Applied Surface Science 569 (2021) 151014

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Full Length Article

Bottom-up colloidal synthesis of PMMA@Au core–shell based

metallodielectric photonic crystals as substrates for surface-enhanced
Raman spectroscopy
Syara Kassim a, Sibu C. Padmanabhan b, c, *, Martyn E. Pemble d, e, *
a
Advanced Nano Materials Research Group (ANoMa), Faculty of Science and Marine Environment, Universiti Malaysia Terengganu, 21030 Kuala Nerus, Terengganu,
Malaysia
b
Advanced Materials and BioEngineering Research (AMBER) Centre, Trinity College Dublin, Dublin 2, Ireland
c
School of Chemistry, Trinity College Dublin, College Green, Dublin 2, Ireland
d
School of Chemistry, University College Cork, Cork, Ireland
e
Tyndall National Institute, University College Cork, Cork, Ireland

A R T I C L E I N F O A B S T R A C T

Keywords: The bottom-up colloidal synthesis of photonic band gap (PBG) materials or photonic crystals (PCs) has attracted
Photonic crystals considerable interest in comparison to top-down approaches due to the relatively simple processing steps
PMMA@Au involved, the potential for large area sample production and the relatively low-costs associated with this
Core–shell
approach for the fabrication of complex 3-dimensional (3D) structures. This research focuses on the colloidal
Metallodielectric
Surface-enhanced Raman scattering
synthesis of poly(methyl methacrylate) (PMMA)@Au core–shell (CS) structures, their bottom-up assembly into
3D metallodielectric PCs (MDPCs) and the demonstration of their potential to be used as surface enhanced
Raman substrates (SERS) using the commonly deployed SERS reporter molecule, 4- aminothiolphenol. Here,
monodispersed spherical PMMA particles were used both as a host material for Au nanoparticles (NPs) and as a
crystal template to produce the MDPC structures. The materials engineering employed which involved
combining the synthesis of monodispersed CS particles and the fabrication of their corresponding MDPCs enabled
us to control the distribution of Au NPs in the PC structure and thereby investigate their light scattering,
reflection and transmission properties including Raman scattering.

1. Introduction
Bi-layered and multi-layered structural designs of colloidal particles
surrounded or covered with metal NPs have recently attracted consid­
erable attention owing to their topological complexity and their useful
optical properties, often resulting from the activity of surface plasmon
resonances (SPRs), which originate from the collective oscillations of
conduction electrons in reaction to optical excitation [1]. Among these
CS structures, particles surrounded with metal NPs typically silver or
gold, are of particular interest. They enable us to manipulate and use the
metal NPs in an effective and convenient way to suit tailored applica­
tions [1–4]. The SPR frequency depends on the particle size, shape and
the surrounding dielectric medium [5]. The incorporation of metallic
nanostructures such as Au is therefore interesting because such nano­
structures possess SPRs, which manifest as additional absorption bands
in the PC structure. For example, the SPR peak of 13 nm spherical Au
colloids are around 520 nm and that of 5–6 nm Ag NPs around 400 nm
[1]. SPR has been explored for use in fabricating optical filters [5],
active surfaces for enhanced Raman spectroscopy [1,6,7] fluorescence
scattering [8], and chemical and biological sensors [6].
The composite NPs that consist of a dielectric core coated with a few
nanometres of metal have shown tremendous promise for the systematic
engineering of the SPR [9,10]. The SPR of these NPs can be varied over
hundreds of nanometres in wavelength, across the visible and into the
infrared region of spectrum, by varying the relative dimensions of the
core and the shell [9,10]. In most studies involving surface plasmons, Au
and Ag are used, because Ag produces a sharp resonance, and Au is more
stable in air and is generally inert [8].
The synthesis of Au NPs onto both silica (Si) and polystyrene (PS)
cores has been reported [9,10]. The advantage of using polymer colloids
instead of silica is that they are easily removed by solvent dissolution or
thermal calcination, when acting as templates for macroporous

* Corresponding authors.
E-mail addresses: chullans@tcd.ie (S.C. Padmanabhan), martyn.pemble@tyndall.ie (M.E. Pemble).

