# Fileset

[monshi-et-al-2025-graphene-enhanced-resonant-arrays-of-silver-nanoparticles-for-sustained-detection-of-raman-signature.pdf](https://mdr.nims.go.jp/filesets/941a7b4f-f50f-48b8-bbf5-110c3978f276/download)

## Creator

Marjan Monshi, [Maziar Moussavi](https://orcid.org/0000-0003-4108-9454), [Nadzeya Khinevich](https://orcid.org/0000-0001-9348-3918), [Tomas Tamulevičius](https://orcid.org/0000-0003-3879-2253), [Asta Tamulevičienė](https://orcid.org/0000-0003-4152-1382), [Joel Henzie](https://orcid.org/0000-0002-9190-2645), [Mindaugas Juodėnas](https://orcid.org/0000-0002-0517-8620), [Sigitas Tamulevičius](https://orcid.org/0000-0002-9965-2724)

## Rights

[Creative Commons BY Attribution 4.0 International](https://creativecommons.org/licenses/by/4.0/)

## Other metadata

[Graphene-Enhanced Resonant Arrays of Silver Nanoparticles for Sustained Detection of Raman Signature](https://mdr.nims.go.jp/datasets/149b2c56-10a8-42ce-8944-9603579bf439)

## Fulltext

Graphene-Enhanced Resonant Arrays of Silver Nanoparticles for Sustained Detection of Raman SignatureGraphene-Enhanced Resonant Arrays of Silver Nanoparticles forSustained Detection of Raman SignatureMarjan Monshi, Maziar Moussavi, Nadzeya Khinevich, Tomas Tamulevicǐus, Asta Tamulevicǐene,̇Joel Henzie, Mindaugas Juodeṅas,* and Sigitas Tamulevicǐus*Cite This: J. Phys. Chem. C 2025, 129, 14983−14992 Read OnlineACCESS Metrics & More Article Recommendations *sı Supporting InformationABSTRACT: Surface-enhanced Raman Scattering spectroscopyhas transformed trace analyte detection by harnessing localizedsurface plasmon resonance. Hybrid plasmonic−photonic modeshave been shown to further improve enhancement factors bytailoring the resonant wavelength. Here, we use a surface latticeresonance-based platform tuned to amplify the Stokes-shiftedRaman emission band produced by using capillarity-assisted Agnanoparticle assembly. Additionally, we transferred graphene ontothese substrates to evaluate its effect on the long-term retention ofthe analyte signal. We monitored the Raman signature of 2-naphthalenethiol on substrates with and without transferredgraphene sheets over 1 year since initial exposure. Signal intensitiesfrom both the unprotected (U) and graphene-protected (G)samples were projected onto the principal components to evaluate the spectral traits and monitor how the spectra change over time.The results showed that both U and G samples initially exhibited a detection score of approximately 80%. While the U samplecompletely lost its Raman signal after 300 days, the G sample retained a detection score of about 30%, which remained stable evenafter 344 days. We attribute the retained signal on the G substrate to two phenomena: (i) graphene prevents the degradation ofplasmonic particles and (ii) helps retain the analyte on the substrate. Moreover, the ratio of Raman peaks coinciding with the latticeresonance vs off-resonance peaks was higher compared to a reference measurement. This underscores the potential of graphene−silver hybrid platforms for applications requiring sustained analyte signature, where a long shelf life and prolonged detection overtime could facilitate repeated measurements or continuous monitoring without the need for frequent sample replacement on site.■ INTRODUCTIONRaman spectroscopy, especially with advancements in surface-enhanced Raman scattering spectroscopy (SERS), has becomea preferred analytical technique for identifying and differ-entiating molecules at low concentrations. This technique,based on the unique material fingerprint of vibrational energylevels, is used across diverse fields, including surface andinterface chemistry, catalysis, biology, biomedicine, foodscience, forensic science, pharmacology, and environmentalanalysis.1−6 The continuous drive for greater sensitivity andbroader applicability in Raman spectroscopy has encouragedinnovations across the field of optical spectroscopy. Forinstance, in coherent techniques like stimulated Ramanscattering microscopy (SRS),7 advances in instrumentation�particularly in beam shaping and aberration correction�areenabling faster, high-resolution imaging at greater tissuedepths. Concurrently, progress in near-field probe design,exemplified by tip-enhanced Raman scattering (TERS),8 isaddressing key limitations such as the weak adsorption ofanalytes on plasmonic surfaces, thereby enhancing signalstrength and spatial resolution. Harnessing this same principleof localized plasmonic enhancement, SERS relies onengineered substrates rather than a single probe.SERS substrates are typically composed of noble metalnanostructures that support localized surface plasmonresonances (LSPRs)�collective oscillations of conductionelectrons excited by an electromagnetic field (EM).9 Amongcommonly used metals for SERS substrates, silver (Ag) is themost effective due to its low optical losses and tunableproperties enabled by advanced wet-chemistry synthesistechniques.6,10−13 Strategies to enhance Raman signals usingsilver-based substrates include the use of diverse supports,6,14periodic arrays exploiting surface lattice resonance,15−17bimetallic nano shells18−20 and isolating silver nanoparticlesfor cross sectional enhancement strategy.21 Despite theseReceived: March 31, 2025Revised: August 3, 2025Accepted: August 6, 2025Published: August 13, 2025Articlepubs.acs.org/JPCC© 2025 The Authors. Published byAmerican Chemical Society14983https://doi.org/10.1021/acs.jpcc.5c02135J. Phys. Chem. C 2025, 129, 14983−14992This article is licensed under CC-BY 4.0Downloaded via NATL INST FOR MATLS SCIENCE (NIMS) on September 3, 2025 at 02:06:16 (UTC).See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.https://pubs.acs.org/action/doSearch?field1=Contrib&text1="Marjan+Monshi"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Maziar+Moussavi"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Nadzeya+Khinevich"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Tomas+Tamulevic%CC%8Cius"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Asta+Tamulevic%CC%8Ciene%CC%87"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Joel+Henzie"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Joel+Henzie"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Mindaugas+Juode%CC%87nas"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Sigitas+Tamulevic%CC%8Cius"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/showCitFormats?doi=10.1021/acs.jpcc.5c02135&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?goto=articleMetrics&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?goto=recommendations&?ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?goto=supporting-info&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?fig=tgr1&ref=pdfhttps://pubs.acs.org/toc/jpccck/129/33?ref=pdfhttps://pubs.acs.org/toc/jpccck/129/33?ref=pdfhttps://pubs.acs.org/toc/jpccck/129/33?ref=pdfhttps://pubs.acs.org/toc/jpccck/129/33?ref=pdfpubs.acs.org/JPCC?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://doi.org/10.1021/acs.jpcc.5c02135?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://pubs.acs.org/JPCC?ref=pdfhttps://pubs.acs.org/JPCC?ref=pdfhttps://acsopenscience.org/researchers/open-access/https://creativecommons.org/licenses/by/4.0/https://creativecommons.org/licenses/by/4.0/https://creativecommons.org/licenses/by/4.0/advantages, silver is highly susceptible to oxidation andsulfuration, especially when exposed to aqueous environ-ments.22 Its usage as SERS-active material faces furtherchallenges in terms of producing inexpensive, reproducible,and highly effective substrates.23 Additionally, the shelf life ofSERS substrates is crucial for preserving their sensitivity. Ifsubstrates degrade or lose their enhancement properties overtime, detection results may become inconsistent andunreliable, even under normal laboratory storage conditions,often due to contamination. To mitigate this issue, substratesthat are not inherently protected should undergo additionaltreatments, such as ion cleaning,24 to remove surfacecontaminants like sulfur, chlorine, carbon, and oxygen, whichcontribute to the degradation of SERS activity.Graphene−plasmonic hybrid platforms have recentlyattracted considerable interest as a possible solution to someof the shortcomings.6,25−29 Graphene, a monolayer of sp2-bonded carbon atoms arranged in a honeycomb-like structure,has great potential in sensing and biosensing.30−33 It is also anexcellent choice for hybridization with metal nanoparticles toenhance their SERS effect due to its electronic properties,chemical inertness and, more