Investigation of Mass-Produced Substrates for Reproducible Surface-Enhanced Raman Scattering Measurements over Large Areas.

Surface-enhanced Raman scattering (SERS) is a versatile spectroscopic technique that suffers from reproducibility issues and usually requires complex substrate fabrication processes. In this article, we report the use of a simple mass production technology based on Blu-ray disc manufacturing technology to prepare large area SERS substrates (∼40 mm2) with a high degree of homogeneity (±7% variation in Raman signal) and enhancement factor of ∼6 × 106. An industrial high throughput injection molding process was used to generate periodic microstructured polymer substrates coated with a thin Ag film. A short chemical etching step produces a highly dense layer of Ag nanoparticles at the polymer surface, which leads to a large and reproducible Raman signal. Finite difference time domain simulations and cathodoluminescence mapping experiments suggest that the sample microstructure is responsible for the generation of SERS active nanostructures around the microwells. Comparison with commercial SERS substrates demonstrates the validity of our method to prepare cost-efficient, reliable, and sensitive SERS substrates.

[1]  Nicolas Guillot,et al.  The electromagnetic effect in surface enhanced Raman scattering: Enhancement optimization using precisely controlled nanostructures , 2012 .

[2]  Younan Xia,et al.  Surface-enhanced Raman scattering: comparison of three different molecules on single-crystal nanocubes and nanospheres of silver. , 2009, The journal of physical chemistry. A.

[3]  M. Ekpanyapong,et al.  Highly-Sensitive Surface-Enhanced Raman Spectroscopy (SERS)-based Chemical Sensor using 3D Graphene Foam Decorated with Silver Nanoparticles as SERS substrate , 2016, Scientific Reports.

[4]  Shuming Nie,et al.  Direct Observation of Size-Dependent Optical Enhancement in Single Metal Nanoparticles , 1998 .

[5]  Sebastian Schlücker,et al.  SERS microscopy: nanoparticle probes and biomedical applications. , 2009, Chemphyschem : a European journal of chemical physics and physical chemistry.

[6]  J. Lombardi,et al.  Review of Surface Enhanced Raman Scattering Applications in Forensic Science. , 2016, Analytical chemistry.

[7]  Suhee Choi,et al.  Highly reproducible surface-enhanced Raman scattering-active Au nanostructures prepared by simple electrodeposition: origin of surface-enhanced Raman scattering activity and applications as electrochemical substrates. , 2013, Analytica chimica acta.

[8]  Odile Stéphan,et al.  Mapping plasmons at the nanometer scale in an electron microscope. , 2014, Chemical Society reviews.

[9]  N. P. Economou,et al.  Surface-enhanced raman scattering from microlithographic silver particle surfaces , 1981 .

[10]  A. Aspuru‐Guzik,et al.  On the chemical bonding effects in the Raman response: benzenethiol adsorbed on silver clusters. , 2009, Physical chemistry chemical physics : PCCP.

[11]  Bich Ha Nguyen,et al.  Rich variety of substrates for surface enhanced Raman spectroscopy , 2016 .

[12]  L. Brus,et al.  Electrochemical ostwald ripening of colloidal ag particles on conductive substrates. , 2005, Nano letters.

[13]  Caryn S. Seney,et al.  Correlation of Size and Surface-Enhanced Raman Scattering Activity of Optical and Spectroscopic Properties for Silver Nanoparticles , 2009 .

[14]  N. Fang,et al.  Imaging of plasmonic modes of silver nanoparticles using high-resolution cathodoluminescence spectroscopy. , 2009, ACS nano.

[15]  Lixin Xia,et al.  Self-assembled dynamics of silver nanoparticles and self-assembled dynamics of 1,4-benzenedithiol adsorbed on silver nanoparticles: Surface-enhanced Raman scattering study. , 2009, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[16]  Yoon Sup Lee,et al.  Raman spectroscopic study of 1,2-ethanedithiol adsorbed on silver surface , 1989 .

[17]  S. Mátéfi-Tempfli,et al.  On-substrate, self-standing Au-nanorod arrays showing morphology controlled properties , 2011 .

[18]  K. Mogensen,et al.  Plasmon resonances of Ag capped Si nanopillars fabricated using mask-less lithography. , 2015, Optics express.

