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org/journal/acsodf Article

Aerosol Jet Printed Surface-Enhanced Raman Substrates:

Application for High-Sensitivity Detection of Perfluoroalkyl
Substances
Colleen McDonnell, Faris M. Albarghouthi, Ryan Selhorst, Nancy Kelley-Loughnane, Aaron D. Franklin,
and Rahul Rao*
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ABSTRACT: Printing technologies offer an attractive means for producing low-cost surface-enhanced Raman spectroscopy (SERS)
substrates with high-throughput methods. The development of these substrates is especially important for field-deployable detection
of environmental contaminants. Toward this end, we demonstrate SERS-based substrates fabricated through aerosol jet printing of
silver nanoparticles and graphene inks on Kapton films. Our printed arrays exhibited measurable intensities for fluorescein and
rhodamine dyes down to concentrations of 10−7 M, with the highest SERS intensities obtained for four print passes of Ag
nanoparticles. The substrates also exhibited an excellent shelf life, with little reduction in fluorescein intensities after 9 months of
shelf storage. We also demonstrated the capability of our substrates to sense perfluoroalkyl substances (PFAS), the so-called forever
chemicals that resist degradation due to their strong C−F bonds and persist in the environment. Interestingly, the addition of
graphene to the Ag nanoparticles greatly enhanced the SERS intensity of the perfluorooctanoic acid (PFOA) and
perfluorooctanesulfonic acid (PFOS) molecules under basic conditions (pH ∼ 9) compared to that of fluorescein and rhodamine.
We were able to successfully detect SERS spectra from nano- and picomolar (∼0.4 ppt) concentrations of PFOA and PFOS,
respectively, demonstrating the viability of deploying our SERS sensors in the environment for the ultrasensitive detection of
contaminants.

■ INTRODUCTION
Surface-enhanced Raman spectroscopy (SERS) is a powerful
analytical technique for chemical detection at high sensitiv-
ities.1,2 Since its discovery,3−5 SERS has been demonstrated for
the detection of a wide variety of analytes down to the single-
molecule level.6 The SERS effect occurs through the
adsorption of analytes onto a metal substrate with nanoscale
roughness (e.g., metal nanoparticles), causing an electro-
magnetic enhancement due to the excitation of surface
plasmons from so-called hotspots in the metal particles and a
chemical enhancement due to charge transfer from the metal
particles to the adsorbed analytes. Electromagnetic enhance-
ment is typically several orders of magnitude higher than the
chemical enhancement.7 Enhancement factors (the ratio of the
SERS intensity to normal Raman intensity) as high as 1014 and
sensitivities down to the attomolar level8 have been reported9
for SERS substrates fabricated with a variety of techniques such
© 2022 The Authors. Published by
American Chemical Society
1597
as e-beam lithography, colloidal aggregation, and self-
assembly.10
The relatively expensive and complex fabrication techniques
typically used for SERS substrates enable precise control over
the size, shape, and organization of the metal nanostructures,
thereby enabling the engineering of SERS hotspots with high
precision. However, this precision often comes at the cost of
portability and ease of implementation, which are critical given
the push for point-of-sampling and point-of-care sensing. For
example, the trace detection of contaminants for explosives or
Received: November 4, 2022
Accepted: November 17, 2022
Published: December 20, 2022
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forensics investigation relies on in situ site testing capabilities.