importantly, impermeability.34These attributes enable graphene to improve Raman signaldetection through mechanisms such as fluorescence quench-ing,35 surface passivation, molecule adsorption, and chemicalmechanism (CM) enhancement.28,36,37 Several studies havedemonstrated the typical characteristics of CM in graphene-enhanced Raman scattering spectroscopy (GERS) includingthe first-layer effect, the distance dependence betweengraphene and analyte molecules,38−40 the energy alignmentbetween the Fermi level and the highest occupied molecularorbital (HOMO) and lowest unoccupied molecular orbital(LUMO) of the molecule,41,42 and the influence of molecularorientation.43 Notably, while the contribution of CM is smallcompared to that of EM, combining both mechanisms ensureshigher SERS performance. It should also be noted that thesurface plasmon resonance of graphene lies in the THz region,therefore EM enhancement by graphene itself can be excludedwhen using excitation in the visible range.26In particular, the protective role of graphene as an overlayeron irregularly distributed silver particles has been highlightedin a few recent studies. Zhang et al.44 presented a sensitiveSERS substrate using a hybrid structure composed ofgraphene, a silver film, and a laser-textured silicon surface.They showed that the graphene layer reduced SERS signal lossto less than 23% after 50 days of exposure to ambient aircompared to significant degradation of substrates withoutgraphene. Osvat́h et al.45 synthesized graphene−silver nano-particle hybrids on highly oriented pyrolytic graphite (HOPG)substrates. They reported that the graphene-covered Ag NPspreserved their LSPR for 3 months, whereas unprotected AgNPs lost the plasmonic properties completely after 1 monthunder ambient conditions. Gong et al.46 have reportedgraphene-coated Ag nanohole arrays. Nevertheless, althoughthe protective nature of graphene is established, its integrationwith resonant plasmonic lattices featuring surface latticeresonances remains unexplored, and key questions regardingpractical long-term signal stability persist.Noble metal nanoparticles in periodic arrays exhibit higherresonance Q-factor values (Q = λ/Δλ = ∼100) than singleparticles (Q = ∼5).47 This effect, called plasmonic surfacelattice resonance (SLR), occurs when the Rayleigh anomaly(RA) spectrally aligns with the LSPR. SLR manifests as anarrow dip in the optical transmission spectrum, which can betuned via the interplay between the RA and LSPR. Eventhough the EM field becomes delocalized because of thehybridization with the photonic mode, the overall EM fieldenhancement in the vicinity of nanoparticles increases.11,48−50In SERS, this resonance can be optimized for the Ramanmeasurement15,17,51,52 with peak enhancement expected whenthe SLR is between the excitation and Stokes-shiftedwavelengths.53 This has been validated in multiple stud-ies.54−56 Kerker et al.57 described this process as (1)enhancement of the incident light at the excitation wavelengthand (2) amplification of Raman-scattered photons at theStokes-shifted wavelength. Kumar et al.58 confirmed that theEF relates to the product of the squared local field amplitudesat both excitation and emission wavelengths.In this work, we demonstrate a year-long study of thestability of a graphene-enhanced SERS platform based onassembled periodic arrays of colloidal silver nanoparticles. Ourplatform is specifically engineered to feature an SLR peaktuned to the Stokes-shifted band of 2-naphthalenethiol (2NT).We employ Principal Component Analysis (PCA) toinvestigate the influence of graphene as an overlayer andstudy the evolution of the Raman signal over a year from theinitial exposure to the analyte. Our findings suggest howgraphene might have a dual role in retaining the SERS signal insuch systems. This study is particularly relevant for applicationssuch as environmental monitoring, food safety, and biomedicalFigure 1. Schematic workflow of the fabrication and analysis process: (A) fabrication of a PDMS substrate by replicating a structured siliconmaster; (B) deposition of Ag nanoparticles onto the PDMS template using the capillarity-assisted particle assembly (CAPA) method, producingtwo identical samples (C) and (D); (E) graphene growth on annealed Cu foil via plasma-enhanced chemical vapor deposition (PECVD); (F)graphene transfer onto the Sample G using a lamination method with a poly(vinyl alcohol) (PVA) film; (G) exposure of both samples to theanalyte; (H) periodic Raman spectroscopy analysis over time.The Journal of Physical Chemistry C pubs.acs.org/JPCC Articlehttps://doi.org/10.1021/acs.jpcc.5c02135J. Phys. Chem. C 2025, 129, 14983−1499214984https://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?fig=fig1&ref=pdfpubs.acs.org/JPCC?ref=pdfhttps://doi.org/10.1021/acs.jpcc.5c02135?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asdiagnostics, where enhanced analyte and signal retention canenable prolonged exposure to trace analytes in repeatedmeasurements or continuous monitoring without frequentsample preparation.■ MATERIALS AND METHODSThe schematic of the fabrication process of SERS substrates,designated as unprotected (U) and graphene-protected (G), isshown in Figure 1 (see Figure S1 for more details). Each stepin the process is detailed in the following sections.■ SERS SUBSTRATE FABRICATIONSilver nanocubes were synthesized using a modified polyolmethod, where polyvinylpyrrolidone (PVP) controlled theshape evolution, yielding monodisperse nanocubes with anaverage size around 77 ± 3 nm, as detailed elsewhere.59 Thetemplates for nanoparticle assembly were prepared by moldinga structured Si stamp onto a polydimethylsiloxane (PDMS)film via soft-lithography. The silicon master stamp wasfabricated using standard lithographic patterning and etchingtechniques presented in previous work60 and comprised a 20mm × 20 mm array of round pillars with a diameter of 180 nm,a height of 100 nm, and periodicity of 400 nm. Thenanoparticles were assembled into the templates usingcapillarity-assisted particle assembly (CAPA).61 Before depo-sition, the concentration of the nanoparticles was increased bycentrifugation and the solvent was replaced with a 1:2 mixtureof ethanol and dimethylformamide (DMF). The polyvinylpyr-rolidone (PVP) coating enhanced colloidal stability in DMF.60The assembly was performed using a custom-built setup, wherea PDMS template was placed on the stage moving at 1 μm/s,and 100 μL of silver nanoparticle suspension was dispensedand confined with a fixed microscope slide. A detaileddescription of the assembly process can be found in ourprevious work.48 Fabricated SERS-active substrates werecleaned with 0.1 M hydrochloric acid for 30 s and then rinsedwith ethanol and deionized water to remove the PVP polymer.■ GRAPHENE LAYER SYNTHESIS AND TRANSFERGraphene layers were synthesized using microwave plasma-enhanced chemical vapor deposition (PECVD) with copperfoil as the catalytic material.62 A commercial copper (Cu) foilwith a thickness of 45 μm and dimensions of 2 cm × 2 cm wasfirst cleaned by sonication in acetone and isopropanol for 5min each to remove organic residues. The cleaned foil wasthen placed in a quartz furnace at atmospheric pressure andsubsequently supplied with 200 sccm of pure argon gas(99.9999%). The foil was annealed at 500 °C for 1 h,promoting the formation of Cu2O layer on the surface. Thisoxidation plays a crucial role in suppressing the nucleationdensity of graphene domains, thereby facilitating the growth oflarger and more continuous graphene films, which arebeneficial for high-quality synthesis.63The Cu foil was then placed in a PECVD chamber on ametal pad featuring a central hole to elevate the foil above thesample holder to maintain a uniform temperature during thesynthesis process. Prior to graphene growth, the Cu foilunderwent a precleaning step using hydrogen (H2) plasma at aflow rate of 200 sccm for 30 min under a pressure of 24 mbar.The plasma power was 1.1 kW, while a constant temperatureof 550 °C was maintained solely through microwave inductionand plasma-species collisions, without any additional heating.Following precleaning, graphene growth was initiated byintroducing methane (CH4) as a carbon source at a flow rateof 25 sccm, while keeping all other parameters unchanged.After a 10 min growth stage, the plasma was turned off,allowing the system to cool down naturally. The devicereturned to room temperature over a period of approximately 2h.The synthesized graphene-coated Cu foil was then extractedfor subsequent transfer and further characterization. Commer-cial water-soluble poly(vinyl alcohol) (PVA) films with paperbacking were used for graphene transfer from the copper foil toSERS substrate. The PVA film was laminated onto thegraphene-coated copper foil using a commercial hot-rolllaminator at 110 °C and operated at low speed to preventbubbling. The laminated foil was then baked on a preheatedhot plate at 110 °C to enhance adhesion between the PVA filmand graphene. The PVA film, along with the graphene, wasdetached from the copper foil and carefully laminated onto theSERS substrate with assembled nanoparticles several times.The paper backing was then removed, and the PVA wasdissolved by immersing the substrate in deionized waterovernight at room temperature.64 This specific set of transferparameters was found to provide an effective balance betweenmaintaining the structural integrity of the graphene layer andachieving sufficient conformal adhesion to the topographicallypatterned PDMS substrate.