15

Figure 3. Powder
Powder XRD
XRD pattern (obtained using Co Kα radiation, λ =
pattern (obtained = 1.79026
1.79026 Å)
Å) of
of the
the Cu/gCN
Cu/gCN material
formed using
using pulsed
pulsedlaser
laserablation
ablationininacetonitrile.
acetonitrile.The
The weak
weak sharp
sharp peaks
peaks duedue to crystalline
to crystalline Cu Cu
NPsNPs
are
are labeled
labeled withwith
theirtheir
{hkl}{hkl} values.
values. The strong
The strong broadbroad features
features aretodue
are due to thesupport
the gCN gCN support generated
generated during
the laserthe
during ablation synthesis
laser ablation from acetonitrile.
synthesis from acetonitrile.

Table 1. Summary of X-ray diffraction data obtained using Co Kα radiation (λ = 1.79026 Å) for a typical
Table 1. Summary of X-ray diffraction data obtained using Co Kα radiation (λ = 1.79026 Å) for a
Cu/gCN material prepared using pulsed laser ablation in acetonitrile. * The assignment of peaks for
typical Cu/gCN material prepared using pulsed laser ablation in acetonitrile. * The assignment of
gCN is discussed in the text.
peaks for gCN is discussed in the text.
Angle (2θ) {hkl} FWHM (2θ) d-spacing (Å) Height (counts) Identification
Angle (2θ) {hkl} FWHM (2θ) d-spacing (Å) Height (counts) Identification
28.9
28.9 ** 3.3
3.3 3.59
3.59 27.2
27.2 gCN
gCN
34.3 * 1.6 3.03 153.9 gCN
34.3 * 1.6 3.03 153.9 gCN
50.7 {111} 0.3 2.09 36.9 Cu
50.7
59.2 {111}
{200} 0.3
0.4 2.09
1.08 36.9
14.6 Cu
Cu
59.2
89.1 {200}
{220} 0.4
3.2 1.08
1.27 14.6
5.4 Cu
Cu
89.1 {220} 3.2 1.27 5.4 Cu
Cu NPs were shown to be distributed throughout the gCN matrix via TEM imaging (Figure 4a–d).
By counting ≈40 particles, the mean diameter was found to be ≈6 nm by analyzing the images using
ImageJ software [72]. A few particles in the field of view were observed to have diameters in the
10–25 nm range. The greater average particle size (≈30 nm) indicated using the XRD results could
have been the result of the presence of large NPs within the bulk materials that were not sampled in
the TEM experiments, although Scherrer analysis of the X-ray peaks is not always reliable. The gCN
supporting matrix revealed a turbostratic texture with an "onion-like" structure developed around the
Cu NPs (Figure 4c).
FTIR spectra of a pressed KBr disc of the powdered Cu/gCN sample contained a strong band
at 3340 cm−1 due to N–H stretching (a) from the gCN material,(b)combined with a contribution from
O–H stretching from surface-adsorbed H2 O (Figure 5a) [78,79]. The peak at 1640 cm−1 was due to
molecular H2 O bending vibrations [78]. The features at 2850–2950 cm−1 indicated the presence of
sp3 -hybridized C–H bonds [80]. Features in the 1000–1450 cm−1 region can be assigned to C–N and
Nanomaterials
Figure 2019, 9, 1223XRD pattern (obtained using Co Kα radiation, λ = 1.79026 Å) of the Cu/gCN material7 of 16
3. Powder
formed using pulsed laser ablation in acetonitrile. The weak sharp peaks due to crystalline Cu NPs
are labeled with their {hkl} values. The strong broad features are due to the gCN support generated
possibly C–O stretching vibrations [44,50]. The sharp peak at 2120 cm−1 was due to terminal C≡N
during the laser ablation synthesis from acetonitrile.
bond stretching within the incompletely condensed carbon nitride matrix [79,80]. The strong Raman
peak at 2155 cm−1 confirmed this assignment (Figure 5b), although it is not clear why there should be
Table 1. Summary of X-ray diffraction data obtained using Co Kα radiation (λ = 1.79026 Å) for a
a 35 cm−1 difference between the IR and Raman data. This could indicate a vibrational interaction
typical Cu/gCN material prepared using pulsed laser ablation in acetonitrile. * The assignment of
between adjacent nitrile groups within the structure giving rise to symmetric and antisymmetric
peaks for gCN is discussed in the text.
combinations; however, typically the IR mode should occur at a higher wavenumber. Our observation
Angleclearly
of this feature (2θ) {hkl}indicatesFWHM (2θ)
that the gCNd-spacing (Å) Height
material produced (counts)
by laser ablationIdentification
from acetonitrile was
28.9 * 3.3 3.59 27.2
not fully polymerized into graphitic sheets. However, the sharp peak in the IR spectrum gCNnear 810 cm−1
Nanomaterials 2019, 9, x FOR PEER REVIEW 7 of 15
was typical34.3of breathing * modes of1.6 3.03
ring units in carbonaceous and153.9
Cx Ny materials. gCN
Also, the Raman
50.7
spectrum contained {111}main bands
two 0.3 at 1346 and2.09 −1 36.9
1540 cm that resembled the “G”Cuand “D” bands
Cu NPs were shown to be distributed throughout the gCN matrix via TEM imaging (Figure 4a–
59.2 {200} 0.4 1.08 14.6
of disordered graphite, amorphous carbon, and graphitic carbon nitride materials, associated with Cu
d). By counting ≈40 particles, the mean diameter was found to be ≈6 nm by analyzing the images
89.1
C–N/C–C stretching {220}
vibrations 3.2 the gCN matrix
within 1.27 [44,50,79,80].5.4 Cu
using ImageJ software [72]. A few particles in the field of view were observed to have diameters in
the 10–25 nm range. The greater average particle size (≈30 nm) indicated using the XRD results could
have been the result of the presence of large NPs within the bulk materials that were not sampled in
the TEM experiments, although Scherrer analysis of the X-ray peaks is not always reliable. The gCN
supporting matrix revealed a turbostratic texture with an "onion-like" structure developed around
the Cu NPs (Figure 4c).
FTIR spectra of a pressed KBr disc of the powdered Cu/gCN sample contained a strong band at
3340 cm−1 due to N–H stretching from the gCN material, combined with a contribution from O–H
stretching from surface-adsorbed H2O (Figure 5a) [78,79]. The peak at 1640 cm−1 was due to molecular
H2O bending vibrations [78]. The features at 2850–2950 cm−1 indicated the presence of sp3-hybridized
C–H bonds [80]. Features in the 1000–1450 (a) cm−1 region can be(b)assigned to C–N and possibly C–O
stretching vibrations [44,50]. The sharp peak at 2120 cm−1 was due to terminal C≡N bond stretching
within the incompletely condensed carbon nitride matrix [79,80]. The strong Raman peak at 2155 cm−1
confirmed this assignment (Figure 5b), although it is not clear why there should be a 35 cm−1
difference between the IR and Raman data. This could indicate a vibrational interaction between
adjacent nitrile groups within the structure giving rise to symmetric and antisymmetric
combinations; however, typically the IR mode should occur at a higher wavenumber. Our
observation of this feature clearly indicates that the gCN material produced by laser ablation from
acetonitrile was not fully polymerized into graphitic sheets. However, the sharp peak in the IR
spectrum near 810 cm−1 was typical (c) of breathing modes of ring (d) units in carbonaceous and CxNy
materials. Also, the Raman spectrum contained two main bands at 1346 and 1540 cm−1 that resembled
Figure 4. TEM images ofofCuCu
NPs embedded in the
in amorphous gCN gCN
support. (a) Low-resolution image
the "G" and4. "D"TEMbandsimagesof NPs
disorderedembedded
graphite, the amorphous
amorphous carbon, support. (a) Low-resolution
and graphitic carbon nitride
obtained using a Zeiss-EM10C-80 kV instrument; (b,c) High-resolution images obtained using
image obtained using a Zeiss-EM10C-80 kV instrument; (b) and (c) High-resolution images obtained a JEOL
materials, associated with C–N/C–C stretching vibrations within the gCN matrix [44,50,79,80].
JEM2010-200
using a JEOL kV TEM. (d) Mean
JEM2010-200 size (d)
kV TEM. (nm) and size
Mean distribution
(nm) andbydistribution ≈40analysis
analysis of by Cu NPs. of ≈40 Cu NPs.