Similarly, the efficiency of SERS diagnostics for food safety and
healthcare can be enhanced significantly through point-of-care
sensing.11,12 With the advent of more affordable handheld and
portable Raman spectrometers, research efforts have shifted
toward the development of rugged field-deployable SERS
substrates, which are key to translating SERS from a laboratory
technique to a robust field research tool.13,14
Realizing SERS sensors that enable field testing in a variety
of environments can be facilitated by moving to simpler
substrate architectures. For example, depositing nanostructures
onto flexible paper or plastic-based substrates allows for wipes
or swabs to collect analytes for SERS sensing.15,16 Further-
more, flexible SERS substrates are attractive due to their lower
production costs and their relative ease of integration into roll-
to-roll processes.17 Early implementations of such substrates
included filter papers loaded with plasmonic nanoparticles,
where the deposition was performed by spray coating or drop-
casting.18,19 A more methodical and reproducible approach is
to fabricate SERS substrates through additive manufacturing
(AM). Another advantage of AM is that features can be easily
patterned in intricate shapes to maximize plasmonic enhance-
ment. Hence, it is similar in principle to lithographic methods
but without all of the added complications. Notable AM
techniques that have been applied for SERS are inkjet, gravure,
and screen printing,20−24 which facilitate SERS measurements
on standard dye molecules with femtomolar detection limits
and enhancement factors of 105. While all of these AM
techniques are typically used to fabricate paper-based SERS
substrates, the primary disadvantage of cellulose substrates is
the inherent Raman background from the cellulose itself. Due
to its organic nature, cellulose exhibits several peaks in its
Raman spectrum that might overlap with the peaks from other
organic or biological analytes. A secondary disadvantage is the
need for a hydrophobic printed surface that would enable
localization of the analyte when drop-cast from a liquid onto
the SERS substrate. Noncellulose substrates would therefore
be advantageous, and some recent studies have demonstrated
the effectiveness of SERS from printed nanoparticles on
polymer substrates such as polyurethane and PET.25,26
One AM technique that has been underexplored for SERS is
aerosol jet printing (AJP), a direct-write method in which a
liquid ink containing functional materials (e.g., plasmonic
nanoparticles) is atomized to produce an aerosol.27 A carrier
gas (such as nitrogen) carries the aerosolized droplets to a
printhead, where a collimated sheath gas directs and
accelerates the stream through a nozzle onto a substrate.28
AJP offers several advantages over other AM methods, such as
high print resolution (10−100 μm)29,30 and the ability to print
directly onto curved surfaces. Importantly, the broad material
compatibility of AJP�in that any material that can be
aerosolized can be printed, including high-viscosity inks�
allows for the printing of complex architectures and
patterns.31,32
With field-deployable sensors in mind, we have fabricated
SERS sensors by AJP on polyimide (Kapton) substrates; these
sensors can potentially be used as swabs to collect analytes
from contaminated surfaces. For this study, we printed 1 mm2
patches of Ag nanoparticles on polyimide (Kapton) that
provide the plasmonic enhancement for the SERS signal. In
addition to the Ag nanoparticles, we also printed graphene
inks, resulting in graphene-coated Ag. The graphene provides
the advantages of high surface areas for analyte adsorption as
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well as higher binding affinities to organic analytes through pi-
stacking and functionalization. We show the ability of our
substrates to measure SERS spectra of standard dyes
(fluorescein and rhodamine) down to concentrations of 10−7
M, and further demonstrate their application for the detection
of trace amounts of perfluorooctanoic acid (PFOA) and
perfluorooctanesulfonic acid (PFOS). PFOA and PFOS are the
most studied compounds of the many per- and poly-fluoroalkyl
substances (PFAS), which are widespread environmental
pollutants known for their resistance to degradation due to
the high strength of the C−F bond (∼130 kcal/mol).33,34
PFAS contamination occurs mainly through aqueous film-
forming foams (AFFFs), which are fluorosurfactants dis-
charged during firefighting. As a result, PFAS are especially
prevalent at airfields and other defense installations, where they
can pollute the surrounding groundwater.35 Several strategies
have been explored for the detection of PFAS molecules, such
as liquid chromatography/mass spectrometry (LC/MS),
colorimetry, fluorescence spectroscopy, and potentiometry,
with the lowest limits of detection around 10 ppt (<0.001 ng/
L).35−40
While the detection limits from existing PFAS detection
strategies are lower than the value suggested by the U.S.
