Sensors & Actuators: B.

Chemical 401 (2024) 134959

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Sensors and Actuators: B. Chemical

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

Nanoplasmonic Au:CuO thin films functionalized with APTES to enhance

the sensitivity of gas sensors
Manuela Proença a, Marco S. Rodrigues a, Cacilda Moura a, Ana V. Machado b, Joel Borges a, c, *,
Filipe Vaz a, c
a
Physics Center of Minho and Porto Universities (CF-UM-UP), University of Minho, Campus de Azurém, 4800-058 Guimarães, Portugal
b
Instituto de Polímeros e Compósitos, Universidade do Minho, Campus de Azurém, 4800-058 Guimarães, Portugal
c
LaPMET–Laboratory of Physics for Materials and Emergent Technologies, University of Minho, Braga, Portugal

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

Keywords: Carbon monoxide (CO) is a highly flammable and toxic gas to humans and animals, that’s why its detection and
Au Nanoparticles monitoring are crucial. A promising technique to develop a robust and cheap gas sensor, operating at room
CuO matrix temperature, is Localized Surface Plasmon Resonance (LSPR) sensing. However, LSPR sensing of inorganic gas
High-resolution LSPR spectroscopy
molecules, such as CO, is challenging due to their extremely small differences in refractive indices. In this work, a
Optical gas sensing
nanoplasmonic thin film, composed of Au NPs semi-embedded in a CuO matrix (Au:CuO) was functionalized
APTES
Self-assembled monolayers with a silane self-assembled monolayer (APTES molecule) that enhanced the sensitivity of the film to a mixture of
CO (50 ppm) in Argon. Three different concentrations of APTES (0.1 %, 1.0 %, and 5.0 %) were silanized on Au:
CuO thin film surface, and all the functionalized Au:CuO thin films showed better sensing results than bare Au:
CuO thin film. The functionalized Au:CuO thin film with 0.1 % of APTES revealed the best sensing character­
istics. Its sensitivity was almost 3 times higher than that of the unmodified Au:CuO thin film. Au:CuO thin films
functionalized with APTES are potentially relevant to developing sensitive and selective LSPR sensors for the
detection of inorganic gases such as CO, in harsh environments.

1. Introduction TiO2 [12,13], and CuO [14–16] are preferred, due to their simple
fabrication, low cost, nano-size, and superior response. However, those
The development of gas sensors with high stability, sensitivity, and conductometric-based gas sensors have certain limitations. They need
selectivity for carbon monoxide (CO) is critically required because CO is electrical contacts to measure the change in conductance, which in­
a colorless and odorless gas, highly flammable and toxic [1,2]. It is troduces noise and additional resistance. Therefore, to achieve greater
mainly produced by the incomplete combustion of carbon-based fuels sensitivity, they require a high operating temperature (150–400 ◦ C),
used in car engines, gas fires, domestic appliances, etc., and it is one of which leads to high energy consumption, risks of explosion when
the main components of atmospheric environmental gaseous pollutants, detecting flammable or explosive analytes and long-term stability
which represents a serious threat to the ecological environment. problems, since the fusion of the grain boundaries of semiconductors
Furthermore, CO is highly poisonous to humans and animals, since might occur at high temperatures [11,17,18]. Furthermore, they have a
haemoglobin has 200 times more affinity for CO as compared to oxygen limited life expectancy due to the deterioration of the gas-sensitive
[3]. According to the World Health Organization (WHO), the acceptable materials in environments with high gas concentration and do not
limit of CO gas concentration and duration in the atmosphere is 9 ppm function in low-oxygen environments [19].
for 8 h and 26 ppm for 1 h without any harmful effect [4]. In the past decades, fundamental progress has been made towards
The most common sensitive materials used to produce current developing room-temperature realizable gas sensors [20–22]. The best
commercial CO gas sensors are metal oxide semiconductors, in which alternatives include the optical sensors, which have some advantages
the variation of resistance upon analyte uptake is measured [2,5]. over conventional gas sensors, owing to their stability due to their low
Generally, metal oxide semiconductors such as ZnO [6,7], SnO2 [8–11], output drift, wide dynamic range, high sensitivity and long lifetime,

* Corresponding author at: Physics Center of Minho and Porto Universities (CF-UM-UP), University of Minho, Campus de Azurém, 4800-058 Guimarães, Portugal.
E-mail address: joelborges@fisica.uminho.pt (J. Borges).