https://doi.org/10.1016/j.apsusc.2021.151014
Received 13 April 2021; Received in revised form 29 July 2021; Accepted 17 August 2021
Available online 20 August 2021
0169-4332/© 2021 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
S. Kassim et al.
materials or inverse opals [11]. The advantages of using PMMA are the
high degree uniformity of the particles as shown in ESI 1 and a
considerably shorter synthesis time (eleven times shorter as compared to
PS particles synthesis). It was reported that silica@Au CS particles were
less stable in terms of forming a PCs film [3]. Typically, the formation of
a second silica shell around the metal NPs, often referred to as core–­
shell-shell (CSS) particles, makes silica@metal CS particles more stable,
and easier to use when making PC films [4].
Here we show that the use of PMMA instead of silica enable us to
successfully immobilize these CS type of particles into a PC film without
any secondary shell formation. A bi-layer technique was developed here
to prepare PMMA@Au CS composite. Polyethyleneimine (PEI) is
employed to act as the linker between Au atoms in Au NPs and PMMA
colloids. We further explore the use of the prepared MDPCs as SERS
substrates, focusing mainly on the novel chemistry used to create the
substrates in question. We then demonstrate their utility using a
commonly-used SERS reporter molecule, 4-aminothiolphenol (4-ATP)
adsorbed on a substrate consisting of Au NPs embedded in the MDPC
structure. Although the SERS data presented are somewhat preliminary,
the optical studies presented here show that it should be possible to
carefully design the PC structure such that the detection of the Raman
signal from an adsorbate can be made easier. In particular the Rayleigh
and Raman scattering can, in principle, be spatially separated using this
approach while the typical dispersion over 4π steradians that is found for
Raman scattering could be focused into a narrow beam by the PC matrix.
2. Experimental section
2.1. Synthesis of PMMA colloidal particles
Methyl methacrylate (MMA) and potassium persulfate were pur­
chased from Aldrich. Millipore water (18.2 MΏ cm) was used as the
medium of reaction. The PMMA colloid of mean particle size 415 nm
(relative standard deviation < 5%) was prepared by an emulsifier-free
emulsion polymerization in water in the presence of the initiator po­
tassium persulfate at a reaction temperature of 80 ◦ C [12–14]. The re­
action mixture was kept stirring throughout the reaction at a speed of
300 RPM. 64 mL of Millipore water was first bubbled with nitrogen gas
for 20 min. After this, 15 mL of MMA was added under nitrogen atmo­
sphere followed by 0.57 g of potassium persulfate. The solution was then
heated to 80 ◦ C and maintained at this temperature for 40 min for the
completion of the polymerization. After the polymerization reaction, the
colloid was centrifuged and washed 5–6 times using Millipore water and
used. The employed emulsifier-free emulsion polymerization method is
known as a versatile method as the polymerization rate and the polymer
size could be controlled by altering the parameters such as the reaction
temperature, amount of initiator, ionic strength of the aqueous phase,
stirring rate and the amount of monomer [15,16].
2.2. Synthesis of Au NPs
The Au NPs were prepared using a NaBH4 reduction method. In a
typical experiment, 5 mL trisodium citrate dihydrate (Na3C6H5O7, TSC),
0.3 mL poly(sodium 4-styrene sulfonate) (PSSS, MW ca. 70, 000 Da) and
0.3 mL NaBH4 were added into a beaker containing 500 mL Millipore
water. 5 mL HAuCl4 (50 wt% in water, 5 mM) was then added into this
drop wise at a rate of 2 mLmin− 1 while stirring. 3 mL TSC was added into
the Au NP sol formed, immediately after the addition of Au precursor
and the mixture stirred for 5 min. This recipe was modified from our
previous work [17,18] to obtain a homogeneous coverage when
combine with PMMA spheres. The NaBH4 reduction method used to
synthesize Au NPs is a size-tunable method. Altering the concentration
of TSC and PSSS will give rise to particles of different size and shape
[4,12,19,20].
2
Applied Surface Science 569 (2021) 151014
2.3. Synthesis of PMMA@Au core–shell NPs
Au NPs were incorporated onto the surface of PMMA spheres in the
presence of polyethyleneimine (PEI) employed as a linker agent. The
PMMA spheres (10 mL of 4% suspension) and 50 mL of PEI (Fluka, Mw
ca. 60 000–100 000) were added into 1500 mL ultrapure water and
stirred for 1 day. The mixture of PEI-decorated PMMA spheres were then
centrifuged and re-dispersed in de-ionized water. This procedure was
repeated 5–6 times and finally the particles were again re-dispersed in
water and stirred. The PEI-modified PMMA particles were subsequently
added to the Au sol drop wise under stirring. The colloid was then stirred
for a further 2 h and then washed and centrifuged at least 5 times.