(a) (b)
Figure 5. (a) FTIR and (b) Raman spectra of Cu/gCN hybrid material synthesized using pulsed laser
ablation in acetonitrile.

3.2. SERS/SERRS Activity of Analytes on Cu/gCN Hybrid Support Produced Using Pulsed Laser Deposition
We tested the SERS/SERRS activity of the CuNP/g-CN hybrid using the dye molecules CV, MB,
and R6G as analyte probes. A drop of each the analyte-decorated Cu/gCN solutions prepared with
−3 −7
Nanomaterials 2019, 9, x FOR PEER REVIEW 8 of 15

Nanomaterials 2019, 9, 1223 8 of 16

Because CV has a main UV-visible absorption band extending between 420–640 nm with its
principal maximum near 580 nm, resonance Raman (RR) effects were expected to occur for the bulk
crystalline
3.2. sampleActivity
SERS/SERRS using 532 nm excitation
of Analytes on Cu/gCN[81].Hybrid
However, using
Support the acquisition
Produced conditions
Using Pulsed applied
Laser Deposition
here, we could barely observe the vibrational peaks of CV rising above the background when
We tested
presented at thethesame
SERS/SERRS activity of the
vertical expansion CuNP/g-CN
as the SERS/SERRShybrid using(Figure
spectra the dye6a).
molecules
For theCV, MB,
analyte
and R6G as analyte probes. A drop of each the analyte-decorated Cu/gCN solutions
deposited on the Cu/gCN support at 10−3 M concentration, we clearly observed the spectrum of CV prepared with
various dueatconcentrations −3 −7
with peaks 794, 901, 942, (10
1168,–10
1368,M)andwas placed
1620 cm−1 on the prepared
(Figure glass slide
6a). Although substrates
the positions separately
and relative
and allowed to dry before recording surface-enhanced spectra. “Normal” and SERS/SERRS
intensities generally resembled those of published spectra of the solid sample obtained with different spectra are
compared in Figure 6, after subtraction of the background fluorescence (Figure S1).
laser wavelengths [81], we observed the most significant enhancement in the intensity of the feature No additional
bands
at 1368were
cm−1 observed froma the
that contains main gCN support material
contribution (Figure S2).
from symmetric ϕ –NAll(ϕspectra
= phenyl)were obtained
stretching using
[81]. As
athe
total integration time of 100 s from 50 accumulated scans with a 2-s exposure. The
concentration of adsorbed CV molecules was reduced by decadic amounts, the main peaks could spectra shown in
Figure 6 have been displaced vertically to more clearly show the
still be clearly distinguished from the background down to 10−7 M (Figure 6a).SERS/SERRS enhancement.

(a) (b)

(c)

Figure 6.6. Raman spectra

spectra of
of (a)
(a)CV,
CV,(b)(b)MB,
MB,andand(c)
(c)R6G
R6Gpowders
powderscompared
compared with
with SERS/SERRS
SERS/SERRS spectra
spectra of
of the
the analytes
analytes withwith different
different concentrations
concentrations decorated
decorated on a Cu/g-CN
on a Cu/g-CN substrate.
substrate. All spectra
All spectra were
were plotted
plotted following
following baselinebaseline subtraction
subtraction (seeS1).
(see Figure Figure
TheS1).
red The
line red line indicates
indicates the characteristic
the characteristic peak usedpeak
to
used to determine
determine the SERSthe SERS(see
activity activity (see Supporting
text and text and Supporting Information).
Information). The spectra The spectra
have beenhave been
vertically
vertically for
displaced displaced
clarity. for
Theclarity.
counts The
showncounts shown correspond
correspond to antime
to an integration integration
of 100 stime
of 50of 100 s of 50
accumulated
accumulated
scans, each withscans,
a each with a 2-speriod.
2-s exposure exposureWe period.
note We
thatnote
for that for the
the CV CV sample
sample prepared
prepared 10−7a
with awith
M −7 M concentration,
10 concentration, an additional
an additional fluorescence
fluorescence background
background contributionremained
contribution remainedthat
thatwas
wasnot
not fully
accountedfor
accounted forbyby
thethe baseline
baseline subtraction
subtraction procedure.
procedure. Thismost
This was waslikely
mostduelikely dueanalyte
to some to some analyte
molecules
that were not completely removed from the underlying glass support by the
molecules that were not completely removed from the underlying glass support by the washing washing procedure.
procedure.
Because CV has a main UV-visible absorption band extending between 420–640 nm with its
principal maximum near 580 nm, resonance Raman (RR) effects were expected to occur for the bulk
crystalline sample using 532 nm excitation [81]. However, using the acquisition conditions applied
Nanomaterials 2019, 9, 1223 9 of 16