■ CHARACTERIZATION TECHNIQUESThe UV−vis transmittance spectra of the fabricated array ofnanoparticles on the patterned PDMS substrate were measuredusing an optical fiber-coupled spectrometer (AvaSpec-2048,Avantes; resolution 1.2 nm) and a custom-made collimatedlight source covering the 400−800 nm range.652NT, a simple aromatic molecule with an extended π-conjugated system, was used to evaluate the long-termretention of its Raman signal on two SERS substrates (Uand G) after immersion in a 10−4 M solution. SERSmeasurements were conducted using a Raman microscopeequipped with a thermoelectrically cooled CCD detector,InVia (Renishaw). Measurements were performed using a 532nm laser excitation source at 0.3 mW power, with an exposuretime of 60 s and a 50× objective lens (other measurementparameters are listed in Table S1 in the SupportingInformation). The U and G samples were measured at eighttime points: immediately after exposure and after 10, 16, 24,35, 108, 303, and 344 days. Reference samples of pure 2NT,PDMS, and graphene were also measured to establish areference data set for evaluation purposes.■ DATA ANALYSISTo systematically analyze the Raman scattering data (range:480−1650 cm−1) and evaluate the spectral characteristics, amultistep data processing workflow was implemented. TheRaman spectra from each sample were imported andpreprocessed using a custom MATLAB script. Noise in theraw spectra was mitigated using a Savitzky−Golay filter toenhance signal clarity. The spectral baseline was correctedusing a nonquadratic asymmetric Huber function,66 whicheffectively removes broad, nonspecific background signalswhile preserving analyte-specific Raman signatures. Unliketraditional least-squares estimation, which minimizes aquadratic cost function, the Huber function minimizes aThe Journal of Physical Chemistry C pubs.acs.org/JPCC Articlehttps://doi.org/10.1021/acs.jpcc.5c02135J. Phys. Chem. C 2025, 129, 14983−1499214985https://pubs.acs.org/doi/suppl/10.1021/acs.jpcc.5c02135/suppl_file/jp5c02135_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.jpcc.5c02135/suppl_file/jp5c02135_si_001.pdfpubs.acs.org/JPCC?ref=pdfhttps://doi.org/10.1021/acs.jpcc.5c02135?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asnonquadratic cost function, offering a more robust solution forthis type of spectral data.All spectra were normalized by dividing the intensity valuesby the Euclidean norm of the spectral vector to ensurecomparability across data sets. The spectra were theninterpolated to a common Raman shift range, enabling aconsistent data alignment for multivariate analysis. Referencespectra (collected from pure crystalline 2NT, the PDMSsubstrate, and graphene layers) were analyzed by usingPrincipal Component Analysis (PCA) to extract principalcomponents (PCs) that capture dominant variance patternsacross the distinct signatures of the reference materials. Ramanspectra from both the U and G samples at various time pointswere projected onto the PCs derived from the referencespectra. See the Supporting Information for more details onthe PCA method.■ RESULTS AND DISCUSSIONCharacteristics of SERS Substrate. SERS enhancementon a resonant lattice is primarily governed by the spectralpositioning of the SLR. Here, we selectively target the Stokes-shifted scattering wavelengths of 2NT in the range of 811−1556 cm−1. For the wavelength of the used excitation laser(532 nm), this range of Raman shifts corresponds to 556−580nm. The RA wavelength at normal incidence for a squaregrating in PDMS is defined by λRA = Λ × n. The SLR closelyfollows the RA, provided that the individual nanoparticledipolar LSPR is blue-shifted with respect to it. Therefore, thecondition for targeted SERS enhancement can be expectedusing a 400 nm square grating in PDMS (Λ = 400 nm,refractive index, n ≃ 1.4), where the RA wavelength is ∼560nm.15,48,67Figure 2A shows the UV−vis extinction spectrum of theperiodic arrays of silver nanoparticles on PDMS measured atnormal incidence following assembly. The spectrum exhibitstwo distinct peaks: a broad peak around 430 nm and a sharperpeak near 570 nm. The broad peak corresponds to thequadrupolar LSPR of the individual silver nanoparticles. Thedipolar LSPR, although imperceptible in the spectrum,hybridizes with the photonic RA mode67 and appears as asharp SLR peak at ∼570 nm, matching the wavelength rangefor the amplification of 2NT signal. Figure 2B presents an SEMmicrograph of the assembled plasmonic structure. Theuniformity of the traps in the patterned substrate ensures aconsistent spacing and geometry across the array, contributingto the reproducibility and scalability of the plasmonicsubstrate.Raman Scattering Spectroscopy. Figure 3 presents theRaman spectrum of graphene used in this study. Seven bandshave been identified in the spectrum: four prominent bands inthe first-region (D, G, D′, and 2D bands) and three less-prominent bands in the second-order region (G*, D+D′, and2D′ bands). The spectral positions and other specifications ofthese bands are listed in Table 1.The D band corresponds to phonons activated only indisordered structures and is associated with sp2 hybridizationfrom double resonance scattering. The G band arises fromsingle-resonance vibrations of the in-plane E2g mode,representing the planar sp2-bonded carbon configuration.The D′ band represents a double resonance mode activatedby a disordered graphitic lattice, with its intensity increasing asmore defects are introduced.The Raman spectrum in Figure 3 confirms the synthesis ofsingle-layer graphene with a significant density of structuraldefects. The definitive evidence for a monolayer is the 2Dpeak, which is sharp, symmetric, and well-fitted by a singleVoigt function with a FWHM of ∼34 cm−1. This conclusion isfurther supported by the high I2D/G intensity ratio of ∼2.68.68The high ID/G ratio of ∼2.2 suggests a high concentration ofdefects, which is expected from a low-temperature growthFigure 2. (A) UV−vis extinction spectrum of periodic arrays of silvernanoparticles on PDMS, measured at normal incidence followinginitial deposition. (B) Scanning electron microscopy (SEM) image ofnanoparticle (NP) arrays on PDMS.Figure 3. A representative Raman spectrum of the reference graphenesample on copper foil with fitted bands overlaid.Table 1. Fitting Results for the Graphene Reference SampleObtained Using the 7-Band Fitting ModelBand Center (cm−1) FWHM (cm−1) Intensity Fit TypeD 1345.1 20.8 1.76 VoigtG 1581.6 21.8 1.00 VoigtD′ 1621.9 15.0 0.24 GaussianG* 2461.2 95.0 0.13 Gaussian2D 2685.5 33.8 2.34 VoigtD+D′ 2940.8 76.1 0.17 Gaussian2D′ 3244.9 45.2 0.20 GaussianThe Journal of Physical Chemistry C pubs.acs.org/JPCC Articlehttps://doi.org/10.1021/acs.jpcc.5c02135J. Phys. Chem. C 2025, 129, 14983−1499214986https://pubs.acs.org/doi/suppl/10.1021/acs.jpcc.5c02135/suppl_file/jp5c02135_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?fig=fig3&ref=pdfpubs.acs.org/JPCC?ref=pdfhttps://doi.org/10.1021/acs.jpcc.5c02135?