2.4. Fabrication of PMMA and PMMA@Au core–shell films
Microscopic glass slides were used as substrates and were cleaned by
ultrasonication in a mixture of 5 : 1 : 1 water : ammonium hydroxide :
hydrogen peroxide solution for 1 h. The substrates were then rinsed with
ultrapure water and dried under nitrogen. The colloidal particles of
PMMA and CS PMMA@Au were then immobilized onto the cleaned
substrates by an evaporation induced self-assembly process [12–14,21].
For this, the prepared hydrophilic glass substrates were placed into the
suspension with a tilt angle of approximately 60◦ . An aluminum block
was introduced as a dry bath heat sink to avoid the fluctuation inside the
oven during deposition of the particles. The evaporation of solvent
enabled the deposition of PMMA@Au MDPC films over the period of 3
days. The films were then allowed to dry completely at room tempera­
ture and examined using scanning electron microscopy (SEM), UV
Spectroscopy and SERS.
2.5. Characterization
A JEOL 2100 transmission electron microscope (TEM) operating at
200 KV was used to collect bright field images of the colloidal particles
and the selected area electron diffraction (SAED) spectra were recorded
to determine the presence of gold in the structure. A Quanta FEG 650
scanning electron microscope (SEM) operating at 6 kV was used to re­
cord SEM images of the films. Zeta potential (ζ–potential) and dynamic
light scattering (DLS) particle size measurements were performed using
a Nano ZS Malvern Zetasizer. The ζ–potential is related to the surface
charge, a property that all materials possess, or acquire, when suspended
in a fluid. It can therefore be used to indicate the stability of colloidal
dispersions. The UV–visible absorption spectra of the colloidal solutions
were measured with an Agilent Technologies 8453 Spectrophotometer
using 1 cm path length quartz cells.
An Ocean Optics UV/visible spectroscopy was used to record the
angle resolved transmission and reflection spectra of the films. Standard
angle-resolved reflectance and transmission measurements provided
information on the PBG and plasmonic resonance effect of the bare
PMMA PC and MDPCs. The Raman spectra were recorded using an InVia
Renishaw Raman microscope operating at room temperature. An argon
ion laser operating at 514.5 nm was used to obtain the Raman spectrum
of MDPC, which was then compared to the Raman spectrum from a bare
PMMA PC. Typically, the system was operated using a spot size of 1 µm,
at a power of 5mW, with signal acquisition times of 30 s.
3. Results and discussion
3.1. Synthesis of PMMA@Au core–shell
This study focusses on the synthesis and characterisation of PMMA
core particles decorated with Au NPs. To the best of our knowledge,
there have been no previous literature reports of gold NPs formed onto
PMMA spheres using PEI as a linker. PMMA@Au CS particles were
synthesised in order to investigate their usefulness in preparing MDPC
for using them as surface enhanced Raman substrates.
S. Kassim et al.
UV–visible absorption spectroscopy was employed to investigate
both the Au NPs and the PMMA@Au colloids for their plasmonic and
combined plasmonic/photonic properties respectively. Metal surface
plasmons arise via the interaction of light with electrons in the surface of
the metallic Au NPs [1,4,22]. Most commonly observed for Au or Ag
NPs, at a specific wavelength of light, collective oscillations of electrons
may be excited via a direct absorption process that often results in the
appearance of intense colours. The particular wavelength of light where
this occurs is strongly dependant on the NP size and shape. A shift to
longer wavelengths of the absorption maximum occurs as the NP size
increases [8]. Here we focus on the use of Au NPs since as noted earlier,
these may be readily prepared and stabilised via surface treatment,
while also being relatively inert. PMMA spheres were then coated with
Au NPs.
The specific issue that was addressed in this work concerned the need
to prepare an outer shell of Au NPs. This required the identification of
suitable chemical linker, in order to attach the Au NPs onto the polymer
core particles which must be used in conjunction with the capping agent
designed to prevent agglomeration. PEI was selected for this purpose.
Accordingly, a method was devised in which a thin PEI shell was
attached to the PMMA particles, which then facilitated attachment of the
Au NPs via rearrangement with the citrate-stabilized Au NPs.