here, we could barely observe the vibrational peaks of CV rising above the background when presented
at the same vertical expansion as the SERS/SERRS spectra (Figure 6a). For the analyte deposited on
the Cu/gCN support at 10−3 M concentration, we clearly observed the spectrum of CV with peaks at
794, 901, 942, 1168, 1368, and 1620 cm−1 (Figure 6a). Although the positions and relative intensities
generally resembled those of published spectra of the solid sample obtained with different laser
wavelengths [81], we observed the most significant enhancement in the intensity of the feature at
1368 cm−1 that contains a main contribution from symmetric φ –N (φ = phenyl) stretching [81]. As the
concentration of adsorbed CV molecules was reduced by decadic amounts, the main peaks could still
be clearly distinguished from the background down to 10−7 M (Figure 6a).
MB exhibited a UV-visible absorption that had barely begun at the 532 nm laser wavelength,
and so it was expected that any RR or pre-resonance effects would be minimal for the bulk sample,
while the background fluorescence should be low [82]. That was consistent with our data for the solid
sample, for which the principal peak recorded at ≈1610 cm−1 in our study was clearly observed for the
counting conditions used here (Figure 6b). However, the Cu NP SPR occurred at 580 nm, which lay
within the electronic absorption profile of the chromophore, and so the SERS enhancement effects
could also include SERRS. We observed SERS-active Raman peaks at 632, 753, 843, 1056, 1174, 1287,
1375, 1440, and 1610 cm−1 for our sample prepared from a 10−3 M analyte solution, with a relative
intensity pattern that resembled that obtained by Anastasopolous et al. for MB molecules at 10−4 M
concentration adsorbed on Ag NPs and excited using a 514.5 nm excitation [82]. We can clearly observe
the dominant 1610 cm−1 peak down to a 10−6 M concentration, with a relative intensity that was only
slightly lower than that for the bulk solid (Figure 6b).
R6G exhibited an electronic absorption maximum at 530 nm that matched the laser excitation
wavelength and also lay close to the SPR of Cu NPs, and so RR effects were expected to be observed for
both the bulk solid and adsorbed molecules in our study using a 532-nm laser excitation. As observed
by previous researchers, the SERRS effect on Au nanoparticles or roughened Cu surfaces resulted in
the appearance of the characteristic Raman peaks of the adsorbed molecules using red (632.8 nm) to
blue (488 nm) excitation lines [83,84]. Our data show that the spectrum could be detected down to
at least 10−6 M, where the relative intensities were comparable to those of the bulk solid (Figure 6c).
Overall, our results demonstrated that the Cu/g-CN hybrid substrate exhibited good SERS/SERRS
sensitivity for the CV, MB, and R6G molecular analytes.

3.3. Estimation of SERS/SERRS Enhancement Factors

In order to further investigate the SERS/SERRS enhancement activities of the Cu/gCN substrate,
the surface was decorated with a sufficiently high concentration of analyte molecules (CV, MB, and R6G,
10−3 M) to ensure full a monolayer coverage of the NP surface. We assumed that the probe molecules
were uniformly adsorbed on the support surfaces. The relative intensities of characteristic peaks for
the three molecules were then compared with those obtained from a dried spot (2 µL; ≈10 mm2 )
of pure analyte solution prepared at the same concentration (Figure 7a–c). The peaks at 1368, 1610,
and 1362 cm−1 were considered for CV, MB, and R6G analytes, respectively. SERS/SERRS enhancement
factors (EFs) were then estimated using the following equation [85–87]:

EF = (ISERS /nSERS )/(IRaman /nRaman ) (1)

Here, nRaman and nSERS were the number of analyte molecules included within the laser beam
sampling volume for the normal Raman and SERS samples, respectively. ISERS and IRaman were the
absolute intensity values measured for the same mode in the Raman and SERS/SERRS spectra of
the analyte. The area of the laser illumination (Alaser ) constituted a circle ≈30 µm in radius (rlaser ).
The focused laser beam penetrated ≈4 µm into the material [86,88]. We considered the Cu NPs to
be spherical with a radius (rNP ) of ≈16 nm (estimated from the XRD and TEM results), and that
the particles were half-way embedded into the gCN matrix. We neglected spaces between the NPs.
Nanomaterials 2019, 9, 1223 10 of 16

The number of analyte molecules illuminated by the laser beam for the solid and SERS samples were
then obtained using:
nSERS = (nNPs .ANP )/(AAnalyte ) (2)

Here, nNPs , ANP , and AAnalyte were the number of NPs in the area illuminated by the laser,
the surface area per NP, and the analyte molecule surface area, respectively. nRaman was then obtained
using the following relation:

nRaman
Nanomaterials 2019, 9, x FOR PEER REVIEW = (NA .VAnalyte .dAnalyte )/(MAnalyte ) 10 of (3)
15

where NA is N
where Avogadro’s number,
A is Avogadro's and VAnalyte
number, and ,VdAnalyte
Analyte and M
, d, Analyte , and Mwere
Analyte Analyte the
wereeffective volumevolume
the effective of analyte
of
in the laser beam, the density, and molecular weights of the related analyte
analyte in the laser beam, the density, and molecular weights of the related analyte (Table 2), (Table 2), respectively.
The EFs wereThe
respectively. then estimated
EFs were then using Equation
estimated (1) Equation
using for the different analytes
(1) for the (Table
different 2). The
analytes determined
(Table 2). The
values were ≈7.2 × 10 7 , 2.3 × 107 , and 1.3 × 107 for the CV, MB, and R6G analytes on the Cu/gCN
determined values were ≈7.2 × 10 , 2.3 × 10 , and 1.3 × 10 for the CV, MB, and R6G analytes on the
7 7 7

substrate,substrate,
Cu/gCN respectively (see Method
respectively (seeS1 for further
Method S1 fordetails).
further details).

(a) (b)

(c)
Figure 7. Comparison
Comparison of the "normal"
“normal”(i.e.,(i.e.,non-SERS)
non-SERS)Raman
Ramanspectra
spectraof of(a)
(a)CV,
CV, (b)
(b) MB, and (c) R6G
with the SERS/SERRS spectra of the three analytes decorated on a Cu/gCN support. The The concentration
concentration
of the analytes was 10 10−3
−3 M for recording
M "normal" Raman
both the “normal” Raman andand SERS spectra. Spectra
Spectra were
plotted following
followingsubtraction
subtractionofofthe
thefluorescence
fluorescencebackground
background from
from thethe organic
organic molecules
molecules (see(see Figure
Figure S1).
S1). Theline
The red redindicates
line indicates the characteristic
the characteristic peak used peak used to determine
to determine the SERS
the SERS activity activity
(see text and(see text and
Supporting
Supporting
Information). Information). The spectra
The spectra have have been
been vertically vertically
displaced for displaced
clarity. Thefor clarity.
counts The counts
represent represent
an integration
time
an of 100 s oftime
integration 50 accumulated
of 100 s of 50scans, each with
accumulated a 2 s each
scans, exposure
with period in all cases.
a 2 s exposure period in all cases.