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asprocess and is likely related to vacancies and nonuniform grainboundaries. These structural defects can also be responsible forother observed spectral features in highly disordered systems.The G band position,69 less prominent bands in the second-order region (2300−3300 cm−1),70 and the G* band71 cansometimes be associated with multiple layers, but here weattribute them to defect-induced compressive strain and/orunintentional doping.Figure 4 presents the averaged Raman spectra obtained frommeasurements of the reference samples, including PDMS,graphene, and 2NT molecules (Figure 4A), along with thetemporal evolution of SERS measurements on U and Gsubstrates over time (Figure 4B). Measurements wereperformed immediately after exposure to the analyte andafter 10, 16, 24, 35, 108, 303, and 344 days. It is important tomention that the substrates were not repeatedly exposed to theanalyte for every measurement. Vertical lines in the figureindicate characteristic peak positions within the Raman shiftrange from 480 to 1650 cm−1.The PDMS reference spectrum exhibits distinct peaks at490, 612, 705, 1260, and 1410 cm−1.15,72 The 2NT moleculepeaks are observed at 515, 599, 766, and 1020 cm−1 whichcorrespond to ring deformation and C−H bending, 1082 cm−1associated with ring breathing coupled with C−S stretchingand in-plane C−H bending, 1380 cm−1 representing the D-mode of the aromatic rings, 1433 and 1455 cm−1 attributed toin-plane C−H bending coupled with ring C�C stretching andC−S stretching, and 1570 and 1622 cm−1 corresponding to thecharacteristic C�C stretching modes of the aromatic ring.SLR-Based SERS Enhancement. To assess the enhance-ment provided by our SERS substrates, we analyzed threerelatively dominant and isolated characteristic Raman peaks ofthe 2NT: Peak I at approximately 766 cm−1, Peak II at 1082cm−1, and Peak III at 1380 cm−1 (see Figure S2). Peak I liesoutside the SLR enhancement range, which is expected toremain unaffected by the SLR and thus serves as an internalreference, whereas Peaks II and III are positioned within theSLR resonance region (556−580 nm). These latter peaks areexpected to be selectively enhanced by the SLR effect.Gaussian peak fitting was applied to both the 2NT referenceand the SERS spectra from both U and G samples obtainedduring the initial month, providing normalized peak intensitiesrelative to Peak I. The calculated enhancement factors reflectselective amplification of Peaks II and III under SERSconditions (Table 2). The comparison clearly illustrates therelative increase in intensity for Peaks II and III, suggestingthat their enhancement correlates directly with the position ofthe SLR peak.Principal Component Analysis. The Raman spectral dataof the reference samples were subjected to PCA to identify thepatterns of variance. It is important to note that Ramananalysis often relies on relative peak intensity ratios or peakfitting to derive metrics. However, these methods struggle withoverlapping peaks and trace concentrations, as they reduce theFigure 4. (A) Averaged and normalized Raman spectra for reference samples: graphene (green), PDMS (purple), and 2NT (yellow), with verticallines indicating characteristic peak positions. Peaks I, II, and III mark the 2NT peaks used for selective amplification analysis. (B) The temporalevolution of Raman spectra for 2NT on SERS substrates on sample G in blue and sample U in orange, recorded over a period from day 1 to day344 since initial exposure to the analyte. The shaded region marks the SLR-enhanced range.Table 2. Normalized Intensities and Calculated Enhancement Factors (EFs) for Characteristic Raman Peaks of 2NTaPeak Position (cm−1) (Reference) Normalized Intensity (Reference) Normalized Intensity (SERS) Enhancement Factor (EF)I (off resonance) 766 1 1 x1II (on resonance) 1082 0.38 ± 0.03 3.39 ± 0.16 x8.92 ± 0.78III (on resonance) 1380 1.92 ± 0.11 6.80 ± 0.30 x3.54 ± 0.26aPeak I (766 cm−1), located outside the SLR range, serves as the normalization reference.The Journal of Physical Chemistry C pubs.acs.org/JPCC Articlehttps://doi.org/10.1021/acs.jpcc.5c02135J. Phys. Chem. C 2025, 129, 14983−1499214987https://pubs.acs.org/doi/suppl/10.1021/acs.jpcc.5c02135/suppl_file/jp5c02135_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?fig=fig4&ref=pdfpubs.acs.org/JPCC?ref=pdfhttps://doi.org/10.1021/acs.jpcc.5c02135?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asspectral data set to a single parameter, leading to a loss ofcritical information.73 PCA addresses these challenges byleveraging the entire spectral data set, capturing bothprominent and subtle variations, and generating a set ofrobust metrics known as principal components (PCs). Byplotting our observation points against the first two principalcomponents in Figure 5A, we visualized 95% of the variance inthe high-dimensional spectral data set, with PC1 capturing∼60% and PC2 accounting for ∼35% of the variance. Thescree plot (Figure S3) confirms that PC1 and PC2 togetherexplain nearly 94% of the total variance, with an elbow point atPC3, justifying the selection of the first two components forspectral differentiation.Distinct clustering of the reference samples for PDMS (+0.7on PC1) and 2NT (−0.65 on PC1) clearly separates theirRaman signatures. Within this PCA space, the measurementstaken on the SERS substrate span intermediate positions from−0.4 to +0.6 on PC1, reflecting the relative contributions ofPDMS and 2NT in the spectra. This projection effectivelyillustrates the relative concentration of each referencesignature. Observations with stronger 2NT signature clusternear the 2NT reference (−0.4 < PC1 < −0.2), while thosedominated by PDMS signature shift toward positive PC1scores, closer to the PDMS reference. These findings confirmPC1 as a reliable metric for evaluating the relativeconcentration of 2NT vs the PDMS background. The secondprincipal component (PC2) primarily distinguishes thegraphene signature at PC2 = −0.7 from the other tworeferences with positive scores. As a result, SERS spectra fromsample G align more closely with the graphene referencecompared to the U series.By normalizing PC1 scores linearly, we created aquantitative score for analyte detection ranging from 0% (no2NT detected) to 100% (pure 2NT detected). We used thismetric to track the time-dependent evolution of the SERSsignal, as illustrated in Figure 5B. Results revealed that both Uand G samples initially showed a detection score of around80%. After 300 days, the U sample completely lost the Ramansignal, while the G sample still exhibited a detection score ofapproximately 30% and retained it after 344 days. The decaycurve for the U sample follows a trend that can beapproximated by an exponential decay, a pattern consistentwith first-order kinetic processes that often govern materialdegradation and analyte desorption.It should be noted that PCA has limitations, particularly inhandling nonlinear combinations of components or variationsin spectral characteristics. For instance, variations in graphene’sD/G ratio across observations result in shifts in PC2, withsome observations from the G sample moving further from thegraphene reference. Peak shifts or new peaks emerging frommolecular bonding can also reduce PCA’s sensitivity, asdemonstrated by the 2NT peak shifting from 1080 cm−1 in itscrystalline form (reference) to 1070 cm−1 on the SERSsubstrate.74 Despite these challenges, PCA proved effective bydetecting the 2NT signal (Detection Score = 30%) in sampleU at Day 108, even when the isolated 1070 cm−1 band was nolonger detectable (Supplementary Figure S4). This under-scores PCA’s capability compared to manual peak-fittingmethods for generalized spectral analysis and long-termmonitoring.■ DISCUSSIONThe results indicate that during the first month, the detectionscore remained relatively stable and even higher for sample U.This observation aligns with the findings of Gong et al.,46 whoreported a slightly higher enhancement factor for bare metalsubstrates. This effect can be attributed to the additionaldistance introduced by graphene layers compared with theFigure 5. (a) PCA score plot showing the clustering of reference signatures (2NT, PDMS, and graphene) and the intermediate positions of SERSobservations from samples U and G over time. PC1 (59.35% variance) separates the 2NT and PDMS reference signatures, while PC2 (34.55%variance) mainly captures the graphene signature. Standard error bands (shaded regions) illustrate the variability of mean scores. (b) Analytedetection scores (based on normalized PC1) for samples U and G as a function of time. Detection scores for sample U decline from 70 to 80%initially to 30% by day 108 and become indistinguishable from PDMS after 300 days. In contrast, sample G retains ∼40% of its initial detectionscore after 100 days, stabilizing at ∼29.7%.The Journal of Physical Chemistry C pubs.acs.org/JPCC Articlehttps://doi.org/10.1021/acs.jpcc.5c02135J. Phys. Chem. C 2025, 129, 14983−1499214988https://pubs.acs.org/doi/suppl/10.1021/acs.jpcc.5c02135/suppl_file/jp5c02135_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acs.jpcc.5c02135/suppl_file/jp5c02135_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?fig=fig5&ref=pdfhttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?fig=fig5&ref=pdfpubs.acs.org/JPCC?ref=pdfhttps://doi.org/10.1021/acs.jpcc.5c02135?