The high affinity of amino groups for Au induces the Au NPs to be
attached to the PEI chains on the surface of PMMA producing nano
islands of Au NPs around PMMA cores, that is, the PMMA@Au CS
composite particles. Ho Youk [23] reported that microspheres having a
net positive charge after protonation of surface amine groups exhibited
excellent adhesion to gold colloids, and this also appears to be the case
here.
The advantage of using PEI as compared to the frequently used silane
coupling agents was threefold. Firstly, the complexity in achieving a
uniform surface coverage using silane coupling agents is avoided when
using PEI. This is because the branches available from each PEI mole­
cule, with multiple –NH2 end groups, are sufficient to achieve complete
surface coverage on the PMMA spheres [4]. Secondly, the use of PEI as a
surface primer results in the PMMA particles being separated electro­
statically by a positive surface charge in the aqueous media.
This also aids complete coverage of each PMMA particle with the Au
NPs. The final advantage of using PEI is that stringent pH control is not
required, unlike when using silane coupling agents. Liz-Marzan’s [3]
group has demonstrated the importance of pH control involved in the
silane coupling process. In our experiments, after PEI treatment, the
particles were washed at least five times with ultrapure water. At this
stage the pH was in the region of 8–9, and at this pH range the PEI
modified PMMA particles are electrostatically separated by their
inherent positive charge. The ζ -potential is also an indicator of the
stability of colloidal dispersions. The magnitude of the ζ - potential in­
dicates the degree of electrostatic repulsion between adjacent, similarly
charged particles in dispersion. For molecules and particles that are
small enough, a high ζ - potential will confer stability, i.e., the solution
or dispersion will resist aggregation. When the potential is small,
attractive forces may exceed this repulsion and the dispersion may
flocculate. Accordingly, colloids with high ζ - potential (negative or
positive) are electrostatically stabilized while colloids with low ζ - po­
tentials tend to coagulate or flocculate.
Table 1 presents the ζ -potentials of the particles employed here at
Table 1
ζ -potential data of colloids at various stages in the preparation of PMMA@Au CS
particles.
Sample ζ -potentials (mV) pH
PMMA − 52.7 4.48
Au sol − 34.2 7.07
PMMA@PEI +54.5 7.50
PMMA@Au − 42.1 6.92
3
Applied Surface Science 569 (2021) 151014
different stages of their preparation. The PMMA surfaces before PEI
treatment show a negative ζ -potential (− 52.7 mV) and the PEI modi­
fication resulted in a change in its ζ -potential to + 54.5 mV as expected
due to the positive charge arising from the PEI layer. The as-prepared
citrate-stabilized Au NPs show a negative ζ -potential (− 34.2 mV),
clearly indicating the difference in surface potentials. The PMMA@Au
CS particles show a ζ -potential value of − 42.1 mV. The high negative
potential observed for the CS particles as compared to neat Au NPs could
arise for three possible reasons: (i) that all the PMMA-PEI surface amine
groups have been used up for Au NP linkages, (ii) that the possible tri­
sodium citrate chelation to Au NPs through two carboxylate groups may
be broken, and those broken carboxyl groups may be dangling on the
particle surface causing a high negative potential, and (iii) the uncoated
surface of the PMMA renders its share of negative ζ -potential. Obser­
vation made using TEM observation suggests that the latter applies,
Fig. 1showing the presence of uncoated areas. The Au NPS are observed
as islands on PMMA spheres instead of the formation of continuous
shells, although we may still refer to this as a ‘shell’ in the context of this
paper.
Fig. 1 confirms the incorporation of Au NPs onto the surface of the
PMMA particles. The determination of particle size from TEM images
(ESI 2) show that the Au NPs have a size distribution in the range of
2–16 nm with an average size of ~ 8 nm with a standard deviation of
0.45 nm. The DLS particle size distribution (Fig. 2a) shows that the Au
NPs are in the size range of 5–50 nm with an average size of ~ 10 nm.
The DLS size distribution indicates the nanoparticles may be aggregated
in the solution which is expected for nanoparticles of size around or
below 10 nm. The slight distortion of the spherical shape of these par­
ticles observed is due to the long-time exposure of the high energy
electron beam causing charging [24]. Although not quantitatively
determined, it is clear from the TEM images that the formation of islands
of Au NPs on PMMA surface increases the nanoscopic surface roughness
as compared to unmodified PMMA spheres [25]. It can also be seen that
the Au NPs are attached homogenously onto the surface of all PMMA
particles as islands. The SAED pattern of the PMMA@Au CS NPs is
presented in ESI 2.