https://doi.org/10.1016/j.snb.2023.134959
Received 8 August 2023; Received in revised form 2 November 2023; Accepted 9 November 2023
Available online 10 November 2023
0925-4005/© 2023 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/).
M. Proença et al. Sensors and Actuators: B. Chemical 401 (2024) 134959

since the operating principle is only related to the physical property of film and for APTES-functionalized thin films, and their LSPR response
the target gas and does not need any chemical reaction between the was compared and discussed.
target gas molecules and the optical sensor, while the detection system is
resistant to electrical interference [23–25]. Recently, localized surface 2. Experimental details
plasmon resonance (LSPR) of noble metal nanoparticles (NPs) has been
extensively studied to detect biomolecules, such as proteins [26,27], and 2.1. Production and optimization of the Au:CuO thin films
gases [28,29], by using its sensitivity toward environmental refractive
index (RI) changes. LSPR occurs when the frequency of incident light Nanocomposite thin films composed of gold dispersed in a copper
causes a collective oscillation of the electron cloud of the metal NP, near oxide matrix (Au:CuO) were deposited by reactive DC magnetron
the interface with the dielectric environment. At the resonance fre­ sputtering onto polished SiO2 (fused silica) and NaCl substrates for
quency, strong light absorption and scattering are observed [30–32]. transmission electron microscopy (TEM) analysis. The substrates were
Noble metal particles such as gold and silver, are the metals of choice for placed in a grounded hexagonal substrate holder rotating at 18 rpm, in
plasmonic applications since they exhibit strong LSPR bands at visible the center of the deposition chamber, at 7 cm from a rectangular Cu
frequencies. Although Ag NPs present the sharpest and strongest bands target (200 ×100 ×6 mm3, 99.99 % purity). In the preferential erosion
among all metals, leading to higher sensitivity factors than Au, Au NPs zone of the target, Au pellets with a total surface area of 1200 mm2 and
are more frequently selected for sensing applications due to their 0.5 mm thick were placed symmetrically. The deposition was performed
chemical stability and resistance to oxidation [33,34]. Besides the type after a vacuum of approximately 3.8 × 10− 4 Pa was reached inside the
of metal, the optical response depends also on the size, shape, and dis­ chamber. The target was sputtered with a current density of 50 A.m− 2
tribution of the NPs, and the nature of the local surrounding medium. for 30 s, in a plasma composed of Ar (flow of 15 sccm, partial pressure of
LSPR band is hence highly sensitive to the RI change in the local 2.4 × 10− 1 Pa) and O2 (flow of 14 sccm, partial pressure of 2.24 × 10− 1
dielectric environment in the range of a few nanometers away from the Pa). Then, an annealing treatment (700 ◦ C for 5 h) was applied to induce
NP surface (exponential decay). So, when target gases flow over the the formation and growth of the NPs throughout the CuO matrix and
nanostructure, the RI changes, thus shifting the LSPR band. This shift thus obtain enhanced LSPR responses. The heating ramp used was 5 ºC/
may be used as an indicator of the LSPR sensor response [35–37]. min, from room temperature to the chosen temperature. The samples
In recent years, nanocomposite materials based on plasmonic NPs cooled down freely inside the furnace, before reaching room tempera­
and metal oxides (e.g. CuO, TiO2, ZnO) have been widely used for gas ture. This method has been optimized and it is described in more detail
detection [38–42]. Beyond metal oxides being optically transparent in elsewhere [54,55].
the visible range, they are considered excellent “host matrixes”, As discussed in a previous study [56], the Au:CuO thin film surface is
providing stability and protection to the NPs, thus preventing optical covered by hydrocarbons and the Au NPs near the film’s surface are
properties degradation [43]. Moreover, its wide surface area also in­ surrounded by a CuO layer. Therefore, to remove those top layers and
creases its potential to be functionalized with organic molecules. Among partially expose the Au NPs to the atmosphere, maximizing the nano­
different possibilities for host metal-oxide matrices, copper (II) oxide plasmonic film’s sensitivity, thin films were subjected to an argon (Ar)
(CuO) was initially selected for the development of a reusable LSPR gas plasma treatment [44]. The Ar plasma (80 Pa) was ignited with the
sensor for CO detection, since CuO has been reported to have good power of the RF generator set to 15 W at room temperature for 5 min in a
sensitivity to CO gas at room temperature [42]. Low-Pressure Plasma Cleaner equipment by Diener Electronic (Zepto
The LSPR based optical gas sensors have several advantages, Model). The plasma treatment time was optimized in a previous work
including simplicity, room temperature operation, fast and reversible [44].
response, portability, wide dynamic range, etc. Nevertheless, LSPR
sensing of inorganic gas molecules (e.g., H2, N2, O2, CO2, CO) is chal­ 2.2. Functionalization of Au:CuO thin films with APTES
lenging due to their extremely small differences in RIs (as small as ~5 ×
10–4 RI units) [44,45]. As the change in the RI of the sensing layer on The functionalization of Au:CuO thin films with APTES was carried
exposure to target gas can be directly related to the concentration of gas out following the methodology reported in the literature [52,57]. As
molecules interacting with it, functionalizing plasmonic nanostructures shown in Fig. 1, before an APTES monolayer can be formed, the thin
with a material that promotes the adsorption of the analyte is a gener­ films must go through a hydroxylation step to activate the surface with
alizable strategy for enhancing the sensor response [45–49]. increased hydroxyl groups (-OH) [57]. Thus, the Au:CuO thin films were
In recent years, researchers have discovered that the organic func­ treated with oxygen plasma (80 Pa, 30 W) for 1 min to add hydroxyl
tionalization of nanostructures’ surfaces with self-assembled mono­ groups to the surface. After that, three APTES solutions (APTES, from
layers (SAMs) is a tool for building efficient sensors. For example, 3- Sigma-Aldrich, St. Louis, MO, USA) with different concentrations were
aminopropyltrimethoxysilane (APTMS) can significantly improve the prepared (0.1 %, 1.0 %, and 5.0 % (v/v)) in absolute ethanol (anhydrous
selectivity of the nanoplasmonic sensor (Au@SiO2) to VOC gas species ethanol, 99.8%). The hydroxylated Au:CuO films were immersed into
[50] and enhance the sensitivity to SO2 [29]. Interestingly, Cueto-Díaz the APTES solutions and kept under stirring for 30 min at 50˚C. After
et al. [51] used bare SiO2 NPs modified with 3-aminopropyltriethoxysi­ APTES silanization on thin films, the samples were rinsed with absolute
lane (APTES) for CO2 sequestration enhancement. APTES was also used ethanol and dried in air.
to enhance the sensors’ response to 2-butanone and ammonia [52,53].
These studies provide a new method for the organic functionalization of 2.3. Characterization analysis
plasmonic nanostructures, but, to our best knowledge, the targeted
detection of CO has not been reported. 2.3.1. Nanostructure of the thin films by scanning transmission electron
In this work, a nanoplasmonic thin film composed of Au NPs semi- microscopy
embedded in a CuO matrix (Au:CuO) was functionalized with a silane The morphology of the nanoplasmonic Au:CuO thin films was stud­
self-assembled monolayer (APTES) to further enhance the CO sensitivity ied by transmission electron microscopy (TEM). For this purpose, the
and selectivity of the LSPR sensor. For that, the surface of Au:CuO thin samples were prepared by depositing and annealing the films in NaCl,
films were functionalized with different APTES concentrations and and then by immersing the NaCl substrates with the Au:CuO thin films,
investigated using several characterization techniques such as atomic in distilled water. After the dissolution of the substrate, the floating layer
force microscopy (AFM), Fourier Transform Infrared (FTIR) and Raman composed of the thin film was transferred onto a nickel grid (400 mesh)
spectroscopy. CO gas sensitivity tests were performed using a custom- with carbon film. The analysis of the size of the NPs embedded in the
made high-resolution LSPR spectroscopy system for bare Au:CuO thin film and its composition was performed in a JEOL JEM 2100 working at