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asdirect interaction between analyte molecules and metalparticles. Over time, however, both samples exhibited a declinein the signal intensity. While the detection score for sample Gstabilized at approximately 29.7%, the score of sample Udropped to zero. The decline is primarily due to oxidation andsulfurization,45 which degrades nanoparticles directly exposedto the analyte and ambient air. In our study, this degradationwas further intensified by the strong chemisorption betweenthe thiol (-SH) groups of 2NT and the silver surface, initiatingchemical reactions that progressively deteriorated theplasmonic properties and, in turn, promoted analytedesorption, leading to a complete loss of the SERS effect inU samples under a natural atmosphere.Despite some degradation in sample G due to inhomoge-neous graphene coverage and defects introduced duringtransfer, the sample retained detectable spectral features ofthe 2NT over extended periods. We attribute this stabilizationto two key factors: (1) physical barrier effect and (2) enhancedadsorption equilibrium. In regions of complete coverage, theimpermeable graphene layer shields the silver nanoparticlesfrom ambient air and the analyte solution, preventing theoxidative and chemical degradation that leads to the loss ofplasmonic properties.45 Second, graphene provides a stablesurface for analyte retention through π−π stacking. Thisinteraction, which is strongest when the aromatic rings of 2-NT are oriented parallel to the graphene surface, alters thelong-term adsorption/desorption equilibrium.75 Although π−πstacking interaction is weaker compared to covalent bondsformed by thiol groups with metal particles, they are stillsignificant when the substrate is an aromatic system likegraphene.76,77 Moreover, it has been shown that the presenceof defects facilitates better attachment of probe molecules.78Smith and Kay79 demonstrated that benzene remains adsorbedon graphene surfaces via van der Waals interactions, exhibitingfirst-order desorption kinetics. Similarly, Chakradhar et al.80showed that while the interaction strength between benzeneand graphene can be modulated by the underlying substrate, itremains sufficiently robust to delay desorption. These twomechanisms result in a stable, long-term population ofadsorbed molecules, explaining the sustained SERS signal onsample G, in stark contrast to the complete signal loss on the Usample, where the degrading silver surface could no longerretain the analyte.■ CONCLUSIONSIn this work, we investigated the year-long stability of agraphene-protected SERS platform based on resonant silvernanoparticle arrays and suggested mechanisms responsible forsignal retention. We demonstrated an efficient approach forfabricating plasmonic SERS substrates with a dry-transferredgraphene overlayer. We followed the SERS signal kinetics of2NT spectra on unprotected (U) and graphene-covered (G)SERS substrates over 344 days and used Principal ComponentAnalysis to evaluate performance. Over time, both samplesexhibited a decline in signal intensity, but the detection scorefor the G sample stabilized at approximately 29.7%, while thescore for the U sample dropped to zero. This stabilization canbe attributed to two key factors: (1) the protective effect ofgraphene, shielding silver nanoparticles from ambient air andanalyte exposure, and (2) enhanced analyte retention via π−πstacking interactions.These graphene-protected substrates show significantpromise for applications requiring long-term stability, such ascontinuous environmental and biomedical monitoring. Futurework could focus on optimizing the trade-off between initialsensitivity and longevity by improving graphene transferuniformity or engineering nanoparticle-graphene spacing.Furthermore, the fabrication and transfer methodologypresented here could be adapted to integrate other 2Dmaterials, opening new possibilities for the design of hybridsensors with tailored properties.■ ASSOCIATED CONTENT*sı Supporting InformationThe Supporting Information is available free of charge athttps://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135.Detailed workflow of the fabrication and analysis process(Figure S1); details on the Principal ComponentAnalysis (PCA) methodology; comparison of averageRaman spectra normalized to the intensity of Peak I(Figure S2); scree plot showing the variance explainedby each principal component (PC) in the Ramanspectral data set (Figure S3); Raman measurementsettings (Table S1); evolution of the normalized peakintensity at 1067 cm−1 for the U and G SERS samplesover time (Figure S4) (PDF)■ AUTHOR INFORMATIONCorresponding AuthorsMindaugas Juodeṅas − Institute of Materials Science, KaunasUniversity of Technology, LT-51423 Kaunas, Lithuania;orcid.org/0000-0002-0517-8620;Email: mindaugas.juodenas@ktu.ltSigitas Tamulevicǐus − Institute of Materials Science, KaunasUniversity of Technology, LT-51423 Kaunas, Lithuania;Department of Physics, Kaunas University of Technology,Kaunas LT-51368, Lithuania; orcid.org/0000-0002-9965-2724; Email: sigitas.tamulevicius@ktu.ltAuthorsMarjan Monshi − Institute of Materials Science, KaunasUniversity of Technology, LT-51423 Kaunas, LithuaniaMaziar Moussavi − Institute of Materials Science, KaunasUniversity of Technology, LT-51423 Kaunas, Lithuania;orcid.org/0000-0003-4108-9454Nadzeya Khinevich − Institute of Materials Science, KaunasUniversity of Technology, LT-51423 Kaunas, Lithuania;orcid.org/0000-0001-9348-3918Tomas Tamulevicǐus − Institute of Materials Science, KaunasUniversity of Technology, LT-51423 Kaunas, Lithuania;Department of Physics, Kaunas University of Technology,Kaunas LT-51368, Lithuania; orcid.org/0000-0003-3879-2253Asta Tamulevicǐene ̇ − Institute of Materials Science, KaunasUniversity of Technology, LT-51423 Kaunas, Lithuania;Department of Physics, Kaunas University of Technology,Kaunas LT-51368, Lithuania; orcid.org/0000-0003-4152-1382Joel Henzie − Research Center for MaterialsNanoarchitectonics (MANA), National Institute forMaterials Science (NIMS), Tsukuba, Ibaraki 305-0044,Japan; orcid.org/0000-0002-9190-2645Complete contact information is available at:https://pubs.acs.org/10.1021/acs.jpcc.5c02135The Journal of Physical Chemistry C pubs.acs.org/JPCC Articlehttps://doi.org/10.1021/acs.jpcc.5c02135J. Phys. Chem. C 2025, 129, 14983−1499214989https://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?goto=supporting-infohttps://pubs.acs.org/doi/suppl/10.1021/acs.jpcc.5c02135/suppl_file/jp5c02135_si_001.pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Mindaugas+Juode%CC%87nas"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0002-0517-8620https://orcid.org/0000-0002-0517-8620mailto:mindaugas.juodenas@ktu.lthttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Sigitas+Tamulevic%CC%8Cius"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0002-9965-2724https://orcid.org/0000-0002-9965-2724mailto:sigitas.tamulevicius@ktu.lthttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Marjan+Monshi"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Maziar+Moussavi"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0003-4108-9454https://orcid.org/0000-0003-4108-9454https://pubs.acs.org/action/doSearch?field1=Contrib&text1="Nadzeya+Khinevich"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0001-9348-3918https://orcid.org/0000-0001-9348-3918https://pubs.acs.org/action/doSearch?field1=Contrib&text1="Tomas+Tamulevic%CC%8Cius"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0003-3879-2253https://orcid.org/0000-0003-3879-2253https://pubs.acs.org/action/doSearch?field1=Contrib&text1="Asta+Tamulevic%CC%8Ciene%CC%87"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0003-4152-1382https://orcid.org/0000-0003-4152-1382https://pubs.acs.org/action/doSearch?field1=Contrib&text1="Joel+Henzie"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0002-9190-2645https://pubs.acs.org/doi/10.1021/acs.jpcc.5c02135?ref=pdfpubs.acs.org/JPCC?ref=pdfhttps://doi.org/10.1021/acs.jpcc.5c02135?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asNotesThe authors declare no competing financial interest.■ ACKNOWLEDGMENTSThe research was implemented within the NANOTRAACESproject carried out under the M-ERA.NET 2 scheme. Thisproject has received funding from the Research Council ofLithuania (LMTLT), agreement No MERANET-22-2.