Fig. 2b presents the UV–visible absorption spectra of an aqueous
suspension of PMMA@Au CS particles and Au NPs (517 nm). In the case
of PMMA@Au CS particles, as the attached Au NPs grew and merged,
the SPR systematically shifted, consistent with previous studies [22].
PMMA spheres decorated with Au NPs show a less intense absorption
peak. For the Au NPs decorated PMMA spheres, the SPR peak shifts to
higher wavelengths (red shift) to approximately ~ 540 nm. The slight
red shift of the plasmonic bands occurring for the CS particles compared
to that of the bare Au NPs may be attributed to i) the change in the
dielectric environment of the Au NPs, and/or ii) owing to the possibility
that some Au NPs are sufficiently close to each other so as to effectively
alter their size and hence the position of the SPR. Almost similar onset of
the plasmonic absorption band for the CS particles to that of Au NPs
suggests that the Au NPs on PMMA are decorated with a wide size range
where many of the NPs are aggregated on the PMMA surface to form
effectively larger Au structures, hence effectively red shifting the plas­
monic absorption.
3.2. Fabrication of PMMA@Au PC films
PMMA@Au CS NPs were deposited on the cleaned glass substrates by
controlled evaporation at 60 ◦ C. As shown in Fig. 3b, the PMMA@Au
MDPC film exhibited brilliant colours that change with the angle of
observation, as expected for PCs.
3.3. Optical properties of the PMMA@Au MDPC films
In order to investigate the optical properties of PMMA@Au MDPC
films, reflection measurements at various angles of incidence were
carried out using films made from both bare PMMA and PMMA@Au
S. Kassim et al.
Fig. 1. TEM images of PMMA@Au CS NPs at different magnifications (a – c) and a high-resolution TEM image of a PMMA@Au CS particle showing crystalline lattice
planes in Au NPs (d).
particles. Fig. 4a and 4b show normalised reflectance spectra of a
PMMA@Au MDPC film recorded at incidence angles between 10◦ to 40◦
and 45◦ to 75◦ , respectively. The reflectance spectrum measured at an
incident angle θ of 10◦ shows a broad band centred at 964 nm and shows
an angle-dependent blue shift with increasing angle of incidence up to
75◦ . This observation is consistent with the expected behaviour for a PC
in terms of the Bragg-Snell relationship. By altering the angle of inci­
dence (θ), the effective refractive index (ηeff) and the inter-planar
spacing (d) can be determined by the following equation [26]:
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
nλ = 2d (η2 ef f − sin2 θ) (1)
The correlation with the Bragg-Snell relationship is further
confirmed by fitting the data points obtained to a plot of the square of
the wavelength maximum (λ2max) for the photonic stop bands recorded
at various angles of incidence, θ, against sin2θ. The linear fit shown in
Fig. 3c is in complete agreement with the Bragg-Snell relationship. Using
the plot shown in Fig. 3c, ηeff can be calculated, and was found to have
increased from 1.43 to 1.51. The analysis of the data suggests that some
shrinkage of the spheres has resulted during the processing, from ca.
415 nm to 393 nm. This shrinkage could result in a slight densification of
the PMMA particles, leading to an increase in the refractive index of said
particles, and a consequent increase in the effective refractive index.
Therefore, Au NPs have less influence on the ηeff of the formed MDPCs.
The influence of the Au NPs on the optical properties of the MDPC
was then evaluated by obtaining the reflection and transmission spectra
of bare PMMA opal and PMMA@Au MDPC at an incidence angle of 10◦ ,
4
Applied Surface Science 569 (2021) 151014
Fig. 4, (a) and (b). The obvious changes in the spectra were, (i) a
considerable reduction in the reflected spectral intensity, and (ii) the
broadening of the stop band as compared to the PCs made from uncoated
PMMA spheres of similar size. Our findings suggest that the reduction in
the reflected intensity is attributable to the metal plasmonic absorption
and scattering. The Bragg peak wavelength for PMMA bare opal is
located at ~ 964 nm. The Au loading did not create any significant
change to the Bragg peak wavelength. However, the percentage reflec­
tance for the PMMA@Au MDPC film is reduced to < 10%, which is due
to the voids being partly infilled with Au NPs that act as plasmonic
absorbance and scattering centres.