Table 2. Physical characteristics of the analytes used to estimate EFs.

Analyte Density (g/mL) Surface Area (nm2) nRaman/nSERS ISERS/IRaman Cu/g-CN EFs
Crystal violet 1 1.2 5.4× 1015π/1.5× 109π 20 7.2 × 107
Methylene blue 0.98 1.3 6.6× 1015π/1.4× 109π 6.6 2.3 × 107
Rhodamine 6G 1.26 0.6 6× 1015π/3× 109π 6.4 1.3 × 107

Because of the several assumptions and approximations used to obtain these EFs, they can only
Nanomaterials 2019, 9, 1223 11 of 16

Table 2. Physical characteristics of the analytes used to estimate EFs.

Density Surface Area

Analyte nRaman /nSERS ISERS /IRaman Cu/g-CN EFs
(g/mL) (nm2 )
Crystal violet 1 1.2 5.4 × 1015 π/1.5 × 109 π 20 7.2 × 107
Methylene blue 0.98 1.3 6.6 × 1015 π/1.4 × 109 π 6.6 2.3 × 107
Rhodamine 6G 1.26 0.6 6 × 1015 π/3 × 109 π 6.4 1.3 × 107

Because of the several assumptions and approximations used to obtain these EFs, they can only
be considered as guide values for comparison with SERS and SERRS EF values recorded for these
and related analytes on noble metal nanoparticles supported on semiconducting surfaces. Su et al.
prepared a Au/MoS2 nanocomposite using in situ growth of Au NPs on MoS2 nanosheet surfaces,
and demonstrated that the Au@MoS2 substrates exhibited an 8.2 × 105 enhancement for the 1362 cm−1
Raman mode of R6G [89]. Jiang et al. reported that g-C3 N4 /Ag NPs exhibited EFs of 4.6 × 108
and 2.1 × 109 using CV as an analyte [70,71]. These authors linked the large EF values to multiple
enhancement contributions, and that charge transfer between the g-C3 N4 and the metal surface
protected the Ag NPs from oxidation. There are only a few literature reports on the use of pure Cu NPs
as a SERS substrate, either supported or in colloidal suspension [16,23–25]. Dendisová-Vyškovská et al.
found EF = 1.7 × 105 for the 1590 cm−1 band of 4-aminobenzenethiol (4-ABT) [16], and Ding et al.
obtained an EF = 1.6 × 107 for CV adsorbed on an array of Cu NPs deposited using sputtering on the
surface of a monolayered colloidal crystal of 350 nm polystyrene spheres [23]. The SERS/SERRS results
varied dramatically as a function of NP size controlled by the deposition time, with the most intense
spectra recorded for an 18 min deposition with particles ≈150–200 nm in size. Although the exciting
wavelength (532 nm) was the same as that used in our study, the SERS/SERRS spectrum recorded for
CV was slightly different to our result in that the 1619 cm−1 band was much more intense. However,
the fact that the EFs obtained in both studies is comparable is encouraging.

4. Conclusions
Our results confirm that Cu/gCN nanomaterial composites can be useful for the development
of SERS/SERRS applications. Our Cu NPs on sp2 -bonded carbon nitride supports were fabricated
using pulsed laser ablation of a Cu plate immersed in acetonitrile solvent. We carried out chemical,
structural, and spectroscopic analyses to study the nature of the Cu NPs and their gCN support.
The N:C ratio of the gCN material determined using bulk analysis was ≈1.3, significantly lower
than the semiconducting carbon nitride compounds based on heptazine- to triazine-based structures,
but it contained close-to-layered gCN materials containing mixed C–N/C–C bonding prepared using
vapor deposition techniques. Such materials might contain locally electronically conducting domains.
The degree of layer polymerization was incomplete, as shown by strong IR and Raman signals
from terminal C≡N bonds. The Cu/gCN hybrid nanocomposites exhibited strong visible absorption
extending toward the near-IR region with an SPR signal from the metal NPs at 580 nm. SERS/SERRS
enhancement activity was tested using three analyte molecules (CV, MB, and R6G) prepared with
initial solution concentrations of 10−3 –10−7 mol/L in acetonitrile and adsorbed onto the Cu/gCN
nanocomposite surfaces. The observed SERS/SERRS enhancement factors were on the order of 107 ,
comparable with EF values found for nanoparticle arrays of Cu produced using sputtering onto
templates and other noble metal NPs supported by gCN materials. Further studies are now needed to
investigate the possibility of cooperative interactions between the gCN support and the metal NPs that
could enhance the optoelectronic effects leading to SERS/SERRS enhancement, as well as in stabilizing
the Cu NPs.
Nanomaterials 2019, 9, 1223 12 of 16

Supplementary Materials: The Supplementary Materials are available online at http://www.mdpi.com/2079-4991/

9/9/1223/s1.
Author Contributions: The study was devised by R.M. and synthesis, Raman, and SERS experiments were
performed by H.D.-A. TEM and XPS characterization was performed by T.S.M. All authors participated in the
interpretation of the results. H.D.-A. wrote a first draft of the manuscript that was completed and edited by P.F.M.
and T.S.M.
Funding: R.M. thanks the Iran Nanotechnology Initiative Council (INIC) for financial support of the pulsed laser
ablation setup. P.F.M. acknowledges support from the EU Graphene Flagship under Horizon 2020 Research and
Innovation program grant agreement No. 696656—Graphene Core2. T.S.M. thanks the UK Engineering Physical
Research Council for support via the EPSRC Postdoctoral Fellowship EP/P023851/1.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design of the
study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to
publish the results.