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Fig. 1. Schematic representation (not to scale) of functionalization of Au:CuO thin films with APTES.

200 kV, with STEM (scanning TEM) mode and EDX (energy dispersive x- gaseous atmosphere that surrounds the sample was switched between
ray spectroscopy). The NPs’ size, nearest neighbor (N.N.) distance, and either pure Helium (He) and a mixture of 50 ppm CO in Ar (50 ppm CO:
aspect ratio distributions were determined by a MATLAB algorithm. Ar), every 120 s for several cycles, at room temperature, while LSPR
transmittance spectra were monitored in real-time. The valves of the
2.3.2. Surface topography of APTES-functionalized thin film by atomic system were adjusted so that the partial pressure of each gas was
force microscopy approximately the same (2.6 ×104 Pa). He/CO:Ar gas cycles were per­
After functionalization of Au:CuO thin films with APTES, the surface formed to ensure the reproducibility of the sensing procedure. A total
topography of the bare and APTES-functionalized films was observed by number of 60 transmittance spectra were acquired for each gaseous
Atomic force microscopy (AFM). AFM experiments were carried out atmosphere, by a modular spectrometer from Ocean Optics (HR4000
with a high-resolution Nano-Observer AFM microscope, from Concept Model). The software NANOPTICS [58] was then used to analyze the
Scientific Instruments. A SPM probe model FORTA (Si, n-type; reso­ LSPR band spectra. It locates the wavelength peak position (minimum
nance frequency 43–81 kHz; spring constant 0.6–3.7 N/m; tip radium < transmittance peak at the LSPR band) over time and calculates the
10 nm) was used. The images, having a scan size of 10 × 10 µm2, were average wavelength shift between the different gaseous atmospheres
collected at a scan speed of 1 line/s with a resolution of 1024 × 1024 px. and the signal-to-noise ratio (SNR) of each gas test.
The freely available software Gwyddion (v. 2.62) was used to analyze
the topography AFM data. 3. Results