Environmental Pollution Agency (70 ng/L), electrical
detection methods require complex device architectures and
equipment for measurements, and mass spectrometry methods
typically require preconcentration steps. Thus, these methods
are not amenable to portable in situ detection at contaminated
sites. Here, we present SERS spectra from picomolar
(equivalent to ∼0.4 ng/L, or 0.4 ppt) and nanomolar
concentrations of PFOS and PFOA, respectively, deposited
onto our aerosol jet printed substrates. The addition of
graphene to the Ag nanoparticles enhanced the adsorption of
the PFOA and PFOS, and exhibited stronger SERS intensities
compared to bare Ag nanoparticles. Our SERS results are
comparable to the lowest limits of detection demonstrated by
LC/MS while achieving a simple, cheap, and portable form
factor that is ideal for point-of-sample field testing.
■ EXPERIMENTAL METHODS
Aerosol Jet Printing of Graphene and Ag Nano-
particles. All aerosol jet printed materials were deposited on
127 μm thick Kapton substrates, which were cleaned in an
isopropanol ultrasonic bath for 5 min, rinsed with DI water,
and gently blown dry with N2. An Optomec AJ300 aerosol jet
printer was used to deposit graphene and Ag nanoparticles
onto the substrates. Aqueous graphene ink (exfoliated
graphene flakes, 500−1500 nm in size and suspended in
water, purchased from Sigma-Aldrich) was diluted to a third of
its concentration in water, yielding a final graphene
concentration of ∼2.3 wt %; 1 mL of this ink was loaded
into the ultrasonic atomizer to print 1 mm2 patches of
graphene at room temperature using a 150 μm nozzle, a 50
SCCM sheath flow rate, a 30 SCCM carrier gas flow rate, a 500
mA ultrasonic current, and a 2 mm/s print speed. Prior to
printing the Ag nanoparticles (UTDAg40X, UT Dots),
Terpineol (Sigma-Aldrich) was added to the ink to yield a
concentration of 10% v/v, resulting in an increase in the
viscosity of the solution for enhanced print quality. The
resulting ink (1 mL) was loaded into the AJP ultrasonic
atomizer, and 1 mm2 patches of Ag were printed at room
temperature using a 150 μm nozzle, a 25 SCCM sheath flow
rate, a 20 SCCM carrier gas flow rate, a 350 mA ultrasonic
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Figure 1. Structure and characterization of AJP SERS sensors on Kapton. (a) Optical image of Ag nanoparticle arrays printed on a Kapton film with
varying print passes (1−4) from the top to bottom row and indicated on the right of the image. (b) Average height of the arrays as a function of
number of print passes as obtained from optical profilometry. (c) Representative SEM image from one of the arrays in (a) showing agglomerated
clusters of Ag nanoparticles. The high-magnification view in the inset shows individual Ag nanoparticles. (d) Absorbance spectrum from an Ag
nanoparticle array in (a), exhibiting a maximum around 570 nm. The Raman excitation wavelengths used in this study (532 and 633 nm) are
indicated as dashed vertical lines in (d).

current, and a 7 mm/s print speed. The Ag nanoparticle arrays
were then sintered at 200 °C for 1 h. All printed squares were
deposited at varying thicknesses, ranging from one to six print
passes.
The height of the printed patches was characterized by
collecting line scans across the printed patches using a
profilometer (Bruker). To determine the appropriate Raman
excitation wavelength, absorbance spectra were collected from
the printed patches in a microspectrophotometer (CRAIC)
wherein the excitation source (xenon lamp) was focused onto
individual patches using a 40× objective lens. The absorbance
of the patches was recorded between 300 and 800 nm. The
morphology of the Ag and Ag/graphene patches was further
characterized using scanning electron microscopy (SEM).
Prior to imaging, the patches were coated with 2 nm of Ir to
reduce charging from the Kapton and images were collected in
a Zeiss Gemini 500 SEM using an acceleration voltage of 2 kV.