References
1. Bell, S.E.J.; Sirimuthu, N.M.S. Surface-Enhanced Raman Spectroscopy (SERS) for Sub-Micromolar Detection
of DNA/RNA Mononucleotides. J. Am. Chem. Soc. 2006, 128, 15580–15581. [CrossRef] [PubMed]
2. Ambrosio, R.C.; Gewirth, A.A. Characterization of Water Structure on Silver Electrode Surfaces by SERS
with Two-Dimensional Correlation Spectroscopy. Anal. Chem. 2010, 82, 1305–1310. [CrossRef] [PubMed]
3. Roguska, A.; Kudelski, A.; Pisarek, M.; Lewandowska, M.; Kurzydłowski, K.; Janik-Czachor, M.
In situ spectroelectrochemical surface-enhanced Raman scattering (SERS) investigations on composite
Ag/TiO2 -nanotubes/Ti substrates. Surf. Sci. 2009, 603, 2820–2824. [CrossRef]
4. Qiu, C.; Zhang, L.; Wang, H.; Jiang, C. Surface-Enhanced Raman Scattering on Hierarchical Porous Cuprous
Oxide Nanostructures in Nanoshell and Thin-Film Geometries. J. Phys. Chem. Lett. 2012, 3, 651–657. [CrossRef]
[PubMed]
5. Fateixa, S.; Nogueira, H.I.S.; Trindade, T.; Caria, S.F.; Nogueira, H.S. Hybrid nanostructures for SERS:
Materials development and chemical detection. Phys. Chem. Chem. Phys. 2015, 17, 21046–21071. [CrossRef]
[PubMed]
6. Han, X.X.; Ji, W.; Zhao, B.; Ozaki, Y. Semiconductor-enhanced Raman scattering: Active nanomaterials and
applications. Nanoscale 2017, 9, 4847–4861. [CrossRef] [PubMed]
7. Lombardi, J.R.; Birke, R.L. A Unified Approach to Surface-Enhanced Raman Spectroscopy. J. Phys. Chem. C
2008, 112, 5605–5617. [CrossRef]
8. Kneipp, K.; Wang, Y.; Kneipp, H.; Perelman, L.T.; Itzkan, I.; Dasari, R.R.; Feld, M.S. Single Molecule Detection
Using Surface-Enhanced Raman Scattering (SERS). Phys. Rev. Lett. 1997, 78, 1667–1670. [CrossRef]
9. Nie, S.; Emory, S.R. Probing single molecules and single nanoparticles by SERS. Science 1997, 275, 1102–1106.
[CrossRef] [PubMed]
10. Xu, H.; Bjerneld, E.J.; Käll, M.; Börjesson, L. Spectroscopy of Single Hemoglobin Molecules by Surface
Enhanced Raman Scattering. Phys. Rev. Lett. 1999, 83, 4357–4360. [CrossRef]
11. Schlücker, S. Surface-Enhanced Raman Spectroscopy: Concepts and Chemical Applications. Angew. Chem.
Int. Ed. 2014, 53, 4756–4795. [CrossRef] [PubMed]
12. Wang, X.; Shi, W.; She, G.; Mu, L. Using Si and Ge Nanostructures as Substrates for Surface-Enhanced Raman
Scattering Based on Photoinduced Charge Transfer Mechanism. J. Am. Chem. Soc. 2011, 133, 16518–16523.
[CrossRef] [PubMed]
13. Ji, W.; Zhao, B.; Ozaki, Y. Semiconductor materials in analytical applications of surface-enhanced Raman
scattering. J. Raman Spectrosc. 2016, 47, 51–58. [CrossRef]
14. Musumeci, A.; Gosztola, D.; Schiller, T.; Dimitrijevic, N.M.; Mujica, V.; Martin, D.; Rajh, T. SERS of
Semiconducting Nanoparticles (TiO2 Hybrid Composites). J. Am. Chem. Soc. 2009, 131, 6040–6041. [CrossRef]
[PubMed]
15. Teguh, J.S.; Xing, B.; Yeow, E.K.L.; Liu, F.; Xing, P.D.B.; Yeow, P.D.E.K.L. Surface-Enhanced Raman Scattering
(SERS) of Nitrothiophenol Isomers Chemisorbed on TiO2 . Chem. Asian J. 2012, 7, 975–981. [CrossRef]
[PubMed]
Nanomaterials 2019, 9, 1223 13 of 16