2.3.3. Chemical analysis by Fourier transform infrared spectroscopy and The NPs’ distribution of the Au:CuO films (deposited onto NaCl
Raman spectroscopy substrates) was studied by STEM imaging in dark field mode (Fig. 2).
The surface chemistry of APTES-functionalized Au-CuO thin films, The presence of a significant number of NPs (white structures) in the
was evaluated by Fourier Transform Infrared Spectroscopy in Attenu­ CuO matrix is noticeable in the STEM images with different magnifica­
ated Total Reflectance (FTIR-ATR) mode, using a Jasco FT-IR4100 tions (Fig. 2(a), (b) and (c)). The results for NPs’ size, nearest neighbor
equipped with a Specac MkII Golden Gate single reflection ZnSe ATR (N.N.) distance, and aspect ratio distributions were obtained by quan­
crystal. ATR-FTIR spectra were recorded with a nominal resolution of tifying the TEM image from Fig. 2(a) and are plotted in histograms of
8 cm− 1 for a total of 64 scans. Fig. 2(d), (e) and (f), respectively. The average Au NPs’ size is 107 nm,
The chemical modification of the film’s surface after functionaliza­ as displayed in Fig. 2(d). Their sizes range from 50 nm to 170 nm,
tion with APTES was also evaluated by Raman spectroscopy. Raman meaning that the scattering efficiency of the nanoparticles dispersed in
spectroscopy was performed with a LabRAM HR Evolution Raman the CuO matrix is high, and thus it is expected that the transmittance
spectrometer (Horiba Scientific) coupled with a Horiba Scientific’s minimum, which corresponds to extinction maximum, is mostly due to
Labspec 6 spectroscopy Suite software for instrument control, data scattering and negligible absorption [59]. The average N.N. distance
acquisition, and processing. The Raman spectra of the samples were (Fig. 2(e)) is about 130 nm, with a broad distribution of distances
acquired with a Laser Quantum Torus of 532 nm with a power of (σ = 51), meaning that the probability of enhanced fields due to the
260 µW on the sample and an acquisition time of 60 s presence of hot spots is residual [34]. The average aspect ratio of the NPs
(Fig. 2(f)) is 1.2, which indicates that most of the NPs have shapes close
2.4. CO sensing system to spherical, although some of them have more elongated shapes, as
verified in the zoomed image of Fig. 2(c). In fact, it is well-known that
To check the effects of APTES functionalization on thin film sensor the NPs size and aspect ratio distributions depend on the temperature
performance, the obtained sensing platforms were tested under gases at and the time of annealing treatment used. NPs can grow through
room temperature, in a custom-made high-resolution LSPR spectroscopy different mechanisms. Au nucleation is the first stage and occurs during
system, pumped by a vacuum system, described elsewhere [54]. The the annealing treatment, or even while the film is being deposited. Then,

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M. Proença et al. Sensors and Actuators: B. Chemical 401 (2024) 134959

Fig. 2. Study of the Au NPs distribution of the Au:CuO thin film annealed at 700 ◦ C using a MATLAB algorithm. (a), (b) and (c) dark field STEM micrographs at
different magnifications; NPs distribution histograms for (d) NPs Feret diameter, (e) nearest neighbor distance and (f) aspect ratio.

Fig. 3. Dark field STEM micrographs and STEM-EDX analysis of NPs present in Au:CuO thin film annealed at 700 ◦ C: (pink) Au and (green) Cu EDX maps in the
selected area.

