Silicon-Based SERS Substrates Fabricated by Electroless Etching

Surface enhanced Raman scattering has recently been proposed as a label free sensing method for diagnostic applications. Raman scattering is an excellent analysis tool because a wealth of information can be obtained using a single measurement, however the weak signal has made it unsuitable for detecting low concentrations of analytes. Using plasmonic nanostructures to create SERS substrates, the Raman signal can be amplified by several orders of magnitude, but SERS substrates have been complicated to fabricate. Here we report low-cost silicon substrates based on simple fabrication method of silver nanoparticles and silicon nanowires decorated with these nanoparticles for use as a convenient practical platform for SERS-active substrates. In addition, the placement of silver nanoparticles on silicon nanowires allowed the autoaligning of the hot spots such that low cost Raman systems with normal incident laser can be used. These substrates have the ability to detect wide range of concentrations of pyridine, as low as 10 –11 M. An enhancement factor of around 6 to 8 × 105 was observed for silver nanoparticles alone. By depositing the same nanoparticles on silicon nanowires, the enhancement factor jumped by orders of magnitude to 1011.

[1]  A. Campion,et al.  Surface-enhanced Raman scattering , 1998 .

[2]  Yingfeng Li,et al.  Silicon nanowire arrays coated with electroless Ag for increased surface-enhanced Raman scattering , 2015 .

[3]  Mohamed A. Swillam,et al.  Efficient fabrication methodology of wide angle black silicon for energy harvesting applications , 2017 .

[4]  B. Man,et al.  Gold@silver bimetal nanoparticles/pyramidal silicon 3D substrate with high reproducibility for high-performance SERS , 2016, Scientific Reports.

[5]  Mohamed A. Swillam,et al.  Vertically aligned crystalline silicon nanowires with controlled diameters for energy conversion applications: Experimental and theoretical insights , 2014 .

[6]  Chao Zhang,et al.  A sensitive, uniform, reproducible and stable SERS substrate has been presented based on MoS2@Ag nanoparticles@pyramidal silicon , 2017 .

[7]  Anand Gole,et al.  Surface-enhanced Raman spectroscopy of self-assembled monolayers: sandwich architecture and nanoparticle shape dependence. , 2005, Analytical chemistry.

[8]  Dinesh Kumar,et al.  Large area fabrication of vertical silicon nanowire arrays by silver-assisted single-step chemical etching and their formation kinetics , 2014, Nanotechnology.

[9]  Junyong Kang,et al.  Surface enhanced Raman scattering of pyridine adsorbed on Au@Pd core/shell nanoparticles. , 2009, The Journal of chemical physics.

[10]  Samuel Hoffmann,et al.  Nanowires enabling signal-enhanced nanoscale Raman spectroscopy. , 2008, Small.

[11]  Charles M. Lieber,et al.  Coaxial silicon nanowires as solar cells and nanoelectronic power sources , 2007, Nature.

[12]  Longhua Tang,et al.  Improved Surface Enhanced Raman Scattering Based on Hybrid Au Nanostructures for Biomolecule Detection , 2016, IEEE Photonics Journal.

[13]  Laurence Latu-Romain,et al.  Growth parameters and shape specific synthesis of silicon nanowires by the VLS method , 2008 .

[14]  E. Palik.  Handbook of Optical Constants of Solids , 1997 .

[15]  Bodo Fuhrmann,et al.  Ordered arrays of silicon nanowires produced by nanosphere lithography and molecular beam epitaxy. , 2005, Nano letters.

[16]  Mohamed A. Swillam,et al.  Facile omnidirectional black silicon based on porous and nonporous silicon nanowires for energy applications , 2016, 2016 Photonics North (PN).

[17]  Kui Zhang,et al.  An effective three-dimensional surface-enhanced Raman scattering substrate based on oblique Si nanowire arrays decorated with Ag nanoparticles , 2016, Journal of Materials Science.

[18]  Yit-Tsong Chen,et al.  Catalytic Growth of Silicon Nanowires Assisted by Laser Ablation , 2004 .

[19]  Lih-Juann Chen,et al.  Silicon nanowires: the key building block for future electronic devices , 2007 .

[20]  Zhipeng Huang,et al.  Metal-assisted chemical etching of silicon and nanotechnology applications , 2014 .

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

[22]  A. Nassiopoulou,et al.  Si nanowires by a single-step metal-assisted chemical etching process on lithographically defined areas: formation kinetics , 2011, Nanoscale research letters.