Fig. 4(b) shows a comparison of transmission spectra at 10◦ inci­
dence between a PMMA bare opal and a PMMA@Au MDPC film. The
MDPC film shows no transmission at 600 nm likely due to the Au NPs
absorbing via their SPRs.
3.4. Surface-enhanced Raman spectroscopy effects
SERS experiments were conducted to explore the possible enhance­
ment of scattering intensity resulting from the Au NPs employed as part
of the architecture of the materials. A 514.5 nm laser excitation was used
to analyse the enhancement of a target analyte 4-aminothiophenol (4-
ATP). Fig. 5a is a typical Raman spectrum recorded from a bare PMMA
opal film without Au NPs. This ‘control’ sample showed no evidence of
any SERS enhancement effect, possibly because the film was flat and
smooth and hence would not be expected to have a plasmon resonance
near the wavelength of the laser line [27]. This spectrum shows a
S. Kassim et al.
Fig. 2. DLS particle size distribution by number of a representative batch of AuNPs (a), UV/Vis extinction spectra of PMMA@Au CS and Au NPs (b), the PMMA@Au
MDPC film showing distinct colour to the naked eye indicating the photonic crystal behaviour of the prepared PC film (c), and the close packed arrangement of the
PMMA@Au MDPC film as revealed by SEM cross section image (d). The SEM image again reveals the level of Au coating on the PMMA core particles.
number of features which are consistent with the structure of the PMMA
(ESI 4) [28]. Fig. 5b is then a Raman spectrum recorded from the MDPC
sample. Clearly some PMMA features are apparent as summarized in ESI
4: Table 1, but from a preliminary comparison of scattering intensities
with Fig. 5a, the spectrum shown in Fig. 5b shows some slight
enhancement in intensity. However, the enhancement factor for Fig. 5b
is quite low, perhaps only between 3x and 5x, as compared to the
‘normal’ Raman spectrum in Fig. 5a. This might be due to a lack of
coupling of the incident radiation to the plasmon associated with the Au
structure, which might be structural, or electronic in nature. Further­
more, the ‘simpler’ spectrum (fewer bands) observed for Fig. 5b in
comparison to that shown in Fig. 5a is reminiscent of the type of SERS
spectra reported previously, where only certain vibrational modes
appear in the SER spectrum- i.e., the SERS process demonstrates the
operation of some new ‘selection rules’ [29]. In the Phatangare work
[30], the prominent peaks at around 1080 cm− 1 and 1590 cm− 1 due to
4–ATP have appeared only at 10-4 M concentration. The continuous
decrease in the gap between the nanometallic and increase in the
decoration density of Ag NPs with the increase in the electron fluence
yielded high values of enhancement factors, which enabled detection of
4–ATP even at 10− 8 M concentration. The same trend was also observed
in the work of Zhang et al. [31] (ESI 3). It is well-known that the
magnitude of the SERS effect is affected by the wavelength of the laser
used and the SPR wavelength of the metal NPs, and thus some matching
of the laser wavelength with the metal compositions is desirable. In the
case of Au this is complicated by the presence of the inter-band transi­
tion [32]. Wavelength-scanned SERS experiments by Schatz et al. [33]
have shown that for a fixed Raman shift the surface plasmon wavelength
should be roughly halfway between the incident laser wavelength and
the Stokes shifted wavelength. They found that the SERS enhancement
factor increases as the LSPR and laser wavelength are simultaneously
5
Applied Surface Science 569 (2021) 151014
shifted toward the red (up to a maximum wavelength of 785 nm).
Our data show that the enhancement in intensity of the Raman
spectrum from the PMMA@Au MDPC at the laser wavelength of 514.5
nm, if indeed there is any, is quite weak. Where gold has been used
previously for SERS experiments this phenomenon has been attributed
to the presence of the inter-band transition near the green region of the
spectrum for Au [34]. Indeed, it has been found that efficient SERS from
gold can only be observed when exciting with longer wavelength radi­
ation, below the energy of the inter-band transition. Thus, it is suggested
that experiments should be repeated using longer wavelength exciting
lines in order to fully test this hypothesis.
Between the Rayleigh line scattering at 514.5 nm and the Raman
scattering at 542.5 nm there is a shift equivalent to 28 nm in wavelength.
Since as shown in Fig. 3(c) the first order Bragg reflections for the ma­
terial in question lie in a wavelength range which is higher than either
the Rayleigh line or the Raman scattering, we cannot use the first order
Bragg reflections to influence these wavelengths. However, we can use
the second order Bragg reflections. Accordingly, we now apply the
second order Bragg-Snell equation to calculate the difference between
the angles at which the Bragg peak associated with each wavelength
would be expected.