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the enhanced Au diffusion promoted by annealing treatment induces the be attributed to the formation of irregular or disordered APTES multi­
“normal” growth and the formation of small-sized Au NPs. Finally, the layers for higher APTES concentrations, in agreement with the literature
growth of NPs occurs through coalescence (when two NPs merge to form [64,65].
one large one) and/or Ostwald ripening (when small NPs are dissolved, To confirm the presence of APTES on the functionalized thin film,
and the atoms are transferred to larger NPs) [60–62]. Only at higher FTIR spectroscopy was employed. FTIR spectra of APTES-functionalized
annealing temperatures, such as 700 ◦ C (the used annealing tempera­ Au:CuO thin films at different concentrations (0 %- reference - solvent
ture), the Au NPs grow to more well-defined shapes, as shown in Fig. 2 only, 0.1 %, 1.0 %, and 5.0 %) and of the pure APTES solution are shown
(a-c), and this distribution gives rise to a relatively narrow LSPR band in Fig. 5. After functionalization of Au:CuO thin films with APTES, one
associated to higher sensitivities [56]. may notice transmittance bands associated with hydrolyzed APTES film,
To establish the nature of the NPs and their chemical composition, an illustrated by different vibrational modes related to NH2 and CH2, and
elementary chemical characterization by STEM-EDX was performed and SiO bonds [67]. As the APTES concentration increased, the FTIR peaks
the results are displayed in Fig. 3. EDX mapping allowed to establish the indexed to APTES became more intense because of the presence of
chemical nature of the NPs and it was possible to map the presence of thicker layers [65], corroborating with AFM results (Fig. 4(d)).
both Au and Cu, independently. The Au composition map (pink color) The deformation mode around 1390 cm− 1 is assigned to the Si-CH2
shows the Au mainly concentrated in the form of NPs, while the Cu bond [67,68], while 1488 cm− 1 and 1564 cm− 1 related peaks corre­
composition map (green color) shows the Cu dispersed throughout the spond to the NH2 deformation modes of the amine groups [65,67,68],
entire matrix, but also covering the NPs domains. These results which are very strongly hydrogen bonded to the silanol groups to form
corroborate the conclusions of previous studies that predicted that the cyclic structures. The spectral region (2800–3700 cm− 1) is characterized
Au NPs are covered by a nanolayer of CuO [44,56] in the prepared thin by two peaks at 2884 cm− 1 and 2925 cm− 1 assigned to stretching modes
film. By Angle Resolved XPS, ARXPS, it was found that the Au NPs near of CH2 [67,69], and two peaks at 3295 cm− 1 and 3375 cm− 1 related to
the film’s surface are surrounded by a CuO layer estimated to be about the symmetric and asymmetric stretching modes of NH2, respectively
0.2 nm and the thin film presents a sub-nanometric layer (~0.6 nm) of [67,69,70]. Furthermore, the first two peaks are also observed in the
hydrocarbons (HC) covering its surface. Hence, the importance of sample without APTES, most likely from C-H stretching vibration of
removing the CuO top layer and partially exposing the NPs is paramount anhydrous ethanol [71]. A broad band in the region of 3200–3700 cm− 1
to make the nanoplasmonic films more sensitive to the environment (e. can also be noticed in APTES-functionalized Au:CuO thin films, which is
g., for gas molecules detection). associated with the stretching mode of hydrogen in Si-OH groups [67,
Therefore, the different Au:CuO thin films (replicas deposited onto 70]. The absence of bands near 2973 cm− 1 of the CH3 group of pure
quartz substrates) were activated with argon plasma, to partially expose APTES solution, suggests that APTES was completely hydrolyzed [72,
the Au NPs, [44], and then treated with oxygen plasma to add hydroxyl 73].
groups on the surface, just before APTES functionalization. The chemical modification of the Au:CuO thin film’s surface after
The surface topographies of the plasma-treated Au:CuO thin films functionalization with APTES was also evaluated by Raman spectros­
after its functionalization with APTES at different concentrations (0 %- copy. Fig. 6 shows the Raman spectra of the APTES functionalized thin
reference - solvent only, 0.1 %, 1.0 %, and 5.0 %) were observed by AFM films and of the pure APTES solution in the two ranges (a)