16. Dendisova-Vyskovska, M.; Prokopec, V.; Člupek, M.; Matějka, P. Comparison of SERS effectiveness of copper
substrates prepared by different methods: What are the values of enhancement factors? J. Raman Spectrosc.
2012, 43, 181–186. [CrossRef]
17. McNay, G.; Eustace, D.; Smith, W.E.; Faulds, K.; Graham, D. Surface-enhanced Raman scattering (SERS) and
resonance Raman scattering (SERRS): A review of applications. Appl. Spectrosc. 2011, 65, 825–837. [CrossRef]
[PubMed]
18. Bell, S.E.J.; McCourt, M.R. SERS enhancement by aggregated Au colloids: Effect of particle size. Phys. Chem.
Chem. Phys. 2009, 11, 7455–7462. [CrossRef] [PubMed]
19. Jung, M.; Kim, S.K.; Lee, S.; Kim, J.H.; Woo, D. Ag nanodot array as a platform for surface-enhanced Raman
scattering. J. Nanophotonics 2013, 7, 073798. [CrossRef]
20. Jung, G.B.; Bae, Y.M.; Lee, Y.J.; Ryu, S.H.; Park, H.-K. Nanoplasmonic Au nanodot arrays as an SERS substrate
for biomedical applications. Appl. Surf. Sci. 2013, 282, 161–164. [CrossRef]
21. Ameer, F.S.; Pittman, C.U.; Zhang, D. Quantification of Resonance Raman Enhancement Factors for
Rhodamine 6G (R6G) in Water and on Gold and Silver Nanoparticles: Implications for Single-Molecule R6G
SERS. J. Phys. Chem. C 2013, 117, 27096–27104. [CrossRef]
22. Roguska, A.; Kudelski, A.; Pisarek, M.; Opara, M.; Janik-Czachor, M. Surface-enhanced Raman scattering
(SERS) activity of Ag, Au and Cu nanoclusters on TiO2 -nanotubes/Ti substrate. Appl. Surf. Sci. 2011,
257, 8182–8189. [CrossRef]
23. Ding, Q.; Hang, L.; Ma, L. Controlled synthesis of Cu nanoparticle arrays with surface enhanced Raman
scattering effect performance. RSC Adv. 2018, 8, 1753–1757. [CrossRef]
24. Nguyen, T.B.; Vu, T.K.T.; Nguyen, Q.D.; Nguyen, T.D.; Nguyen, T.A.; Trinh, T.H. Preparation of metal nanoparticles
for surface enhanced Raman scattering by laser ablation method. Adv. Nat. Sci. Nanosci. Nanotechnol. 2012,
3, 025016. [CrossRef]
25. Muniz-Miranda, M.; Gellini, C.; Giorgetti, E. Surface-Enhanced Raman Scattering from Copper Nanoparticles
Obtained by Laser Ablation. J. Phys. Chem. C 2011, 115, 5021–5027. [CrossRef]
26. Khan, A.; Rashid, A.; Younas, R.; Chong, R. A chemical reduction approach to the synthesis of copper
nanoparticles. Int. Nano Lett. 2016, 6, 21–26. [CrossRef]
27. Soomro, R.A.; Sirajuddin, S.T.H.S.; Memon, N.; Shah, M.R.; Kalwar, N.H.; Hallam, K.R.; Shah, A. Synthesis
of Air Stable Copper Nanoparticles and Their Use in Catalysis. Adv. Mater. Lett. 2014, 5, 191–198. [CrossRef]
28. Dang, T.M.D.; Le, T.T.T.; Fribourg-Blanc, E.; Dang, M.C. Synthesis and optical properties of copper
nanoparticles prepared by a chemical reduction method. Adv. Nat. Sci. Nanosci. Nanotechnol. 2011, 2, 015009.
[CrossRef]
29. Matikainen, A.; Nuutinen, T.; Itkonen, T.; Heinilehto, S.; Puustinen, J.; Hiltunen, J.; Lappalainen, J.; Karioja, P.;
Vahimaa, P. Atmospheric oxidation and carbon contamination of silver and its effect on surface-enhanced
Raman spectroscopy (SERS). Sci. Rep. 2016, 6, 37192. [CrossRef]
30. Zeng, F.; Xu, D.; Zhan, C.; Liang, C.; Zhao, W.; Zhang, J.; Feng, H.; Ma, X. Surfactant-Free Synthesis of
Graphene Oxide Coated Silver Nanoparticles for SERS Biosensing and Intracellular Drug Delivery. ACS Appl.
Nano Mater. 2018, 1, 2748–2753. [CrossRef]
31. Neddersen, J.; Chumanov, G.; Cotton, T.M. Laser Ablation of Metals: A New Method for Preparing SERS
Active Colloids. Appl. Spectrosc. 1993, 47, 1959–1964. [CrossRef]
32. Gondal, M.A.; Qahtan, T.F.; Dastageer, M.A.; Maganda, Y.W.; Anjum, D.H. Synthesis of Cu/Cu2 O nanoparticles
by laser ablation in deionized water and their annealing transformation into CuO nanoparticles. J. Nanosci.
Nanotechnol. 2013, 13, 5759–5766. [CrossRef] [PubMed]
33. Aghdam, H.D.; Azadi, H.; Esmaeilzadeh, M.; Bellah, S.M.; Malekfar, R. Ablation time and laser fluence
impacts on the composition, morphology and optical properties of copper oxide nanoparticles. Opt. Mater.
2019, 91, 433–438. [CrossRef]
34. Abdulateef, S.A.; MatJafri, M.Z.; Omar, A.F.; Ahmed, N.M.; Azzez, S.A.; Ibrahim, I.M.; Al-Jumaili, B.E.B.
Preparation of CuO nanoparticles by laser ablation in liquid. AIP Conf. Proc. 2016, 1733, 020035.
35. Kudelski, A.; Grochala, W.; Janik-Czachor, M.; Bukowska, J.; Szummer, A.; Dolata, M. Surface-enhanced
Raman scattering (SERS) at Copper(I) oxide. J. Raman Spectrosc. 1998, 29, 431–435. [CrossRef]
36. Amendola, V.; Rizzi, G.A.; Polizzi, S.; Meneghetti, M. Synthesis of Gold Nanoparticles by Laser Ablation in
Toluene: Quenching and Recovery of the Surface Plasmon Absorption. J. Phys. Chem. B 2005, 109, 23125–23128.
[CrossRef] [PubMed]
Nanomaterials 2019, 9, 1223 14 of 16