[19]  Wang Lin,et al.  Surface-enhanced Raman scattering and density functional theory study of 1,4-benzenedithiol and its silver complexes. , 2013, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[20]  Jörg Hübner,et al.  Large Area Fabrication of Leaning Silicon Nanopillars for Surface Enhanced Raman Spectroscopy , 2012, Advanced materials.

[21]  Elizabeth Vargis,et al.  Nanoparticle Properties and Synthesis Effects on Surface-Enhanced Raman Scattering Enhancement Factor: An Introduction , 2015, TheScientificWorldJournal.

[22]  A. Boisen,et al.  Detection of nerve gases using surface-enhanced Raman scattering substrates with high droplet adhesion. , 2016, Nanoscale.

[23]  Meikun Fan,et al.  A review on the fabrication of substrates for surface enhanced Raman spectroscopy and their applications in analytical chemistry. , 2011, Analytica chimica acta.

[24]  Xiaoping Song,et al.  A route to increase the enhancement factor of surface enhanced Raman scattering (SERS) via a high density Ag flower-like pattern , 2008 .

[25]  L. Brus,et al.  Optical forces between metallic particles. , 2005, Proceedings of the National Academy of Sciences of the United States of America.

[26]  Liguang Xu,et al.  Building SERS-active heteroassemblies for ultrasensitive Bisphenol A detection. , 2016, Biosensors & bioelectronics.

[27]  N. Larsen,et al.  Injection molding of high aspect ratio sub-100 nm nanostructures , 2013 .

[28]  Pablo G. Etchegoin,et al.  Surface Enhanced Raman Scattering Enhancement Factors: A Comprehensive Study , 2007 .

[29]  S. Schlücker Surface-enhanced Raman spectroscopy: concepts and chemical applications. , 2014, Angewandte Chemie.

[30]  G. Ayoko,et al.  Reproducible and label-free biosensor for the selective extraction and rapid detection of proteins in biological fluids , 2015, Journal of Nanobiotechnology.

[31]  P. Liao,et al.  Surface-enhanced Raman scattering on gold and aluminum particle arrays. , 1982, Optics letters.

[32]  Jürgen Popp,et al.  The many facets of Raman spectroscopy for biomedical analysis , 2014, Analytical and Bioanalytical Chemistry.

[33]  G. Stucky,et al.  Large Format Surface-Enhanced Raman Spectroscopy Substrate Optimized for Enhancement and Uniformity. , 2016, ACS nano.

[34]  Shengli Zou,et al.  Mechanistic Study of Continuous Reactive Aromatic Organothiol Adsorption onto Silver Nanoparticles , 2013 .

[35]  Peter T C So,et al.  High resolution live cell Raman imaging using subcellular organelle-targeting SERS-sensitive gold nanoparticles with highly narrow intra-nanogap. , 2015, Nano letters.

[36]  N. Gadegaard,et al.  Injection moulding of ultra high aspect ratio nanostructures using coated polymer tooling , 2014 .

[37]  A. Shen,et al.  Combined Labelled and Label-free SERS Probes for Triplex Three-dimensional Cellular Imaging , 2016, Scientific Reports.

[38]  M. Temperini,et al.  Critical assessment of enhancement factor measurements in surface-enhanced Raman scattering on different substrates. , 2015, Physical chemistry chemical physics : PCCP.

[39]  Pablo G. Etchegoin,et al.  Rigorous justification of the |E|4 enhancement factor in Surface Enhanced Raman Spectroscopy☆ , 2006 .

[40]  Qiangfei Xia,et al.  Fractal structure formation from Ag nanoparticle films on insulating substrates. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[41]  R. Frontiera,et al.  SERS: Materials, applications, and the future , 2012 .

[42]  H. S. Han,et al.  Raman-Spectroscopic Study of 1,4-Benzenedithiol Adsorbed on Silver , 1995 .

[43]  Christy L. Haynes,et al.  Plasmon-Sampled Surface-Enhanced Raman Excitation Spectroscopy † , 2003 .

[44]  George C. Schatz,et al.  Modeling the effect of small gaps in surface-enhanced Raman spectroscopy , 2012 .

[45]  A. Boisen,et al.  Silver‐capped silicon nanopillar platforms for adsorption studies of folic acid using surface enhanced Raman spectroscopy and density functional theory , 2015 .