and analyzed in the scanning area of 10 × 10 µm2 (Fig. 4(a-d)). The 1100–1800 cm− 1 and (b) 2700–3020 cm− 1, respectively. As verified in
mean roughness (Ra), the root mean square (RMS) and the mean height the FTIR results (Fig. 6), the Raman spectra are more intense for higher
(<height>) are displayed in Fig. 4(e), and the height distribution pro­ APTES concentrations due to the presence of thicker APTES layers, while
files are shown in Fig. a (f). While the Ra is the arithmetic mean devi­ for the lowest APTES concentration, the signal-to-noise-ratio is low to
ation of all points’ roughness profile from a mean line over the distinguish the peaks.
evaluation length, RMS is the average of the measured height deviations In the spectral region of 1100–1800 cm− 1 (Fig. 6(a)), a distinct band
taken within the evaluation length and measured from the mean line appears at 1308 cm− 1 and it is assigned to the stretching vibration of
[63]. CH2 [74,75], whereas those at 1413 cm− 1 and 1454 cm− 1 link to the
The AFM scans on the surface of bare thin film (Fig. 4(a)), showed the presence of C-N [74] and CH2 [74,75] scissoring mode bonded to Si
presence of many hills and fewer valleys (mean roughness (Sa) = 4.8 nm atom (Si single bond CH2) respectively, proving the presence of silane
and RMS roughness (Sq)= 6.2 nm), which certainly is related to the molecules belonging to APTES attached at the surface of Au:CuO thin
presence of Au NPs and it is in agreement with previous results [44]. films. Two broad bands at 2890 cm− 1 and 2920 cm− 1 are also noticed
However, after the thin film functionalization with an APTES concen­ for the functionalized thin film with 1.0 % and 5.0 % of APTES (Fig. 6
tration of 0.1 % (Fig. 4(b)), the roughness and height parameters (b)) and are assigned to the symmetric and asymmetric stretching modes
changed. The mean and the RMS roughness decreased slightly to 3.5 and of CH2 groups of APTES molecules [74]. Once again, these results also
4.1 nm, respectively, while the mean height (<height>) decreased from suggest the success of APTES silanization onto the Au: CuO thin film.
23.4 nm (0 % APTES) to 14.5 nm (0.1 % APTES), as observed in Fig. 4 The efficiency of the APTES–Au:CuO thin film binding was also
(e). Furthermore, the height distribution became narrower for smaller studied through transmittance measurements in the HR-LSPR spectros­
grains (Fig. 4(f)). Such alteration on the thin film surface after APTES copy system [54]. The addition of the APTES to the Au:CuO thin film
silanization suggests that the copper oxide matrix was efficiently func­ surface caused LSPR band shifts towards longer wavelengths, as
tionalized with an APTES monolayer. APTES filled the plan regions observed in the transmittance spectra of Fig. 7. These LSPR redshifts are
between the NPs, leading to a decrease in roughness and height distri­ related to an increase in the RI of the region surrounding the NPs,
bution parameters. induced by APTES molecules that are bound to the thin film surface [29,
With increasing APTES concentration to 1.0 % and 5.0 % (Fig. 4(c) 76,77]. Moreover, the results showed that these LSPR band shifts were
and (d), respectively), the surface became increasingly heterogeneous. greater as APTES concentration increased [78,79]. The LSPR peak
This result was accompanied by a considerable increase in surface wavelength (λmax) of the bare Au:CuO thin film redshifted 2.8 nm,
roughness and mean height for higher APTES concentrations (Fig. 4(e)), 3.8 nm, and 6.4 nm when the film was functionalized with 0.1 %, 1.0 %,
which nicely follows the behavior observed in other concentration and 5.0 % APTES, respectively. Once again, these results, obtained by
studies [64–66]. The measured Ra and RMS roughness values were 14.0 LSPR spectroscopy, suggest that the thin films’ surface was successfully
and 17.4 nm, respectively, and the mean height value was 78.7 nm, for functionalized with the different concentrations of APTES and that
an APTES concentration of 5.0 %. Also, the height distribution became higher APTES concentrations lead to a higher number of APTES layers
broader for higher grains at 5 % APTES (Fig. 4(f)), due to the presence of on the surface of the film.
huge aggregates, as observed in AFM scans (Fig. 4(d)). These results can The gas sensing performance of the APTES-functionalized Au:CuO