■ REFERENCES(1) Zheng, X.; Ye, Z.; Akmal, Z.; He, C.; Zhang, J.; Wang, L. RecentProgress in SERS Monitoring of Photocatalytic Reactions. Chem. Soc.Rev. 2024, 53 (2), 656−683.(2) Karlo, J.; Razi, S. S.; Phaneeswar, M. S.; Vijay, A.; Singh, S. P.Metallic Nanoparticles for Surface-Enhanced Raman Scattering BasedBiosensing Applications. Photochem 2024, 4 (4), 417−433.(3) Moldovan, R.; Vereshchagina, E.; Milenko, K.; Iacob, B. C.;Bodoki, A. E.; Falamas, A.; Tosa, N.; Muntean, C. M.; Farcaǔ, C.;Bodoki, E. Review on Combining Surface-Enhanced Raman Spec-troscopy and Electrochemistry for Analytical Applications. Anal. Chim.Acta 2022, 1209, 339250.(4) Srivastava, S.; Wang, W.; Zhou, W.; Jin, M.; Vikesland, P. J.Machine Learning-Assisted Surface-Enhanced Raman SpectroscopyDetection for Environmental Applications: A Review. Environ. Sci.Technol. 2024, 58 (47), 20830−20848.(5) Cao, Y.; Cheng, Y.; Sun, M. Graphene-Based SERS for Sensorand Catalysis. Appl. Spectrosc. Rev. 2023, 58 (1), 1−38.(6) Tong, Q.; Wang, W.; Fan, Y.; Dong, L. Recent ProgressivePreparations and Applications of Silver-Based SERS Substrates. TrACTrends in Analytical Chemistry 2018, 106, 246−258.(7) Wang, W.; Huang, Z.; Pirone, D.; Sirico, D.; Miccio, L.; Bianco,V.; Mugnano, M.; Del Giudice, D.; Pasquinelli, G.; Valente, S.; et al.Stimulated Raman Scattering Microscopy with Phase-ControlledLight Focusing and Aberration Correction for Rapid and Label-Free,Volumetric Deep Tissue Imaging. Opto-Electronic Advances 2024, 7(9), 240064.(8) Xie, Z.; Meng, C.; Yue, D.; Xu, L.; Mei, T.; Zhang, W. Tip-Enhanced Raman Scattering of Glucose Molecules. Opto-ElectronicScience 2025, 4 (5), 240027.(9) Han, X. X.; Rodriguez, R. S.; Haynes, C. L.; Ozaki, Y.; Zhao, B.Surface-Enhanced Raman Spectroscopy. Nature Reviews MethodsPrimers 2021, 1 (1), 1−17.(10) Li, Y.; Liao, Q.; Hou, W.; Qin, L. Silver-Based Surface PlasmonSensors: Fabrication and Applications. International Journal ofMolecular Sciences 2023, 24 (4), 4142.(11) Deng, S.; Li, R.; Park, J. E.; Guan, J.; Choo, P.; Hu, J.; Smeets,P. J. M.; Odom, T. W. Ultranarrow Plasmon Resonances fromAnnealed Nanoparticle Lattices. Proc. Natl. Acad. Sci. U. S. A. 2020,117 (38), 23380−23384.(12) Juodeṅas, M.; Peckus, D.; Tamulevicǐus, T.; Yamauchi, Y.;Tamulevicǐus, S.; Henzie, J.; Henzie, J. Effect of Ag NanocubeOptomechanical Modes on Plasmonic Surface Lattice Resonances.ACS Photonics 2020, 7 (11), 3130−3140.(13) Rycenga, M.; Cobley, C. M.; Zeng, J.; Li, W.; Moran, C. H.;Zhang, Q.; Qin, D.; Xia, Y. Controlling the Synthesis and Assembly ofSilver Nanostructures for Plasmonic Applications. Chem. Rev. 2011,111 (6), 3669−3712.(14) Khinevich, N.; Juodeṅas, M.; Tamulevicǐene,̇ A.; Bandarenka,H.; Tamulevicǐus, S. Tailoring Mesoporous Silicon Surface to Form aVersatile Template for Nanoparticle Deposition. Coatings 2021, 11(6), 699.(15) Khinevich, N.; Juodeṅas, M.; Tamulevicǐene,̇ A.; Tamulevicǐus,T.; Talaikis, M.; Niaura, G.; Tamulevicǐus, S. Wavelength-TailoredEnhancement of Raman Scattering on a Resonant Plasmonic Lattice.Sens Actuators B Chem. 2023, 394, 134418.(16) Ragheb, I.; Braïk, M.; Lau-Truong, S.; Belkhir, A.;Rumyantseva, A.; Kostcheev, S.; Adam, P. M.; Chevillot-Biraud, A.;Lévi, G.; Aubard, J.; et al. Surface Enhanced Raman Scattering onRegular Arrays of Gold Nanostructures: Impact of Long-RangeInteractions and the Surrounding Medium. Nanomaterials 2020, 10(11), 2201.(17) Alam, K.; Kabusure, K. M.; Asamoah, B. O.; Nuutinen, T.;Baah, M.; Mohamed, S.; Matikainen, A.; Heikkinen, J.; Rekola, H.;Roussey, M.; et al. Double Resonant Plasmonic Lattices for RamanStudies. Nanoscale 2020, 12 (45), 23166−23172.(18) Alvarez-Puebla, R. A.; Ross, D. J.; Nazri, G. A.; Aroca, R. F.Surface-Enhanced Raman Scattering on Nanoshells with TunableSurface Plasmon Resonance. Langmuir 2005, 21 (23), 10504−10508.(19) Wang, L.; Wang, E.; Tang, J. Facile Synthesis of Flower-like AgNanocube@mesoporous SiO2 and Their Sensitive SERS Perform-ance. J. Nanopart. Res. 2019, 21 (3), 1−7.(20) Zhang, H.; Song, D.; Gao, S.; Zhang, J.; Zhang, H.; Sun, Y.Novel SPR Biosensors Based on Metal Nanoparticles Decorated withGraphene for Immunoassay. Sens Actuators B Chem. 2013, 188, 548−554.(21) Cao, Z.; He, P.; Huang, T.; Yang, S.; Han, S.; Wang, X.; Ding,G. Plasmonic Coupling of AgNPs near Graphene Edges: A Cross-Section Strategy for High-Performance SERS Sensing. Chem. Mater.2020, 32 (9), 3813−3822.(22) Sultan, M. F. An Investigation of the Influence of the GrapheneLayers Number on the Performance of Surface Plasmon ResonanceBiosensors with Various Thicknesses of Silver. J. Opt 2024, 53 (5),4893−4900.(23) Pérez-Jiménez, A. I.; Lyu, D.; Lu, Z.; Liu, G.; Ren, B. Surface-Enhanced Raman Spectroscopy: Benefits, Trade-Offs and FutureDevelopments. Chem. Sci. 2020, 11 (18), 4563−4577.(24) Nuntawong, N.; Eiamchai, P.; Wong-Ek, B.; Horprathum, M.;Limwichean, K.; Patthanasettakul, V.; Chindaudom, P. Shelf TimeEffect on SERS Effectiveness of Silver Nanorod Prepared by OADTechnique. Vacuum 2013, 88 (1), 23−27.(25) Zhang, Z.; Lee, Y.; Haque, M. F.; Leem, J.; Hsieh, E. Y.; Nam,S. W. Plasmonic Sensors Based on Graphene and Graphene HybridMaterials. Nano Convergence 2022, 9 (1), 28.(26) Lin, J.; Zhang, N.; Tong, L.; Zhang, J. Enhanced RamanScattering on Graphene and Beyond. Frontiers of Plasmon EnhancedSpectroscopy Vol. 2; ACS Symposium Series; American ChemicalSociety, 2016; No. 1246, pp 97−119, DOI: 10.1021/bk-2016-1246.ch005.(27) Zhang, N.; Tong, L.; Zhang, J. Graphene-Based EnhancedRaman Scattering toward Analytical Applications. Chem. Mater. 2016,28 (18), 6426−6435.(28) Lai, H.; Xu, F.; Zhang, Y.; Wang, L. Recent Progress onGraphene-Based Substrates for Surface-Enhanced Raman ScatteringApplications. J. Mater. Chem. B 2018, 6 (24), 4008−4028.(29) Zhang, N.; Tong, L.; Zhang, J. Graphene-Based EnhancedRaman Scattering toward Analytical Applications. Chem. Mater. 2016,28 (18), 6426−6435.(30) Pourmadadi, M.; Dinani, H. S.; Tabar, F. S.; Khassi, K.; Janfaza,S.; Tasnim, N.; Hoorfar, M. Properties and Applications of Grapheneand Its Derivatives in Biosensors for Cancer Detection: AComprehensive Review. Biosensors 2022, 12 (5), 269.(31) Bhatt, S.; Punetha, V. D.; Pathak, R.; Punetha, M. Two-Dimensional Carbon Nanomaterial-Based Biosensors: Micromachinesfor Advancing the Medical Diagnosis. Advanced Structured Materials2023, 190, 181−225.(32) Cao, Y.; Cheng, Y.; Sun, M. Graphene-Based SERS for Sensorand Catalysis. Appl. Spectrosc Rev. 2023, 58 (1), 1−38.(33) Zhao, Y.; Li, X. G.; Zhou, X.; Zhang, Y. N. Review on theGraphene Based Optical Fiber Chemical and Biological Sensors. SensActuators B Chem. 2016, 231, 324−340.(34) Bunch, J. S.; Verbridge, S. S.; Alden, J. S.; Van Der Zande, A.M.; Parpia, J. M.; Craighead, H. G.; McEuen, P. L. ImpermeableAtomic Membranes from Graphene Sheets. Nano Lett. 2008, 8 (8),2458−2462.(35) Xie, L.; Ling, X.; Fang, Y.; Zhang, J.; Liu, Z. Graphene as aSubstrate to Suppress Fluorescence in Resonance Raman Spectros-copy. J. Am. Chem. Soc. 2009, 131 (29), 9890−9891.The Journal of Physical Chemistry C pubs.acs.org/JPCC Articlehttps://doi.org/10.1021/acs.jpcc.5c02135J. Phys. Chem. C 2025, 129, 14983−1499214990https://doi.org/10.1039/D3CS00462Ghttps://doi.org/10.1039/D3CS00462Ghttps://doi.org/10.3390/photochem4040026https://doi.org/10.3390/photochem4040026https://doi.org/10.1016/j.aca.2021.339250https://doi.org/10.1016/j.aca.2021.339250https://doi.org/10.1021/acs.est.4c06737?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/acs.est.4c06737?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1080/05704928.2021.1910286https://doi.org/10.1080/05704928.2021.1910286https://doi.org/10.1016/j.trac.2018.06.018https://doi.org/10.1016/j.trac.2018.06.018https://doi.org/10.29026/oea.2024.240064https://doi.org/10.29026/oea.2024.240064https://doi.org/10.29026/oea.2024.240064https://doi.org/10.29026/oes.2025.240027https://doi.org/10.29026/oes.2025.240027https://doi.org/10.1038/s43586-021-00083-6https://doi.org/10.3390/ijms24044142https://doi.org/10.3390/ijms24044142https://doi.org/10.1073/pnas.2008818117https://doi.org/10.1073/pnas.2008818117https://doi.org/10.1021/acsphotonics.0c01187?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/acsphotonics.0c01187?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/cr100275d?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/cr100275d?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.3390/coatings11060699https://doi.org/10.3390/coatings11060699https://doi.org/10.1016/j.snb.2023.134418https://doi.org/10.1016/j.snb.2023.134418https://doi.org/10.3390/nano10112201https://doi.org/10.3390/nano10112201https://doi.org/10.3390/nano10112201https://doi.org/10.1039/D0NR05255Hhttps://doi.org/10.1039/D0NR05255Hhttps://doi.org/10.1021/la051645l?