37. Nikov, R.G.; Nedyalkov, N.N.; Atanasov, P.A.; Karashanova, D.B. Laser-assisted fabrication and size
distribution modification of colloidal gold nanostructures by nanosecond laser ablation in different liquids.
Appl. Phys. A 2017, 123, 490. [CrossRef]
38. Cho, H.-G. Matrix Infrared Spectra and DFT Computations of CH2 CNH and CH2 NCH Produced from
CH3 CN by Laser-Ablation Plume Radiation. Bull. Korean Chem. Soc. 2013, 34, 1361–1365. [CrossRef]
39. Andrews, L.; Citra, A. Infrared Spectra and Density Functional Theory Calculations on Transition Metal
Nitrosyls. Vibrational Frequencies of Unsaturated Transition Metal Nitrosyls. Chem. Rev. 2002, 102, 885–912.
[CrossRef]
40. Cho, H.-G.; Andrews, L. Matrix Infrared Spectra and Density Functional Calculations of the H2 CCN and
H2 CNC Radicals Produced from CH3 CN. J. Phys. Chem. A 2011, 115, 8638–8642. [CrossRef]
41. Amendola, V.; Meneghetti, M. What controls the composition and the structure of nanomaterials generated
by laser ablation in liquid solution? Phys. Chem. Chem. Phys. 2013, 15, 3027–3046. [CrossRef] [PubMed]
42. Hamad, S.; Podagatlapalli, G.K.; Rao, S.V.; Syed, H.; Soma, V.R. Explosives Detection with Copper
Nanostructures Fabricated using Ultrafast Laser Ablation in Acetonitrile. Light Energy Environ. 2014. [CrossRef]
43. Kessler, F.K.; Zheng, Y.; Schwarz, D.; Merschjann, C.; Schnick, W.; Wang, X.; Bojdys, M.J. Functional carbon
nitride materials—Design strategies for electrochemical devices. Nat. Rev. Mater. 2017, 2, 17030. [CrossRef]
44. Miller, T.; Jorge, A.B.; Suter, T.M.; Sella, A.; Corà, F.; McMillan, P.F. Carbon nitrides: Synthesis and
characterization of a new class of functional materials. Phys. Chem. Chem. Phys. 2017, 19, 15613–15638.
[CrossRef] [PubMed]
45. Wen, J.; Xie, J.; Chen, X.; Li, X. A review on g-C 3 N 4 -based photocatalysts. Appl. Surf. Sci. 2017, 391, 72–123.
[CrossRef]
46. Mansor, N.; Miller, T.S.; Dedigama, I.; Jorge, A.B.; Jia, J.; Brázdová, V.; Mattevi, C.; Gibbs, C.; Hodgson, D.;
Shearing, P.R.; et al. Graphitic Carbon Nitride as a Catalyst Support in Fuel Cells and Electrolyzers.
Electrochim. Acta 2016, 222, 44–57. [CrossRef]
47. Algara-Siller, G.; Severin, N.; Chong, S.Y.; Björkman, T.; Palgrave, R.G.; Laybourn, A.; Antonietti, M.;
Khimyak, Y.Z.; Krasheninnikov, A.V.; Rabe, J.P.; et al. Triazine-Based Graphitic Carbon Nitride: A Two-Dimensional
Semiconductor. Angew. Chem. 2014, 126, 7580–7585. [CrossRef]
48. Wirnhier, E.; Doblinger, M.; Gunzelmann, D.; Senker, J.; Lotsch, B.V.; Schnick, W. Poly(triazine imide) with
intercalation of lithium and chloride ions [(C3N3)2(NHxLi1-x)3•LiCl]: A crystalline 2D carbon nitride
network. Chem. Eur. J. 2011, 17, 3213–3221. [CrossRef]
49. Ladva, S.A.; Travis, W.; Quesada-Cabrera, R.; Rosillo-Lopez, M.; Afandi, A.; Li, Y.; Jackman, R.B.; Bear, J.C.;
Parkin, I.P.; Blackman, C.; et al. Nanoscale, conformal films of graphitic carbon nitride deposited at room
temperature: A method for construction of heterojunction devices. Nanoscale 2017, 9, 16586–16590. [CrossRef]
50. Suter, T.M.; Brazdova, V.; McColl, K.; Miller, T.S.; Nagashima, H.; Salvadori, E.; Sella, A.; Howard, C.A.;
Kay, C.W.M.; Cora, F.; et al. Synthesis, Structure and Electronic Properties of Graphitic Carbon Nitride Films.
J. Phys. Chem. C 2018, 122, 25183–25194. [CrossRef]
51. Zhang, Z.J.; Fan, S.; Lieber, C.M. Growth and composition of covalent carbon nitride solids. Appl. Phys. Lett.
1995, 66, 3582–3584. [CrossRef]
52. Rodil, S.E.; Muhl, S.; Maca, S.; Ferrari, A. Optical gap in carbon nitride films. Thin Solid Films 2003, 433, 119–125.
[CrossRef]
53. Inagaki, M.; Toyoda, M.; Soneda, Y.; Morishita, T. Nitrogen-doped carbon materials. Carbon 2018, 132, 104–140.
[CrossRef]
54. González, P.; Soto, R.; Parada, E.; Redondas, X.; Chiussi, S.; Serra, J.; Pou, J.; Leon, B.; Pérez-Amor, M. Carbon
nitride films prepared by excimer laser ablation. Appl. Surf. Sci. 1997, 109, 380–383. [CrossRef]
55. Bulíř, J.; Jelínek, M.; Vorlicek, V.; Zemek, J.; Perina, V. Study of nitrogen pressure effect on the laser-deposited
amorphous carbon films. Thin Solid Films 1997, 292, 318–323. [CrossRef]
56. Zhao, X.; Ong, C.W.; Tsang, Y.C.; Wong, Y.W.; Chan, P.W.; Choy, C.L. Reactive pulsed laser deposition of CNx
films. Appl. Phys. Lett. 1995, 66, 2652–2654. [CrossRef]
57. Ong, C.W.; Zhao, X.-A.; Tsang, Y.; Choy, C.; Chan, P. Effects of substrate temperature on the structure and
properties of reactive pulsed laser deposited CNx films. Thin Solid Films 1996, 280, 1–4. [CrossRef]
58. Alexandrescu, R.; Huisken, F.; Pugna, G.; Crunteanu, A.; Petcu, S.; Cojocaru, S.; Cireasa, R.; Morjan, I.;
Cojocaru, C.S. Preparation of carbon nitride fine powder by laser induced gas-phase reactions. Appl. Phys. A
1997, 65, 207–213. [CrossRef]
Nanomaterials 2019, 9, 1223 15 of 16