Taking the composite refractive index ηeff as 1.51 and assuming a
layer spacing of 393 nm based on the diameter of the PMMA spheres, we
obtain for the two wavelengths concerned:
( )1/2
514.5nm = 2 × 393nm (1.51)2 − sin2 θ1 (2)
( )1/2
542.5nm = 2 × 393nm (1.51)2 − sin2 θ2 (3)
From these two equations the values of θ1 and θ2 are found to be
48.80◦ and 37.74◦ respectively. Thus, the angular separation between the
exciting line (Rayleigh scattering) and the Raman line Bragg peaks is
S. Kassim et al. Applied Surface Science 569 (2021) 151014

Fig. 3. Angle-resolved reflectance spectra of PMMA@Au MDPC obtained at incident angles of 10◦ to 40◦ (a) and 45 to 75◦ (b) with respect to the normal to the
surface. Spectra were shifted in the Y axis for clarity. A fit of the reflectance data to the Bragg-Snell equation. From this plot the ηeff of the composite was determined
to have increased from 1.43 to 1.51 (c).

estimated to be 11.06◦ . Therefore, it may be seen that an experiment approach of surfactant-free emulsion polymerisation and self-assembly
could be devised where the Raman scattered light could be preferen­ method, substituting water as dispersion medium, and poly­
tially reflected from the sample as compared to the Rayleigh line. ethyleneimine (PEI) as linking agent for other harmful chemicals that
However, in order to maximize these effects, it would be better to are hazardous to the environment, making the material a generally more
properly design the material such that the first order Bragg reflections lie sustainable and environment-friendly SERS substrate alternative while
in the wavelength range covered by the Rayleigh line and the Raman also being easier, faster and more cost-effective. Although the focus of
scattering. this paper aims at the synthesis of PMMA@Au PC film, a brief consid­
eration on the prospects of this material as a SERS substrate will be
touched on in this section.
3.5. Potential applications of PMMA@Au MDPC thin film
In bioanalytical sensing, SERS bring about advantages over other
types of assays in molecular detection. Raman signal enhancement is
As noted previously, SERS is an exceptional vibrational spectroscopic
essentially built into the assay, easing detection of very low concentra­
technique for the characterisation of minute molecule bound near
tion. Easy distinction of different molecules via Raman peaks also give
plasmonic surfaces. It shows significant promise in biological and
way to multiplexing. One of the advantages in PMMA@Au PC film is its
chemical applications as it overcomes the sensitivity and selectivity is­
charges. This factor allows for physisorption, shortening the proximity
sues previously present in Raman spectroscopy while maintaining the
between the analyte and surface, thus strengthening enhancement of
characteristic advantages such as its simplicity, relative low cost, and
Raman signal. The material can therefore be integrated into SERS
rapid analysis time [35,36].
nanotag assays as signal enhancement element [38].
Among the challenges of SERS spectroscopy in industrial applica­
The ability of SERS to detect small molecules of minimal concen­
tions are the reproducibility and uniformity in localised SPR and SERS
tration made it well suited for food regulation and public health, namely
effects. Given Au NPs give rise to more reproducible signal intensities
monitoring certain components in food. There exist dangerous in­
[37] while the copolymerisation of methyl methacrylate and styrene
gredients in foods, such as certain antimicrobials, colorants, and ille­
allows for versatility and high tunability in morphology and composi­
gally added adulterants such as melamine [39,40]. Food additives
tion, as well as being relatively cheap, this research sought to offer a
require constant testing to ensure the levels of trace contaminants within
potential solution to the aforementioned issues by the fabrication of
food is safe for consumption. In a study by [41], The material syn­
novel PMMA@Au in 3D MDPC thin film structure. This could not only
thesised in this study should give an edge in toxicity assessment due to
lessen a cause of said problems; aggregation of NPs, but also possibly
the relatively inert property of Au NPs and the good stability of the
ease production process, minimise production costs, while ensuring a
overall substrate.
medium of intense plasmonic cloud.
Environmental monitoring of organic pollutants in soil and water,
The synthesis of PMMA@Au PC film is centred around a greener

6
S. Kassim et al.
Fig. 4. Reflection spectra of PMMA bare opal and PMMA@Au film(a) and
transmission spectra of PMMA bare opal and PMMA@Au MDPC film(b).