[46]  T. Krauss,et al.  Aging induced Ag nanoparticle rearrangement under ambient atmosphere and consequences for nanoparticle-enhanced DNA biosensing. , 2010, Analytical chemistry.

[47]  Michael S. Feld,et al.  SURFACE-ENHANCED RAMAN SCATTERING : A NEW TOOL FOR BIOMEDICAL SPECTROSCOPY , 1999 .

[48]  Zhilin Yang,et al.  A facile method for the synthesis of large‐size Ag nanoparticles as efficient SERS substrates , 2016 .

[49]  Jeffrey N. Anker,et al.  Surface-enhanced Raman spectroscopy of benzenethiol adsorbed from the gas phase onto silver film over nanosphere surfaces: determination of the sticking probability and detection limit time. , 2009, The journal of physical chemistry. A.

[50]  S. Joo,et al.  Adsorption of 1,4-Benzenedithiol on Gold and Silver Surfaces: Surface-Enhanced Raman Scattering Study. , 2001, Journal of colloid and interface science.

[51]  C. Kendall,et al.  Raman spectroscopy for medical diagnostics--From in-vitro biofluid assays to in-vivo cancer detection. , 2015, Advanced drug delivery reviews.

[52]  G. Glaspell,et al.  Surface Enhanced Raman Spectroscopy Using Silver Nanoparticles: The Effects of Particle Size and Halide Ions on Aggregation , 2005 .

[53]  L. Fu,et al.  Ultrasensitive SERS performance in 3D "sunflower-like" nanoarrays decorated with Ag nanoparticles. , 2017, Nanoscale.

[54]  Matthew N. O’Brien,et al.  Uniform circular disks with synthetically tailorable diameters: two-dimensional nanoparticles for plasmonics. , 2015, Nano letters.

[55]  P. Vikesland,et al.  Surface-Enhanced Raman Spectroscopy (SERS) Cellular Imaging of Intracellulary Biosynthesized Gold Nanoparticles , 2014 .

[56]  Zhibin Chen,et al.  Research on the temperature effect characteristics of SERS enhancement factor , 2016 .

[57]  S. Joo,et al.  Interfacial Structure of 1,3-Benzenedithiol and 1,3-Benzenedimethanethiol on Silver Surfaces : Surface-Enhanced Raman Scattering Study and Theoretical Calculations , 2008 .

[58]  Yong‐Lai Zhang,et al.  Superhydrophobic SERS Substrates Based on Silver-Coated Reduced Graphene Oxide Gratings Prepared by Two-Beam Laser Interference. , 2015, ACS applied materials & interfaces.

[59]  Yibin Ying,et al.  Reproducible E. coli detection based on label-free SERS and mapping. , 2016, Talanta.

[60]  Younan Xia,et al.  Silver nanocrystals with concave surfaces and their optical and surface-enhanced Raman scattering properties. , 2011, Angewandte Chemie.

[61]  Haibo Zhou,et al.  Early apoptosis real-time detection by label-free SERS based on externalized phosphatidylserine. , 2016, The Analyst.

[62]  Soumyo Mukherji,et al.  Size-controlled silver nanoparticles synthesized over the range 5–100 nm using the same protocol and their antibacterial efficacy , 2014 .

[63]  Ya-Hong Xie,et al.  Label-Free SERS Selective Detection of Dopamine and Serotonin Using Graphene-Au Nanopyramid Heterostructure. , 2015, Analytical chemistry.

[64]  M. Ritala,et al.  High Aspect-Ratio Iridium-Coated Nanopillars for Highly Reproducible Surface-Enhanced Raman Scattering (SERS). , 2015, ACS applied materials & interfaces.

[65]  T. S. Alstrøm,et al.  Mathematical Model for Biomolecular Quantification Using Large-Area Surface-Enhanced Raman Spectroscopy Mapping. , 2015, RSC advances.

[66]  Homan Kang,et al.  Ag shell-Au satellite hetero-nanostructure for ultra-sensitive, reproducible, and homogeneous NIR SERS activity. , 2014, ACS applied materials & interfaces.

[67]  S. Nie,et al.  Single-Molecule and Single-Nanoparticle SERS: From Fundamental Mechanisms to Biomedical Applications , 2008 .

[68]  Yue-sheng Li,et al.  Synthesis of High Performance Cyclic Olefin Polymers (COPs) with Ester Group via Ring-Opening Metathesis Polymerization , 2015 .