[23]  H. Gerischer,et al.  Surface enhanced Raman scattering from pyridine and halide ions adsorbed on silver and gold sol particles , 1980 .

[24]  Alessandro Alabastri,et al.  Plasmon based biosensor for distinguishing different peptides mutation states , 2013, Scientific Reports.

[25]  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.

[26]  Hui Pan,et al.  Growth of Si nanowires by thermal evaporation , 2005 .

[27]  Mohamed A. Swillam,et al.  Black silicon based on simple fabrication of mesoporous silicon nanowires for solar energy harvesting , 2016, 2016 IEEE 43rd Photovoltaic Specialists Conference (PVSC).

[28]  R. W. Christy,et al.  Optical Constants of the Noble Metals , 1972 .

[29]  A. Henglein,et al.  Laser ablation of films and suspended particles in a solvent : formation of cluster and colloid solutions , 1993 .

[30]  J. M. Harris,et al.  Characterization of silane-modified immobilized gold colloids as a substrate for surface-enhanced Raman spectroscopy. , 2001, Analytical chemistry.

[31]  Dinesh Kumar,et al.  Room temperature growth of wafer-scale silicon nanowire arrays and their Raman characteristics , 2010 .

[32]  Eric C. Le Ru,et al.  Principles of Surface-Enhanced Raman Spectroscopy: And Related Plasmonic Effects , 2008 .

[33]  Alexandre G. Brolo,et al.  Surface-Enhanced Raman Spectra of Pyridine and Pyrazine Adsorbed on a Au(210) Single-Crystal Electrode , 1997 .

[34]  Zoraida P. Aguilar,et al.  Shape-dependent surface-enhanced Raman scattering in gold–Raman-probe–silica sandwiched nanoparticles for biocompatible applications , 2012, Nanotechnology.

[35]  Meizhen Huang,et al.  Raman Enhancement in Metal-Cladding Waveguide and the Influence of the Metal Film Surface Roughness , 2016, Journal of Lightwave Technology.

[36]  S. T. Lee,et al.  Fabrication of Single‐Crystalline Silicon Nanowires by Scratching a Silicon Surface with Catalytic Metal Particles , 2006 .

[37]  David A. Weitz,et al.  Colloidal aggregation revisited: New insights based on fractal structure and surface-enhanced Raman scattering , 1985 .

[38]  Yong Qing Fu,et al.  Deep reactive ion etching as a tool for nanostructure fabrication , 2009 .

[39]  Andrea Toma,et al.  Breaking the diffusion limit with super-hydrophobic delivery of molecules to plasmonic nanofocusing SERS structures , 2011 .

[40]  L. Liz‐Marzán,et al.  High-yield synthesis and optical response of gold nanostars , 2008, Nanotechnology.

[41]  Lucian Baia,et al.  Controlling gold nanoparticle assemblies for efficient surface-enhanced Raman scattering and localized surface plasmon resonance sensors , 2007 .

[42]  David L. Carroll,et al.  Synthesis and Characterization of Truncated Triangular Silver Nanoplates , 2002 .

[43]  J. Teng,et al.  High aspect ratio SiNW arrays with Ag nanoparticles decoration for strong SERS detection , 2014, Nanotechnology.

[44]  R. S. Wagner,et al.  VAPOR‐LIQUID‐SOLID MECHANISM OF SINGLE CRYSTAL GROWTH , 1964 .

[45]  Mohamed A. Swillam,et al.  Silicon-based nanostructures as surface enhanced Raman scattering substrates , 2016, 2016 Photonics North (PN).

[46]  Marek Procházka,et al.  SE(R)RS microspectroscopy of porphyrins on immobilized Au nanoparticles: Testing spectral sensitivity and reproducibility , 2012 .

[47]  Mohamed A. Swillam,et al.  Optical biosensor based on a silicon nanowire ridge waveguide for lab on chip applications , 2015 .

[48]  Ratan Das,et al.  Synthesis of silver nanoparticles and their optical properties , 2010 .

[49]  Zhongwei Chen,et al.  Subeutectic growth of single-crystal silicon nanowires grown on and wrapped with graphene nanosheets: high-performance anode material for lithium-ion battery. , 2014, ACS applied materials & interfaces.

[50]  Younan Xia,et al.  Shape‐Controlled Synthesis of Gold and Silver Nanoparticles. , 2003 .