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/la051645l?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1007/s11051-019-4509-2https://doi.org/10.1007/s11051-019-4509-2https://doi.org/10.1007/s11051-019-4509-2https://doi.org/10.1016/j.snb.2013.07.055https://doi.org/10.1016/j.snb.2013.07.055https://doi.org/10.1021/acs.chemmater.9b05293?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/acs.chemmater.9b05293?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1007/s12596-024-01754-9https://doi.org/10.1007/s12596-024-01754-9https://doi.org/10.1007/s12596-024-01754-9https://doi.org/10.1039/D0SC00809Ehttps://doi.org/10.1039/D0SC00809Ehttps://doi.org/10.1039/D0SC00809Ehttps://doi.org/10.1016/j.vacuum.2012.08.006https://doi.org/10.1016/j.vacuum.2012.08.006https://doi.org/10.1016/j.vacuum.2012.08.006https://doi.org/10.1186/s40580-022-00319-5https://doi.org/10.1186/s40580-022-00319-5https://doi.org/10.1021/bk-2016-1246.ch005?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/bk-2016-1246.ch005?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/bk-2016-1246.ch005?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/bk-2016-1246.ch005?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/acs.chemmater.6b02925?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/acs.chemmater.6b02925?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1039/C8TB00902Chttps://doi.org/10.1039/C8TB00902Chttps://doi.org/10.1039/C8TB00902Chttps://doi.org/10.1021/acs.chemmater.6b02925?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/acs.chemmater.6b02925?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.3390/bios12050269https://doi.org/10.3390/bios12050269https://doi.org/10.3390/bios12050269https://doi.org/10.1007/978-3-031-28942-2_9https://doi.org/10.1007/978-3-031-28942-2_9https://doi.org/10.1007/978-3-031-28942-2_9https://doi.org/10.1080/05704928.2021.1910286https://doi.org/10.1080/05704928.2021.1910286https://doi.org/10.1016/j.snb.2016.03.026https://doi.org/10.1016/j.snb.2016.03.026https://doi.org/10.1021/nl801457b?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/nl801457b?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/ja9037593?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/ja9037593?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/ja9037593?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-aspubs.acs.org/JPCC?ref=pdfhttps://doi.org/10.1021/acs.jpcc.5c02135?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-as(36) Zhou, Q.; Jin, M.; Wu, W.; Fu, L.; Yin, C.; Karimi-Maleh, H.Graphene-Based Surface-Enhanced Raman Scattering (SERS) Sens-ing: Bibliometrics Based Analysis and Review. Chemosensors 2022, Vol.10, Page 317 2022, 10 (8), 317.(37) Nurrohman, D. T.; Chiu, N. F. A Review of Graphene-BasedSurface Plasmon Resonance and Surface-Enhanced Raman ScatteringBiosensors: Current Status and Future Prospects. Nanomaterials2021, 11 (1), 216.(38) Ling, X.; Xie, L.; Fang, Y.; Xu, H.; Zhang, H.; Kong, J.;Dresselhaus, M. S.; Zhang, J.; Liu, Z. Can Graphene Be Used as aSubstrate for Raman Enhancement? Nano Lett. 2010, 10 (2), 553−561.(39) Ling, X.; Zhang, J. First-Layer Effect in Graphene-EnhancedRaman Scattering. Small 2010, 6 (18), 2020−2025.(40) Dai, Z. G.; Xiao, X. H.; Wu, W.; Zhang, Y. P.; Liao, L.; Guo, S.S.; Ying, J. J.; Shan, C. X.; Sun, M. T.; Jiang, C. Z. Plasmon-DrivenReaction Controlled by the Number of Graphene Layers andLocalized Surface Plasmon Distribution during Optical Excitation.Light: Science & Applications 2015, 4 (10), No. e342.(41) Xu, H.; Xie, L.; Zhang, H.; Zhang, J. Effect of Graphene FermiLevel on the Raman Scattering Intensity of Molecules on Graphene.ACS Nano 2011, 5 (7), 5338−5344.(42) Xu, H.; Chen, Y.; Xu, W.; Zhang, H.; Kong, J.; Dresselhaus, M.S.; Zhang, J. Modulating the Charge-Transfer Enhancement in GERSUsing an Electrical Field under Vacuum and an n/p-DopingAtmosphere. Small 2011, 7 (20), 2945−2952.(43) Ling, X.; Wu, J.; Xu, W.; Zhang, J. Probing the Effect ofMolecular Orientation on the Intensity of Chemical EnhancementUsing Graphene-Enhanced Raman Spectroscopy. Small 2012, 8 (9),1365−1372.(44) Zhang, C.; Lin, K.; Huang, Y.; Zhang, J. Graphene-Ag Hybridson Laser-Textured Si Surface for SERS Detection. Sensors 2017, 17(7), 1462.(45) Osváth, Z.; Pálinkás, A.; Piszter, G.; Molnár, G. Synthesis andCharacterization of Graphene-Silver Nanoparticle Hybrid Materials.Materials 2020, 13 (20), 4660.(46) Gong, T.; Luo, Y.; Zhao, C.; Yue, W.; Zhang, J.; Zhu, Y.; Pu,M.; Zhang, Z.; Wang, C.; Luo, X. Highly Reproducible and StableSurface-Enhanced Raman Scattering Substrates of Graphene-AgNanohole Arrays Fabricated by Sub-Diffraction Plasmonic Lithog-raphy. OSA Contin 2019, 2 (3), 582.(47) Huttunen, M. J.; Rasekh, P.; Boyd, R. W.; Dolgaleva, K. UsingSurface Lattice Resonances to Engineer Nonlinear Optical Processesin Metal Nanoparticle Arrays. Phys. Rev. A 2018, 97 (5), 053817.(48) Juodenas, M.; Tamulevic ̌ius, T.; Henzie, J.; Erts, D.;Tamulevicǐus, S. Surface Lattice Resonances in Self-Assembled Arraysof Monodisperse Ag Cuboctahedra. ACS Nano 2019, 13 (8), 9038−9047.(49) Esteban, R.; Taylor, R. W.; Baumberg, J. J.; Aizpurua, J. HowChain Plasmons Govern the Optical Response in Strongly InteractingSelf-Assembled Metallic Clusters of Nanoparticles. Langmuir 2012, 28(24), 8881−8890.(50) Törmä, P.; Huttunen, M. J.; Dolgaleva, K.; Boyd, R. W. Ultra-Strong Polarization Dependence of Surface Lattice Resonances without-of-Plane Plasmon Oscillations. Opt. Express 2016, 24 (25),28279−28289.(51) Charconnet, M.; Kuttner, C.; Plou, J.; García-Pomar, J. L.;Mihi, A.; Liz-Marzán, L. M.; Seifert, A. Mechanically Tunable Lattice-Plasmon Resonances by Templated Self-Assembled Superlattices forMulti-Wavelength Surface-Enhanced Raman Spectroscopy. SmallMethods 2021, 5 (10), 2100453.(52) Ragheb, I.; Braïk, M.; Lau-Truong, S.; Belkhir, A.;Rumyantseva, A.; Kostcheev, S.; Adam, P. M.; Chevillot-Biraud, A.;Lévi, G.; Aubard, J.; et al. Surface Enhanced Raman Scattering onRegular Arrays of Gold Nanostructures: Impact of Long-RangeInteractions and the Surrounding Medium. Nanomaterials 2020, 10(11), 2201.(53) Weitz, D. A.; Garoff, S.; Gramila, T. J. Excitation Spectra ofSurface-Enhanced Raman Scattering on Silver-Island Films. Opt. Lett.1982, 7 (4), 168.(54) Félidj, N.; Aubard, J.; Lévi, G.; Krenn, J. R.; Hohenau, A.;Schider, G.; Leitner, A.; Aussenegg, F. R. Optimized Surface-Enhanced Raman Scattering on Gold Nanoparticle Arrays. Appl.Phys. Lett. 2003, 82 (18), 3095−3097.(55) Haynes, C. L.; Van Duyne, R. P. Plasmon-Sampled Surface-Enhanced Raman Excitation Spectroscopy. J. Phys. Chem. B 2003, 107(30), 7426−7433.(56) McFarland, A. D.; Young, M. A.; Dieringer, J. A.; Van Duyne,R. P. Wavelength-Scanned Surface-Enhanced Raman ExcitationSpectroscopy. J. Phys. Chem. B 2005, 109 (22), 11279−11285.(57) Chew, H.; Wang, D.-S.; Kerker, M. Surface Enhanced RamanScattering (SERS) by Molecules Adsorbed at Spherical Particles. Appl.Opt. 1980, 19 (19), 3373−3388.(58) Kumar, S.; Tokunaga, K.; Namura, K.; Fukuoka, T.; Suzuki, M.Experimental Evidence of a Twofold Electromagnetic EnhancementMechanism of Surface-Enhanced Raman Scattering. J. Phys. Chem. C2020, 124 (38), 21215−21222.(59) Tao, A.; Sinsermsuksakul, P.; Yang, P.; Tao, A.;Sinsermsuksakul, P.; Yang, P. Polyhedral Silver Nanocrystals withDistinct Scattering Signatures. Angew. Chem. Int. Ed 2006, 45, 4597−4601.(60) Juode ̇nas, M.; Khinevich, N.; Klyvis, G.; Henzie, J.;Tamulevicǐus, T.; Tamulevicǐus, S. Lasing in an Assembled Array ofSilver Nanocubes. Nanoscale Horiz. 2024, 10, 142−149.(61) Ni, S.; Isa, L.; Wolf, H. Capillary Assembly as a Tool for theHeterogeneous Integration of Micro- and Nanoscale Objects. SoftMatter 2018, 14 (16), 2978−2995.(62) Li, M.; Liu, D.; Wei, D. D.; Song, X.; Wei, D. D.; Wee, A. T. S.Controllable Synthesis of Graphene by Plasma-Enhanced ChemicalVapor Deposition and Its Related Applications. Advanced Science2016, 3 (11), 1600003.(63) Zhou, H.; Yu, W. J.; Liu, L.; Cheng, R.; Chen, Y.; Huang, X.;Liu, Y.; Wang, Y.; Huang, Y.; Duan, X. Chemical Vapour DepositionGrowth of Large Single Crystals of Monolayer and Bilayer Graphene.Nat. Commun. 2013, 4 (1), 1−8.(64) Shivayogimath, A.; Whelan, P. R.; MacKenzie, D. M. A.; Luo,B.; Huang, D.; Luo, D.; Wang, M.; Gammelgaard, L.; Shi, H.; Ruoff,R. S.; et al. Do-It-Yourself Transfer of Large-Area Graphene Using anOffice Laminator and Water. Chem. Mater. 2019, 31 (7), 2328−2336.