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Fig. 4. AFM topography 2D and 3D images (i and ii, respectively) for functionalized Au:CuO with (a) 0 %, (b) 0.1 %, (c) 1.0 % and (d) 5.0 % of APTES. (e) Surface
mean roughness (Sa), root mean square roughness (Sq), mean height (<height>), and (f) height distribution profiles (AFM analysis using the Gwyddion software) of
the Au:CuO thin films as a function of APTES concentration.

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gas are perfectly noticeable. In all the thin films, the LSPR peak shifts to
longer wavelengths during CO:Ar exposure, returning to its initial po­
sition after re-introducing the He gas, due to the higher RI of CO:Ar
mixture relative to He. As observed in Fig. 8, on the right, the average
peak wavelength shifts were, 0.064 ± 0.011 nm (SNR=2.9) for the bare
Au:CuO thin film, and 0.163 ± 0.014 nm (SNR= 6), 0.114 ± 0.017 nm
(SNR= 3), and 0.095 ± 0.005 nm (SNR= 3) for functionalized Au:CuO
thin film with 0.1 %, 1.0 % and 5.0 % of APTES, respectively. Indeed, the
presence of APTES molecules on the thin film and its concentration in­
fluence the gas sensing ability. All functionalized Au:CuO thin films with
APTES showed better sensing results than the bare Au:CuO thin film.
This enhancement may possibly result from the hydrogen-bonding
interaction between the adsorbed CO gas and APTES amino group
[29], which leads to an effective RI much higher than that of the bulk
gas. Noteworthy, is the functionalized Au:CuO thin film with 0.1 % of
Fig. 5. ATR-FTIR spectra of functionalized Au:CuO thin films with 0 %, 0.1 %,
APTES that revealed the best sensing characteristics, possessing a
1.0 %, and 5.0 % of APTES, and of the pure APTES solution.
maximum sensitivity and response to target gas, which is almost a
three-fold increase compared to the bare Au:CuO thin film. Moreover, its
SNR doubled, meaning the sensor’s detection limit may decrease twice.
As aforementioned, the functionalized Au: CuO thin film with 0.1 % of
APTES is probably covered by an APTES monolayer, or a few mono­
layers, covering the areas between the NPs, whereas the functionalized
Au:CuO thin films with higher APTES concentrations were associated to
thicker and irregular APTES multilayers. Since the LSPR band is highly
sensitive to the RI change in the range of a few nanometers away from
the NP surface and its sensitivity decreases with distance, the presence of
a monolayer could be more advantageous than a thicker multilayer that
would greatly increase such distance. Thus, all tested thin films,
including unmodified Au:CuO thin film, showed excellent sensing re­
sults as they can measure extremely small changes in bulk RI, as low as
10− 5RIU [44]. Yet, the functionalized Au: CuO thin film with only 0.1 %
of APTES proved to be the most promising to be further explored as an
LSPR-based gas sensor, namely, to ascertain selectivity and specificity to
other gases.

4. Conclusions

In this paper, it is demonstrated that the gas sensitivity of a nano­

plasmonic thin film, composed of Au NPs semi-embedded in a CuO
matrix (Au:CuO), can be enhanced through its functionalization with a
silane self-assembled monolayer (APTES).
Through surface topography and chemical composition analysis of
the functionalized Au:CuO thin films it was concluded that the thin
films’ surface was successfully functionalized with the different con­
centrations of APTES (0.1 %, 1.0 %, and 5.0 %) and that higher APTES
concentrations lead to thicker APTES layers on the thin film’s surface.
Furthermore, all the APTES-functionalized Au:CuO thin films showed
better sensing results than the bare Au:CuO thin film. However, the
functionalized Au:CuO thin film with 0.1 % of APTES revealed the best
sensing performance, possessing a maximum sensitivity and response to
target gas. Its sensitivity increased three-fold and the sensor’s detection
limit decreased twice, compared to the bare Au:CuO thin film.
APTES-functionalized thin films fabricated in this study demonstrate
that modification of Au:CuO surface with a functional group plays an
important role in enhancing the sensitivity to the target gases, particu­
larly in CO detection. These results open the possibility of developing a
Fig. 6. Raman spectra of the functionalized Au:CuO thin film with 0.1 %, 1.0 prototype device for optical CO detection, to be used in places where
%, and 5.0 % of APTES, and of the pure APTES solution in the (a) conductometric-based gas sensors cannot work properly. For example,
1100–1500 cm− 1 and (b) 2700–3020 cm− 1 wavelength range. in flammable or explosive atmospheres, in applications of non-contact
sensing, or where electrical contacts are not desirable. However,
thin films was evaluated by loading He and a mixture of 50 ppm CO in further studies are needed to better understand the sensing mechanism
Ar (CO:Ar) in the HR-LSPR spectroscopy system, alternately for 5 cycles, of APTES-functionalized Au: CuO thin films, and its selectivity con­
at room temperature. The last cycle is used as a reference and was made cerning various gases has to be investigated in further works.
with two half-cycles of He (background gas) only. Real-time responses in
the LSPR peak wavelength for the bare and functionalized Au:CuO thin
films are displayed in Fig. 8, on the left, where the cycles between each

7
M. Proença et al. Sensors and Actuators: B. Chemical 401 (2024) 134959

Fig. 7. Transmittance spectra of the functionalized Au:CuO thin film with 0 %, 0.1 %, 1.0 %, and 5.0 % of APTES.

Fig. 8. LSPR peak wavelength shift measurements of functionalized Au:CuO thin film with 0 %, 0.1 %, 1.0 %, and 5.0 % of APTES during the He and a mixture of
50 ppm CO in Ar (CO:Ar) cycling (left). The bar graphs on the right, demonstrate the average wavelength red-shift for each cycle, respectively.