Fig. 5. Raman spectra of 4-ATP on PMMA bare opal film (a) and 4-ATP on PMMA@Au MDPC film (b). The excitation wavelength used was λ = 514.5 nm, using a
spot size of 1 µm diameter, with a laser power of 5mW and accumulation time of 30 s.
7
Applied Surface Science 569 (2021) 151014
rural and urban areas, that could leak into food supply and wreak havoc
in the ecosystem should be performed recurrently for public safety.
Moreover, much of these ecological contaminants are associated with
elevated cancer rates [42]. SEM cross section imaging revealed
PMMA@Au MDPC film possesses uniform close packed arrangement,
contrary to the challenge presented for many of pollutant detections:
poor Raman cross section that prompts the need for special enhance­
ment materials [43].
Raman spectroscopy can provide information about the chemical
structure and identity of compounds down to single molecular level
[44], is non-destructive, and does not require careful sample preparation
that is necessary with alternative methods, such as infrared spectros­
copy. The availability of portable detection devices, such as the hand­
held Raman spectrometers, made advancement in SERS technology
exceedingly desirable for law enforcement [45]. The fabricated
PMMA@Au film could be a favourable candidate for forensic analysis of
biological (blood, saliva, etc.) or synthetic (gun powder, narcotic, etc.)
materials because it possesses high stability, versatile SPR tunability,
and Au NPs surfaces that are more easily functionalized for bio­
conjugation [37].
Time is of the essence when it comes to disease detection. The quick
and accurate detection window of SERS bring excellent prospects,
particularly when it comes to a pressing novel human virus infection
outbreak that has yet a vaccine [46] or cancer diagnosis [47]. SERS
PMMA@Au, with a considerably short production time, could be
incorporated into plasmonic biosensors and point-of-care devices in
testing and monitoring of diseases. Additionally, the Au NPs surfaces are
relatively safe, non-cytotoxic, and showed good biocompatibility [48]
encouraging further study on in vivo applications [49,50].
To summarise, the main advantages to the fabrication of the
PMMA@Au in 3D MDPC thin film is that it is vastly modifiable and has
great variability in photonic capabilities because of its high tunability. In
addition, the photonic band gap associated with the materials syn­
thesised here could, in principle, be used to enhance the detection of the
Raman scattering by spatially separating this light from the Rayleigh
line as shown here. Due to its relative novelty, more studies on the
factors affecting the SERS enhancement could be explored to gauge the
potential of this material across a myriad of different fields.
S. Kassim et al.
4. Conclusions
We have established a simple reproducible method for the synthesis
of highly monodispersed PMMA@Au CS particles using a linker agent
which has not been previously employed for PMMA particle decoration.
We were able to use these particles to assemble into a reasonably high
quality MDPC films. The optical data revealed a slight increase in
effective refractive index along with a decrease of the particles size in
the composite material. The angle resolved optical reflectance spectra of
this MDPC material fabricated by assembling dielectric@metal CS par­
ticles showed a good agreement with the Bragg–Snell correlation sug­
gesting their good PC properties. Their reflection and transmission
spectra further showed that they have good visible light scattering/
concentration/dispersion capability with very little visible light trans­
mission/reflection. Preliminary Raman scattering investigation showed
a threefold increase of the Raman signal with the MDPC as compared to
the bare PMMA PC, although considerably more investigation is
required to understand their potential to be used as SERS substrates.
CRediT authorship contribution statement
Syara Kassim: Investigation, Data curation, Formal analysis, Meth­
odology. Sibu C. Padmanabhan: Conceptualization, Methodology,
Supervision, Writing – review & editing. Martyn E. Pemble: Concep­
tualization, Resources, Project administration, Supervision, Writing –
review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The authors would like to thank the Ministry of Education of
Malaysia for Fundamental Research Grant Scheme (FRGS) 59630
(FRGS/1/2020/STG05/UMT/02/4) and Universiti Malaysia Ter­
engganu, SFI grants (PI Grant No. 07/NI.1/I787 and AMBER SFI Centre
grant 12/RC/2278-P2) for funding this research. We also would like to
acknowledge the Electron Microscopy facilities in the Biosciences
Institute, University College Cork and EMAF, Tyndall National Institute
for assistance in preparing and imaging materials for this research.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.apsusc.2021.151014.
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