SERS Measurements. Surface-enhanced Raman spectra
were collected in a Renishaw Raman microscope with 532 and
633 nm excitations. For the dye measurements, controlled
amounts of fluorescein (Sigma-Aldrich) and rhodamine 6G
(R6G, Sigma-Aldrich) were dissolved in methanol to produce
solutions ranging from 10−3 to 10−7 M. Using a micropipette, 2
μL of the solutions was drop-cast on the Ag/graphene and Ag
patches with varying print passes (1−6) and allowed to dry for
2 min. Raman spectra were collected by focusing the excitation
laser through a 50× long working distance objective lens. The
laser power was set to 0.5 mW (measured at the sample) to
avoid heating by the laser, and spectral collection times ranged
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between 5 and 30 s. Due to their increased absorbance at
particular wavelengths, spectra were collected from fluorescein
and R6G using 532 and 633 nm excitations, respectively. For
the SERS measurements on PFOS and PFOA, controlled
amounts of both chemicals (Sigma-Aldrich) were dissolved in
deionized water to produce a stock solution with 10−3 M
concentration. The pH of the solutions was adjusted using
either 1 M NaOH in deionized water (to make pH 9 solutions)
or 0.1 M HCl (for pH 5 solutions). These were further diluted
with deionized water to produce solutions ranging from 10−6
to 10−12 M. Similar to the dyes, 2 μL of the PFOS and PFOA
solutions were drop-cast onto the Ag/graphene and Ag patches
(4 print passes) and allowed to dry for 30−60 min before
collecting SERS spectra. For these measurements, we chose
633 nm as the excitation wavelength. All spectra were baseline-
corrected and fitting was performed using Igor Pro software;
two-dimensional Raman maps were generated using the
Renishaw WiRE software.
■ RESULTS AND DISCUSSION
Printing and Characterization of SERS Sensors. As
mentioned above, cellulose exhibits Raman peaks that might
overlap with the peaks of an organic analyte. For this reason, a
polyimide film (Kapton) was chosen as the substrate, and Ag
nanoparticles were selected for plasmonic enhancement in the
visible wavelength region. Kapton exhibits weak Raman activity
in the visible wavelength region, and hence does not exhibit
any Raman peaks that might interfere with accurate sensing of
organic analytes. For the SERS substrate configuration, we
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chose to print 1 mm2 arrays on Kapton films with an 8 mm

separation between each patch. Figure 1a shows an optical
image of one of our SERS substrates with printed Ag
nanoparticles. The substrate in Figure 1a was printed with
increasing print passes (1 to 4) from top to bottom. The layout
of the patches with the 8 mm separation between patches was
chosen to allow for drop-casting of the analyte onto an
individual patch without spilling over and contaminating
neighboring patches. The arrays in Figure 1a were produced by
four sequential print passes over the Kapton films. As
mentioned above and discussed further below, we also added
graphene to the Ag nanoparticles for increased adsorption of
organic analytes. One print pass of graphene ink did not result
in any difference in SERS intensities compared to the Ag
nanoparticles. On the other hand, two and three print passes
exhibited similar differences in SERS intensities (discussed
further below). Hence, the graphene ink was kept to two print
passes throughout this study. We evaluated the SERS
performance of one to four print passes of Ag nanoparticles
(with and without added graphene), with each print pass
yielding a thicker Ag nanoparticle film, as confirmed by optical
profilometry. The profilometry scans from the printed Ag
nanoparticles revealed relatively uniform height profiles across
all of the patches, as shown in Figure S1. The average
thicknesses were calculated from the height profiles and are
presented in Figure 1b as a function of the number of print
passes. The data indicate a linear increase in thickness, with
each pass adding approximately a micron-thick layer of Ag
nanoparticles.