59. Sharma, A.K.; Ayyub, P.; Multani, M.S.; Adhi, K.P.; Ogale, S.B.; Sunderaraman, M.; Upadhyay, D.D.;
Banerjee, S. Synthesis of crystalline carbon nitride thin films by laser processing at a liquid–solid interface.
Appl. Phys. Lett. 1996, 69, 3489–3491. [CrossRef]
60. Yang, L.; May, P.W.; Yin, L.; Brown, R.; Scott, T.B. Direct Growth of Highly Organized Crystalline Carbon
Nitride from Liquid-Phase Pulsed Laser Ablation. Chem. Mater. 2006, 18, 5058–5064. [CrossRef]
61. Li, H.; Xu, Y.; Sitinamaluwa, H.; Wasalathilake, K.; Galpaya, D.; Yan, C. Cu nanoparticles supported on
graphitic carbon nitride as an efficient electrocatalyst for oxygen reduction reaction. Chin. J. Catal. 2017,
38, 1006–1010. [CrossRef]
62. Le, S.; Fang, B.; Jiang, T.; Zhao, Q.; Liu, X.; Li, Y.; Gong, M. Cu-doped mesoporous graphitic carbon nitride
for enhanced visible-light driven photocatalysis. RSC Adv. 2016, 6, 38811–38819. [CrossRef]
63. Muniandy, L.; Adam, F.; Mohamed, A.R.; Iqbal, A.; Rahman, N.R.A. Cu2+ coordinated graphitic carbon
nitride (Cu-g-C3 N4 ) nanosheets from melamine for the liquid phase hydroxylation of benzene and VOCs.
Appl. Surf. Sci. 2017, 398, 43–55. [CrossRef]
64. Gao, J.; Wang, J.; Qian, X.; Dong, Y.; Xu, H.; Song, R.; Yan, C.; Zhu, H.; Zhong, Q.; Qian, G.; et al. One-pot
synthesis of copper-doped graphitic carbon nitride nanosheet by heating Cu–melamine supramolecular
network and its enhanced visible-light-driven photocatalysis. J. Solid State Chem. 2015, 228, 60–64. [CrossRef]
65. Tahir, B.; Tahir, M.; Amin, N.A.S. Photo-induced CO2 reduction by CH4 /H2 O to fuels over Cu-modified
g-C3 N4 nanorods under simulated solar energy. Appl. Surf. Sci. 2017, 419, 875–885. [CrossRef]
66. Shi, G.; Yang, L.; Liu, Z.; Chen, X.; Zhou, J.; Yu, Y. Photocatalytic reduction of CO2 to CO over copper
decorated g-C3 N4 nanosheets with enhanced yield and selectivity. Appl. Surf. Sci. 2018, 427, 1165–1173.
[CrossRef]
67. Wolosiuk, A.; Tognalli, N.G.; Martínez, E.D.; Granada, M.; Fuertes, M.C.; Troiani, H.; Bilmes, S.A.; Fainstein, A.;
Soler-Illia, G.J.A.A. Silver Nanoparticle-Mesoporous Oxide Nanocomposite Thin Films: A Platform for
Spatially Homogeneous SERS-Active Substrates with Enhanced Stability. ACS Appl. Mater. Interfaces 2014,
6, 5263–5272. [CrossRef] [PubMed]
68. Yang, K.-H.; Liu, Y.-C.; Hsu, T.-C.; Juang, M.-Y. Strategy to improve stability of surface-enhanced raman
scattering-active Ag substrates. J. Mater. Chem. 2010, 20, 7530–7535. [CrossRef]
69. Mai, F.-D.; Yang, K.-H.; Liu, Y.-C.; Hsu, T.-C. Improved stabilities on surface-enhanced Raman scattering-active
Ag/Al2 O3 films on substrates. Analyst 2012, 137, 5906–5912. [CrossRef] [PubMed]
70. Jiang, J.; Zhu, L.; Zou, J.; Ou-Yang, L.; Zheng, A.; Tang, H. Micro/nano-structured graphitic carbon nitride—Ag
nanoparticle hybrids as surface-enhanced Raman scattering substrates with much improved long-term
stability. Carbon 2015, 87, 193–205. [CrossRef]
71. Jiang, J.; Zou, J.; Wee, A.T.S.; Zhang, W. Use of Single-Layer g-C3 N4 /Ag Hybrids for Surface-Enhanced
Raman Scattering (SERS). Sci. Rep. 2016, 6, 34599. [CrossRef] [PubMed]
72. Schneider, C.A.; Rasband, W.S.; Eliceiri, K.W. NIH Image to ImageJ: 25 years of Image Analysis. Nat. Methods
2012, 9, 671–675. [CrossRef] [PubMed]
73. Biesinger, M.C.; Payne, B.P.; Grosvenor, A.P.; Lau, L.W.; Gerson, A.R.; Smart, R.S. Resolving surface chemical
states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni. Appl. Surf.
Sci. 2011, 257, 2717–2730. [CrossRef]
74. Liu, P.; Wang, H.; Li, X.; Rui, M.; Zeng, H. Localized surface plasmon resonance of Cu nanoparticles by laser
ablation in liquid media. RSC Adv. 2015, 5, 79738–79745. [CrossRef]
75. Zambon, A.; Mouesca, J.M.; Gheorghiu, C.; Bayle, P.A.; Pécaut, J.; Claeys-Bruno, M.; Gambarelli, S.; Dubois, L.
s-Heptazine oligomers: Promising structural models for graphitic carbon nitride. Chem. Sci. 2016, 7, 945–950.
[CrossRef] [PubMed]
76. Fina, F.; Callear, S.K.; Carins, G.M.; Irvine, J.T.S. Structural Investigation of Graphitic Carbon Nitride via
XRD and Neutron Diffraction. Chem. Mater. 2015, 27, 2612–2618. [CrossRef]
77. Tyborski, T.; Merschjann, C.; Orthmann, S.; Yang, F.; Lux-Steiner, M.-C.; Schedel-Niedrig, T. Crystal structure
of polymeric carbon nitride and the determination of its process-temperature-induced modifications. J. Phys.
Condens. Matter 2013, 25, 395402. [CrossRef]
78. Bonner, O.; Curry, J.D. Infrared spectra of liquid H2 O and D2 O. Infrared Phys. 1970, 10, 91–94. [CrossRef]
79. Rodil, S.E.; Ferrari, A.; Robertson, J.; Muhl, S. Infrared spectra of carbon nitride films. Thin Solid Films 2002,
420, 122–131. [CrossRef]
Nanomaterials 2019, 9, 1223 16 of 16

80. Ferrari, A.C.; Rodil, S.E.; Robertson, J. Interpretation of infrared and Raman spectra of amorphous carbon
nitrides. Phys. Rev. B 2003, 67, 155306. [CrossRef]
81. Angeloni, L.; Smulevich, G.; Marzocchi, M.P. Resonance Raman spectrum of crystal violet. J. Raman Spectrosc.
1979, 8, 305–310. [CrossRef]
82. Anastasopoulos, J.; Beobide, A.S.; Manikas, A.; Voyiatzis, G. Quantitative surface-enhanced resonance Raman
scattering analysis of methylene blue using silver colloid. J. Raman Spectrosc. 2017, 48, 1762–1770. [CrossRef]
83. Mo, Y.; Lei, J.; Li, X.; Wächter, P. Surface enhanced Raman scattering of rhodamine 6G and dye 1555 adsorbed
on roughened copper surfaces. Solid State Commun. 1988, 66, 127–131. [CrossRef]
84. Ujihara, M.; Dang, N.M.; Imae, T. Surface-Enhanced Resonance Raman Scattering of Rhodamine 6G in
Dispersions and on Films of Confeito-Like Au Nanoparticles. Sensors 2017, 17, 2563. [CrossRef] [PubMed]
85. Le Ru, E.C.; Blackie, E.; Meyer, M.; Etchegoin, P.G. Surface Enhanced Raman Scattering Enhancement Factors:
A Comprehensive Study. J. Phys. Chem. C 2007, 111, 13794–13803. [CrossRef]
86. Jiang, L.; You, T.; Yin, P.; Shang, Y.; Zhang, D.; Guo, L.; Yang, S. Surface-enhanced Raman scattering spectra
of adsorbates on Cu2 O nanospheres: Charge-transfer and electromagnetic enhancement. Nanoscale 2013,
5, 2784–2789. [CrossRef] [PubMed]
87. He, S.; Chua, J.; Tan, E.K.M.; Kah, J.C.Y. Optimizing the SERS enhancement of a facile gold nanostar
immobilized paper-based SERS substrate. RSC Adv. 2017, 7, 16264–16272. [CrossRef]
88. Xu, Y.; Konrad, M.P.; Trotter, J.L.; McCoy, C.P.; Bell, S.E.J. Rapid One-Pot Preparation of Large Freestanding
Nanoparticle-Polymer Films. Small 2016, 13, 1602163. [CrossRef] [PubMed]
89. Su, S.; Zhang, C.; Yuwen, L.; Chao, J.; Zuo, X.; Liu, X.; Song, C.; Fan, C.; Wang, L. Creating SERS Hot Spots on
MoS2 Nanosheets with in Situ Grown Gold Nanoparticles. ACS Appl. Mater. Interfaces 2014, 6, 18735–18741.
[CrossRef]

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