(65) Tamulevicǐus, T.; Šeperys, R.; Andrulevicǐus, M.; Kopustinskas,V.; Mesǩinis, Š.; Tamulevicǐus, S.; Mikalayeva, V.; Daugelavicǐus, R.Application of Holographic Sub-Wavelength Diffraction Gratings forMonitoring of Kinetics of Bioprocesses. Appl. Surf. Sci. 2012, 258(23), 9292−9296.(66) Mazet, V. Background correction. Annu. Rep. Anal. At. Spectrosc.1983, 13, 52−54.(67) Juodeṅas, M.; Peckus, D.; Tamulevicǐus, T.; Yamauchi, Y.;Tamulevicǐus, S.; Henzie, J.; Henzie, J. Effect of Ag NanocubeOptomechanical Modes on Plasmonic Surface Lattice Resonances.ACS Photonics 2020, 7 (11), 3130−3140.(68) Hwangbo, Y.; Lee, C. K.; Mag-Isa, A. E.; Jang, J. W.; Lee, H. J.;Lee, S. B.; Kim, S. S.; Kim, J. H. Interlayer Non-Coupled OpticalProperties for Determining the Number of Layers in ArbitrarilyStacked Multilayer Graphenes. Carbon 2014, 77, 454−461.(69) Wang, H.; Wang, Y.; Cao, X.; Feng, M.; Lan, G. VibrationalProperties of Graphene and Graphene Layers. J. Raman Spectrosc.2009, 40 (12), 1791−1796.(70) Jorio, A. Raman Spectroscopy in Graphene-Based Systems:Prototypes for Nanoscience and Nanometrology. InternationalScholarly Research Notices 2012, 2012, 234216.(71) Monshi, M.; Moussavi, M.; Peckus, D.; Rajackaite ̇, E.;Vasiliauskas, A.; Andrulevicǐus, M.; Tamulevicǐus, T.; Tamulevicǐus,S. Correlation Study of Graphitic Shell Encapsulated Nickel: A Multi-Spectroscopic Approach. Carbon 2025, 232, 119704.(72) Agarwal, N. R.; Lucotti, A.; Tommasini, M.; Neri, F.; Trusso,S.; Ossi, P. M. SERS Detection and DFT Calculation of 2-The Journal of Physical Chemistry C pubs.acs.org/JPCC Articlehttps://doi.org/10.1021/acs.jpcc.5c02135J. Phys. Chem. C 2025, 129, 14983−1499214991https://doi.org/10.3390/chemosensors10080317https://doi.org/10.3390/chemosensors10080317https://doi.org/10.3390/nano11010216https://doi.org/10.3390/nano11010216https://doi.org/10.3390/nano11010216https://doi.org/10.1021/nl903414x?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/nl903414x?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1002/smll.201000918https://doi.org/10.1002/smll.201000918https://doi.org/10.1038/lsa.2015.115https://doi.org/10.1038/lsa.2015.115https://doi.org/10.1038/lsa.2015.115https://doi.org/10.1021/nn103237x?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/nn103237x?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1002/smll.201100546https://doi.org/10.1002/smll.201100546https://doi.org/10.1002/smll.201100546https://doi.org/10.1002/smll.201102223https://doi.org/10.1002/smll.201102223https://doi.org/10.1002/smll.201102223https://doi.org/10.3390/s17071462https://doi.org/10.3390/s17071462https://doi.org/10.3390/ma13204660https://doi.org/10.3390/ma13204660https://doi.org/10.1364/OSAC.2.000582https://doi.org/10.1364/OSAC.2.000582https://doi.org/10.1364/OSAC.2.000582https://doi.org/10.1364/OSAC.2.000582https://doi.org/10.1103/PhysRevA.97.053817https://doi.org/10.1103/PhysRevA.97.053817https://doi.org/10.1103/PhysRevA.97.053817https://doi.org/10.1021/acsnano.9b03191?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/acsnano.9b03191?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/la300198r?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/la300198r?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/la300198r?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1364/OE.24.028279https://doi.org/10.1364/OE.24.028279https://doi.org/10.1364/OE.24.028279https://doi.org/10.1002/smtd.202100453https://doi.org/10.1002/smtd.202100453https://doi.org/10.1002/smtd.202100453https://doi.org/10.3390/nano10112201https://doi.org/10.3390/nano10112201https://doi.org/10.3390/nano10112201https://doi.org/10.1364/OL.7.000168https://doi.org/10.1364/OL.7.000168https://doi.org/10.1063/1.1571979https://doi.org/10.1063/1.1571979https://doi.org/10.1021/jp027749b?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/jp027749b?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/jp050508u?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/jp050508u?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1364/AO.19.003373https://doi.org/10.1364/AO.19.003373https://doi.org/10.1021/acs.jpcc.0c07930?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/acs.jpcc.0c07930?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1002/anie.200601277https://doi.org/10.1002/anie.200601277https://doi.org/10.1039/D4NH00263Fhttps://doi.org/10.1039/D4NH00263Fhttps://doi.org/10.1039/C7SM02496Ghttps://doi.org/10.1039/C7SM02496Ghttps://doi.org/10.1002/advs.201600003https://doi.org/10.1002/advs.201600003https://doi.org/10.1038/ncomms3096https://doi.org/10.1038/ncomms3096https://doi.org/10.1021/acs.chemmater.8b04196?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/acs.chemmater.8b04196?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1016/j.apsusc.2012.04.022https://doi.org/10.1016/j.apsusc.2012.04.022https://doi.org/10.1039/aa9831300052https://doi.org/10.1021/acsphotonics.0c01187?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/acsphotonics.0c01187?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1016/j.carbon.2014.05.050https://doi.org/10.1016/j.carbon.2014.05.050https://doi.org/10.1016/j.carbon.2014.05.050https://doi.org/10.1002/jrs.2321https://doi.org/10.1002/jrs.2321https://doi.org/10.5402/2012/234216https://doi.org/10.5402/2012/234216https://doi.org/10.1016/j.carbon.2024.119704https://doi.org/10.1016/j.carbon.2024.119704https://doi.org/10.1016/j.snb.2016.06.143pubs.acs.org/JPCC?ref=pdfhttps://doi.org/10.1021/acs.jpcc.5c02135?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asNaphthalene Thiol Adsorbed on Ag and Au Probes. Sens Actuators BChem. 2016, 237, 545−555.(73) Son, J.; Kim, G. H.; Lee, Y.; Lee, C.; Cha, S.; Nam, J. M.Toward Quantitative Surface-Enhanced Raman Scattering withPlasmonic Nanoparticles: Multiscale View on Heterogeneities inParticle Morphology, Surface Modification, Interface, and AnalyticalProtocols. J. Am. Chem. Soc. 2022, 144 (49), 22337−22351.(74) Yaghobian, F.; Korn, T.; Schüller, C. Frequency Shift inGraphene-Enhanced Raman Signal of Molecules. ChemPhysChem2012, 13 (18), 4271−4275.(75) Arshad, F.; Nabi, F.; Iqbal, S.; Khan, R. H. Applications ofGraphene-Based Electrochemical and Optical Biosensors in EarlyDetection of Cancer Biomarkers. Colloids Surf. B Biointerfaces 2022,212, 112356.(76) Karton, A. π-π Interactions between Benzene and Graphene byMeans of Large-Scale DFT-D4 Calculations. Chem. Phys. 2022, 561,111606.(77) Lechner, C.; Sax, A. F. Adhesive Forces between AromaticMolecules and Graphene. J. Phys. Chem. C 2014, 118 (36), 20970−20981.(78) Yoon, J. C.; Thiyagarajan, P.; Ahn, H. J.; Jang, J. H. A CaseStudy: Effect of Defects in CVD-Grown Graphene on GrapheneEnhanced Raman Spectroscopy. RSC Adv. 2015, 5 (77), 62772−62777.(79) Smith, R. S.; Kay, B. D. Desorption Kinetics of Benzene andCyclohexane from a Graphene Surface. J. Phys. Chem. B 2018, 122(2), 587−594.(80) Chakradhar, A.; Sivapragasam, N.; Nayakasinghe, M. T.;Burghaus, U. Adsorption Kinetics of Benzene on Graphene: AnUltrahigh Vacuum Study. Journal of Vacuum Science & Technology A:Vacuum, Surfaces, and Films 2016, 34 (2), 021402.The Journal of Physical Chemistry C pubs.acs.org/JPCC Articlehttps://doi.org/10.1021/acs.jpcc.5c02135J. Phys. Chem. C 2025, 129, 14983−1499214992https://doi.org/10.1016/j.snb.2016.06.143https://doi.org/10.1021/jacs.2c05950?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/jacs.2c05950?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/jacs.2c05950?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/jacs.2c05950?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1002/cphc.201200642https://doi.org/10.1002/cphc.201200642https://doi.org/10.1016/j.colsurfb.2022.112356https://doi.org/10.1016/j.colsurfb.2022.112356https://doi.org/10.1016/j.colsurfb.2022.112356https://doi.org/10.1016/j.chemphys.2022.111606https://doi.org/10.1016/j.chemphys.2022.111606https://doi.org/10.1021/jp505894p?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/jp505894p?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1039/C5RA11100Ehttps://doi.org/10.1039/C5RA11100Ehttps://doi.org/10.1039/C5RA11100Ehttps://doi.org/10.1021/acs.jpcb.7b05102?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1021/acs.jpcb.7b05102?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://doi.org/10.1116/1.4936337https://doi.org/10.1116/1.4936337pubs.acs.org/JPCC?ref=pdfhttps://doi.org/10.1021/acs.jpcc.5c02135?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://www.cas.org/solutions/biofinder-discovery-platform?utm_campaign=GLO_ACD_STH_BDP_AWS&utm_medium=DSP_CAS_PAD&utm_source=Publication_ACSPubs