A representative scanning electron microscope (SEM) image
from one of the Ag nanoparticle patches is displayed in Figure
1c. As expected for printed Ag nanoparticle-based inks, the Figure 2. SERS detection of fluorescein. (a) SERS spectra collected
particles undergo significant agglomeration upon drying and using 532 nm excitation from 10−4 to 10−7 M fluorescein deposited
sintering and can be seen clearly in the SEM image. The inset onto four print pass Ag nanoparticles. (b) Average intensity of the
in Figure 1c shows a higher-magnification view, with individual 1185 cm−1 peak as a function of fluorescein concentration. The filled
and empty data points correspond to intensities with and without
nanoparticles (10−20 nm diameter) visible within the
graphene, respectively. (c) Optical image of a printed Ag nanoparticle
agglomerates. Representative SEM images from the gra- patch loaded with 10−4 M fluorescein and the (d) corresponding
phene-capped Ag patches are shown in Figure S2. Absorbance Raman map showing the intensity of the 1185 cm−1 peak from
spectra were collected from individual printed Ag patches fluorescein.
using a microspectrophotometer, and a representative
spectrum from one of the patches in Figure 1a is shown in
Figure 1d. The patch exhibits a maximum absorbance around overall spectral intensity decreases with decreasing fluorescein
570 nm, suggesting that Raman excitation wavelengths of 532 concentration, with the phenolic bend mode still clearly
and 633 nm would be appropriate for SERS measurements. measurable for 10−7 M fluorescein.
SERS Spectra from Standard Dyes. To test the viability To identify the effect of the number of Ag print passes, we
of our printed substrates for SERS, we collected Raman spectra measured SERS spectra from fluorescein deposited on Ag and
from fluorescein and rhodamine 6G (R6G) by drop-casting Ag/graphene patches, fabricated with one to four print passes
controlled amounts (10−4 to 10−7 M) of both dyes (dissolved and calculated the intensities of the 1185 cm−1 peak from
in deionized water, pH = 7) onto the printed Ag and Ag/ several spectra. In these measurements, we kept the number of
graphene patches. Figure 2a shows SERS spectra collected with graphene print passes constant (2 passes). The average
532 nm excitation from various concentrations of fluorescein intensity of the 1185 cm −1 peak against fluorescein
deposited onto four print pass Ag nanoparticle patches. The concentration as a function of Ag print passes is shown in
spectra in Figure 2a were normalized with respect to the input Figure 2b. Similar to the data shown in Figure 2a, the intensity
power and acquisition time. For each concentration of of the 1185 cm−1 peak decreased with fluorescein concen-
fluorescein, the individual Raman spectra (gray) collected tration across all of the measurements. The highest intensities
from random spots on the Ag nanoparticle patches are were observed for four print passes of Ag, and in all cases, the
displayed with the average spectrum (green) overlaid on top. intensities with and without graphene were similar. The reason
Fluorescein exhibits several skeletal fingerprint Raman modes for the higher SERS intensities with four print passes can be
around 1185, 1330, 1410, 1550, 1598, and 1635 cm−1, the attributed to a denser coverage (and thus more SERS
most distinct among them being the phenolic bend mode hotspots) of the Ag nanoparticles, as revealed by SEM imaging
around 1185 cm−1.41 These peaks from the fluorescein are (Figure S4). We also measured SERS spectra from five and six
sharper than the background spectra exhibited from the bare print pass samples and saw an overall decrease in SERS
Ag and Ag/graphene substrates (Figure S3). As expected, the intensities, indicating that four print passes was the optimum
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for achieving highest SERS intensities (Figure S5). While the
graphene-coated Ag nanoparticles did not exhibit a substantial
difference in SERS intensities from fluorescein with respect to
the uncoated Ag nanoparticles, the addition of graphene can
indeed boost the SERS intensity of other adsorbates such as
PFAS, as shown further below.
The uniformity of our patches for SERS activity was
measured through Raman spectral mapping. Figure 2c shows
an optical microscope image of a four print pass Ag patch, with
the corresponding two-dimensional Raman intensity map of
the 1185 cm−1 peak plotted in Figure 2d. Overall, the intensity
of the fluorescein Raman mode is highly uniform, showing that
SERS spectra from analytes dropped anywhere over a patch
should be measurable and accurately representative of the
analyte concentration. SERS spectra from R6G deposited on
the printed Ag patches exhibited similar intensities to the
fluorescein and are shown in Figure S6.