Funding Marco S. Rodrigues: Formal analysis, Software, Data curation. Cacilda

Moura: Methodology, Supervision. Ana V. Machado: Methodology,
This research was sponsored by the Portuguese Foundation for Sci­ Resources. Joel Borges: Conceptualization, Methodology, Resources,
ence and Technology (FCT) in the framework of the Strategic Funding Writing – review & editing, Supervision, Funding acquisition. Filipe
UIDB/04650/2020, and by the project CO2Plasmon with reference Vaz: Supervision, Funding acquisition, Project administration.
EXPL/CTM-REF/0750/2021. Manuela Proença acknowledges her Ph.D.
Scholarships from FCT, with reference SFRH/BD/137076/2018 and Declaration of Competing Interest
COVID/BD/153223/2023, and for research grant 58/ECUM/CFUM/
2022. The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
CRediT authorship contribution statement the work reported in this paper.

Manuela Proença: Conceptualization, Methodology, Formal anal­

ysis, Investigation, Data curation, Visualization, Writing – original draft.

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M. Proença et al. Sensors and Actuators: B. Chemical 401 (2024) 134959

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Manuela Proença is a Ph.D. Student at the Doctoral Program in Physics (MAP-Fis),
[59] D.J. de Aberasturi, A.B. Serrano-Montes, L.M. Liz-Marzán, Modern applications of
University of Minho. Her main research topics concern plasmonic thin films for gas sensing
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A. Cavaleiro, T. Polcar, M.I. Vasilevskiy, F. Vaz, Broadband optical absorption Marco S. Rodrigues is Ph.D. researcher and his main research areas are nanostructured
caused by the plasmonic response of coalesced Au nanoparticles embedded in a thin films with Localized Surface Plasmon Resonance behavior for sensing applications. He
TiO2 matrix, J. Phys. Chem. C 120 (2016) 16931–16945, https://doi.org/10.1021/ is also specialized in characterization technique as SEM, TEM, AFM and in the develop­
acs.jpcc.6b03684. ment of Matlab algorithms.
[61] M.S. Rodrigues, D. Costa, R.P. Domingues, M. Apreutesei, P. Pedrosa, N. Martin, V.
M. Correlo, R.L. Reis, E. Alves, N.P. Barradas, P. Sampaio, J. Borges, F. Vaz,
Cacilda Moura is an Assistant Professor at CF-UM-UP, University of Minho. Her main
Optimization of nanocomposite Au/TiO2 thin films towards LSPR optical-sensing,
research topic is related to materials characterization by Raman spectroscopy.
Appl. Surf. Sci. 438 (2018) 74–83, https://doi.org/10.1016/J.
APSUSC.2017.09.162.
[62] B. Ingham, T.H. Lim, C.J. Dotzler, A. Henning, M.F. Toney, R.D. Tilley, How Ana Vera Machado is an Associate Professor with Habilitation in the Department of
nanoparticles coalesce: an in situ study of Au nanoparticle aggregation and grain Polymer Engineering at the University of Minho, in Portugal. The main areas of scientific
growth, Chem. Mater. (2011), https://doi.org/10.1021/cm200354d. research are polymerization, copolymerization, polymer modification, polymers blends
[63] R.R.L. De, D.A.C. Albuquerque, T.G.S. Cruz, F.M. Yamaji, F.L. Leite, Measurement and nanocomposites to develop nanostructured, sustainable, functional, intelligent ma­
of the nanoscale roughness by atomic force microscopy: basic principles and terials and polymers from natural resources.
applications, At. Force Microsc. Imaging, Meas. Manip. Surf. At. Scale (2012),
https://doi.org/10.5772/37583. Joel Borges is an Assistant Researcher at CF-UM-UP, University of Minho. His main
[64] N. Aissaoui, L. Bergaoui, J. Landoulsi, J.F. Lambert, S. Boujday, Silane layers on research topic is related to the development of nanoplasmonic thin film materials
silicon surfaces: mechanism of interaction, stability, and influence on protein composed by noble metal nanoparticles (Au, Ag) dispersed in dielectric/semiconductor
adsorption, Langmuir 28 (2012) 656–665, https://doi.org/10.1021/LA2036778/ matrixes, for different sensing applications.
ASSET/IMAGES/MEDIUM/LA-2011-036778_0005.GIF.
[65] N.S.K. Gunda, M. Singh, L. Norman, K. Kaur, S.K. Mitra, Optimization and
characterization of biomolecule immobilization on silicon substrates using (3- Filipe Vaz is an Associated Professor with Habilitation, University of Minho. His main
aminopropyl)triethoxysilane (APTES) and glutaraldehyde linker, Appl. Surf. Sci. research topics concern nanostructured thin films for sensing applications, optical thin
305 (2014) 522–530, https://doi.org/10.1016/J.APSUSC.2014.03.130. film systems and films with Localized Surface Plasmon Resonance behavior.

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