Long-Term Stability. An important consideration when
preparing SERS substrates is long-term stability. While solid
SERS substrates afford higher stabilities than those based on
colloidal metal nanoparticles (increased flocculation), the shelf
life of the typical commercial SERS substrates is typically
between 30 and 60 days. Some of the problems that plague
metal nanoparticle-based SERS substrates are oxidation and
surface contamination, leading to reduced SERS intensities.
These issues might be mitigated through chemical treatments
or by storing the substrates in ultrahigh vacuum,42,43 but a
long-term shelf life of several months under ambient
conditions remains highly desirable for SERS substrates.
With this in mind, we measured SERS spectra from fluorescein
on our printed Ag patches up to 9 months after the fabrication
date. The substrates were placed in sample storage boxes and
stored under standard laboratory conditions in a drawer, and
fluorescein was deposited onto the Ag patches periodically.
Figure 3 shows average SERS spectra obtained from mapping a
dozen random spots on each patch. Overall, the spectra
collected over 9 months are identical in shape, and the patches
Figure 3. Long-term stability of the AJP SERS substrates. SERS
spectra collected with 532 nm excitation from 10−4 M fluorescein
deposited on printed Ag nanoparticles over time. Each spectrum
corresponds to an average of Raman spectra collected from over a
dozen spots on a patch. The fluorescein was deposited on different
patches each time, and spectra were collected with the same
acquisition parameters. The inset shows the intensity of the 1185
cm−1 peak over time.
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exhibited little degradation up to 7 months, with an ∼10% loss
in intensity of the fluorescein peak in the SERS spectrum after
9 months. The inset in the top right of Figure 3 shows the
intensity of the 1185 cm−1 peak from fluorescein over time.
While we expect Ag nanoparticles to oxidize and we indeed see
evidence for oxidation from the low-frequency Ag-O Raman
peak around 200 cm−1 (not shown here), the surface oxide on
the Ag nanoparticles ostensibly provides enough passivation to
keep them active for SERS. A more detailed examination of the
long-term chemical and structural stability of our Ag patches
will be the subject of a future study.
SERS Detection of PFAS. Having established that our
printed substrates demonstrate SERS activity for standard dyes,
we next focus on the detection of trace amounts of PFAS. In
this study, we picked PFOS and PFOA, which are the two
most commonly produced PFAS. The molecular structure of
both PFOA and PFOS is linear and consists of a hydrophobic
n-octyl tail with a carboxylate and sulfonate head group,
respectively (structures are shown in Figure 4). For the SERS
measurements, we dissolved PFOS and PFOA in deionized
water to various concentrations (10−3−10−12 M) and drop-cast
2 μL of the solutions onto the SERS patches. Both Ag (4 print
passes) and Ag/graphene patches (4 print passes of Ag
followed by 3 print passes of graphene) were tested.
Furthermore, the pH of the PFOS and PFOA solutions was
varied from basic (pH = 9) to acidic (pH = 5) to see if it
improved the binding of the PFAS molecules to the SERS
patches. Our measurements revealed a few important
observations: (1) The addition of graphene to the Ag
nanoparticles greatly improved the SERS intensity for both
PFAS molecules and (2) the highest Raman intensity was
obtained with pH 9 solutions.
The SERS spectra from PFOS adsorbed onto Ag/graphene
patches are shown in Figure 4a, with the spectrum from bulk
powder displayed at the bottom, and decreasing concentrations
(10−3 to 10−12 M) of analyte displayed from bottom to top.
PFOS exhibits a number of intense peaks, notably the CF2
symmetric stretching mode around 725 cm−1, SO3 stretching
modes around 1045 and 1140 cm−1, and the CF stretching
mode around 1350 cm−1.44,45 These peaks are commonly
found in fluorine-containing organic compounds and can be
easily identified among the several peaks typically observed in
Raman spectra from complex organic molecules. These peaks
can also be observed in the SERS spectra along with the
broader background peaks from the graphene itself (between
1300 and 1600 cm−1). We also observe additional peaks whose
origin is not known at this time but their appearance could be
attributed to the SERS effect, i.e., the enhancement of
vibrational modes that are otherwise not observable in normal
Raman spectroscopy measurements. The additional peaks
could also be attributed to the much lower concentrations of
the PFAS on the SERS patches compared to bulk powders,
which can quench certain vibrational modes. A detailed
experimental and theoretical analysis of the phonon modes
from various PFAS molecules can help resolve these open
questions. The persistence of the C−F peaks down to the
lowest concentration of PFOS (10−12 M) highlights the
capability of our SERS sensors to measure trace amounts of
PFOS. The picomolar concentration of PFOS corresponds to
∼0.5 ng/L (or 0.5 ppt), which is well below the EPA-suggested
detection limit of 70 ng/L (70 ppt).38 Our results are also
better than the lowest limits of detection (∼10 ppt) from mass
spectrometry measurements of PFAS.37,39,40
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Figure 4. SERS detection of PFOS and PFOA using AJP Ag +
graphene arrays. Surface-enhanced Raman spectra collected with 633
nm excitation from (a) PFOS and (b) PFOA. The structure of each
molecule is shown above the Raman spectra.
Figure 4b shows Raman and SERS spectra from PFOA.
Similar to Figure 4a, the spectrum from as-purchased powder is
displayed at the bottom of Figure 4b. PFOA exhibits several
peaks common with PFOA, e.g., the CF deformation mode
around 730 cm−1 and the CC stretching mode around 1350
cm−1. The concentration-dependent SERS spectra from PFOA
(Figure 4b) do not appear to be as intense as those from
PFOS. In fact, we were unable to measure any peaks at the
lowest concentrations (10−12 M), resulting in a PFOA limit of
detection of 10−9 M.
To compare the SERS intensities with and without
graphene, we measured the intensity of the CF stretching
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mode around 1350 cm−1 in baseline-corrected spectra
collected from at least 24 spots from PFOS and PFOA
(concentration and pH were 10−6 M and 9, respectively)
adsorbed onto the printed Ag/graphene and Ag patches. The
results are presented in a box and whisker plot in Figure 5 (see
Figure 5. SERS intensities from PFOS and PFOA with and without
graphene. Box plots showing the interquartile range and total range of
SERS intensities of the CF stretching mode around 1350 cm−1 from
(a) PFOS and (b) PFOA. The mean and extreme values (1 and 99%)
are indicated by the square and triangle data points, respectively. The
raw data with superimposed normal distributions are plotted to the
left of the boxes. For both PFOS and PFOA, the addition of graphene
to the Ag nanoparticles resulted in higher SERS intensities.
the caption for a detailed description of the box plot) with the
measured intensities plotted next to the boxes along with
overlaid normal distributions. For both PFOS and PFOA, the
SERS intensities of the CF stretching mode were higher with
graphene.
We tentatively attribute the increase in intensities from the
Ag/graphene patches to higher adsorption of the PFAS
molecules onto graphene. In general, PFAS adsorption can
occur through electrostatic interactions, ion exchange, or
hydrophobic interactions. Graphene has been shown to
supplement the enhancement factor of SERS systems by
increasing the surface area for analyte adsorption via hydrogen-
bonding or van der Waals pi−pi interaction.46,47 Thus, we
hypothesize that the enhancement upon the addition of
graphene is due to additional charge transfer from Ag to
graphene, increased surface area for hydrophobic interactions,
and/or further electronic coupling of the graphene with Ag
surface plasmons. As mentioned above, we also saw highest
SERS intensities from both PFOS and PFOA with pH 9
solutions (example spectra from PFOS with varying pH are
shown in Figure S7). Enhancement due to the higher pH could
indicate that there is increased adsorption of deprotonated
PFAS to the silver nanoparticles, causing them to act as ligands
or capping agents as they bind to the silver surface
electrostatically. These factors could also lead to increased
sensitivity over other organic pollutants in real-world water
samples and warrant further investigations beyond the scope of
this study.
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Finally, the reason for the higher sensitivity of our SERS
patches for PFOS compared to PFOA is unclear at this time,
and further studies are needed to understand this phenomen-
on. One possible explanation could be attributed to the higher
hydrophobicity of PFOS, which has previously been observed
to adsorb more strongly than PFOA onto single- and
multiwalled carbon nanotubes.48,49 Other possibilities are the
lower pKa of PFOS and the higher number of hydrogen-
bonding sites per molecule of PFOS. A possible solution to
enhance PFOA adsorption would be functionalization of
graphene with positively charged functional groups like amine-
functionalized graphene.50 Such approaches could enhance
selectivity for certain PFAS molecules and could be
implemented as strategies for multiplexed printed SERS
patches. This will be important for future SERS measurements
of real-world contaminated water and surfaces, which are
expected to contain a variety of PFAS molecules among other
possible contaminants.
■ CONCLUSIONS
We have presented a platform for SERS sensing based on
aerosol jet printed patches on Kapton substrates. The SERS
enhancement is made possible through printing of Ag
nanoparticle inks, with the addition of graphene to the Ag
nanoparticles affording higher binding efficiencies to organic
analytes. We first demonstrated the viability of our SERS
substrates toward the detection of standard dyes like
fluorescein and R6G (down to 10−7 M). Next, we showed
that our SERS substrates are capable of detecting trace
amounts of PFOS (down to 10−12 M) and PFOA (down to
10−9 M). The SERS intensity was higher for graphene-coated
Ag nanoparticle inks and under basic conditions (pH = 9). The
ability of AJP to print plasmonic nanoparticles on a variety of
substrates will enable our SERS sensors to be deployed in the
field as swabs for the sensing of trace amounts of environ-
mental contaminants as well as other toxic analytes. Future
studies will be conducted in this direction along with
multiplexing strategies for increased selective detection and
statistical methods to isolate spectral features from the PFAS
compared to other organic contaminants.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsomega.2c07134.
Ag nanoparticle height profiles, additional SEM images,
SERS spectra from bare substrates as well as rhodamine,
and spectra from PFAS molecules at various pH values
(PDF)
■ AUTHOR INFORMATION
Corresponding Author
Rahul Rao − Materials and Manufacturing Directorate, Air
Force Research Laboratory, WPAFB, Ohio 45433, United
States; orcid.org/0000-0002-6415-0185;
Email: rahul.rao.2@us.af.mil
Authors
Colleen McDonnell − Materials and Manufacturing
Directorate, Air Force Research Laboratory, WPAFB, Ohio
45433, United States; UES Inc., Dayton, Ohio 45433,
1603
Article
United States; Department of Biology, University of Dayton,
Dayton, Ohio 46469, United States
Faris M. Albarghouthi − Department of Electrical &
Computer Engineering, Duke University, Durham, North
Carolina 27708, United States; orcid.org/0000-0001-
5777-710X
Ryan Selhorst − Materials and Manufacturing Directorate,
Air Force Research Laboratory, WPAFB, Ohio 45433,
United States; UES Inc., Dayton, Ohio 45433, United States
Nancy Kelley-Loughnane − Materials and Manufacturing
Directorate, Air Force Research Laboratory, WPAFB, Ohio
45433, United States; orcid.org/0000-0003-2974-644X
Aaron D. Franklin − Department of Electrical & Computer
Engineering, Duke University, Durham, North Carolina
27708, United States; Department of Chemistry, Duke
University, Durham, North Carolina 27708, United States;
orcid.org/0000-0002-1128-9327
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsomega.2c07134
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
C.M., R.S., and R.R. acknowledge funding from the Polymers
and Responsive Materials Research Team and the Biological
Materials and Processing Research Team at AFRL. F.M.A. and
A.D.F. acknowledge support from the National Institutes of
Health (NIH) under award no. 1R01HL146849. The content
presented in this manuscript represents the views of the
authors and does not necessarily represent the views of the
NIH.
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