Controlling the properties of silver nanoparticles deposited on surfaces using supercritical carbon dioxide for surface-enhanced Raman spectroscopy

Silver nanoparticles (AgNPs) have been deposited on silicon and glass surfaces via a supercritical carbon dioxide (sc-CO2) synthesis route for application in surface-enhanced Raman spectroscopy (SERS). Arrhenius plots revealed that nucleation and growth processes in this system depend on both temperature and surface chemistry. Results also demonstrated that temperature and surface chemistry could be varied to control nanoparticle properties, such as the mean nanoparticle size, density, and surface coverage, providing two useful variables for manipulating the properties of AgNPs deposited on surfaces in this system. These data also provide scientific insight into the underlying mechanisms governing heterogeneous AgNP deposition on a substrate in a sc-CO2 system in addition to engineering insight into the variables that can be used to manipulate AgNP characteristics. The mean particle size could be tuned over the range 20–200 nm, the interparticle distance could be tuned over the range 70 nm–1 μm, and the surface coverage could be tuned over the range 0.035–0.58. Products were analyzed by scanning electron microscopy with image analysis, transmission electron microscopy, X-ray diffraction, and SERS. The silver nanoparticle-coated substrates were successfully applied in SERS, detecting the model analyte Rhodamine 6G at a concentration of 1 μM, a three orders of magnitude improvement over SERS surfaces previously fabricated in sc-CO2 systems. Such surfaces can find use in trace concentration analyte detection in biomedical, chemical, and environmental applications.

[1]  Henry Du,et al.  In situ SERS study of Rhodamine 6G adsorbed on individually immobilized Ag nanoparticles , 2006 .

[2]  H. S. Fogler,et al.  Elements of Chemical Reaction Engineering , 1986 .

[3]  Yiping Zhao,et al.  Silver Nanorod Array Substrates Fabricated by Oblique Angle Deposition: Morphological, Optical, and SERS Characterizations , 2010 .

[4]  P. Hildebrandt,et al.  Surface-enhanced resonance Raman spectroscopy of Rhodamine 6G adsorbed on colloidal silver , 1984 .

[5]  C. Eckert,et al.  Phase Behavior and Modeling of CO2/Methanol/Tetramethylammonium Bicarbonate and CO2/Methanol/Tetramethylammonium Bicarbonate/Water Mixtures at High Pressures , 2004 .

[6]  M. Hosseinpour,et al.  Hydrothermal Synthesis of CuO Nanoparticles: Study on Effects of Operational Conditions on Yield, Purity, and Size of the Nanoparticles , 2011 .

[7]  C. Wai,et al.  ChemInform Abstract: Synthesis of Silver and Copper Nanoparticles in a Water-in-Supercritical-Carbon Dioxide Microemulsion. , 2002 .

[8]  Qin Zhou,et al.  Arrays of aligned, single crystalline silver nanorods for trace amount detection , 2008 .

[9]  James J. Watkins,et al.  Deposition of Copper by the H 2-Assisted Reduction of Cu ( tmod ) 2 in Supercritical Carbon Dioxide : Kinetics and Reaction Mechanism , .

[10]  M. Engelhard,et al.  Immersion Deposition of Metal Films on Silicon and Germanium Substrates in Supercritical Carbon Dioxide , 2003 .

[11]  J. Watkins,et al.  Deposition of Cu films from supercritical fluids using Cu(I) β-diketonate precursors , 2002 .

[12]  B. Vlčková,et al.  SERS-activating effect of chlorides on borate-stabilized silver nanoparticles: formation of new reduced adsorption sites and induced nanoparticle fusion. , 2008, Physical chemistry chemical physics : PCCP.

[13]  Yong Wang,et al.  Supercritical fluid synthesis and characterization of catalytic metal nanoparticles on carbon nanotubes , 2004 .

[14]  T. J. McCarthy,et al.  Chemical Fluid Deposition: Reactive Deposition of Platinum Metal from Carbon Dioxide Solution , 1999 .

[15]  A. Bruckbauer,et al.  On the chloride activation in SERS and single molecule SERS , 2003 .

[16]  Li Lu,et al.  Hydrothermal synthesis of MnO2/CNT nanocomposite with a CNT core/porous MnO2 sheath hierarchy architecture for supercapacitors , 2012, Nanoscale Research Letters.

[17]  Yuehe Lin,et al.  PtRu/carbon nanotube nanocomposite synthesized in supercritical fluid: a novel electrocatalyst for direct methanol fuel cells. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[18]  James J. Watkins,et al.  Deposition of Copper by the H2-Assisted Reduction of Cu(tmod)2 in Supercritical Carbon Dioxide: Kinetics and Reaction Mechanism , 2005 .

[19]  J. K. Yoon,et al.  Novel fabrication of Ag thin film on glass for efficient surface-enhanced Raman scattering. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[20]  H. Shinno,et al.  Growth of silicon oxide on silicon in the thin film region in an oxygen plasma , 1992 .

[21]  Yuehe Lin,et al.  Platinum/Carbon nanotube nanocomposite synthesized in supercritical fluid as electrocatalysts for low-temperature fuel cells. , 2005, The journal of physical chemistry. B.

[22]  R. Penner,et al.  Investigations of Electrochemical Silver Nanocrystal Growth on Hydrogen-Terminated Silicon(100) , 1999 .

[23]  Madhu Anand,et al.  Precise and rapid size selection and targeted deposition of nanoparticle populations using CO2 gas expanded liquids. , 2005, Nano letters.

[24]  P. D. Brown,et al.  Silver Nanoparticle Impregnated Polycarbonate Substrates for Surface Enhanced Raman Spectroscopy , 2008 .

[25]  W. Cheng,et al.  Supercritical carbon dioxide-assisted synthesis of silver nano-particles in polyol process , 2007 .

[26]  C. Haynes,et al.  Nanosphere lithography: Tunable localized surface plasmon resonance spectra of silver nanoparticles , 2000 .

[27]  Kevin G. Stamplecoskie,et al.  Optimal Size of Silver Nanoparticles for Surface-Enhanced Raman Spectroscopy , 2011 .

[28]  C. Wai,et al.  Synthesizing and Dispersing Silver Nanoparticles in a Water-in-Supercritical Carbon Dioxide Microemulsion. , 1999, Journal of the American Chemical Society.

[29]  N. Minaev,et al.  Synthesis of silver nanocomposites by SCF impregnation of matrices of synthetic opal and Vycor glass by the Ag(hfac)COD precursor , 2009 .

[30]  Yiping Zhao,et al.  Aligned silver nanorod arrays produce high sensitivity surface-enhanced Raman spectroscopy substrates , 2005 .

[31]  Edgar Voges,et al.  Periodically structured metallic substrates for SERS , 1998 .

[32]  P. Temple,et al.  Multiphonon Raman Spectrum of Silicon , 1973 .

[33]  Ajay Agarwal,et al.  3D arrays of SERS substrate for ultrasensitive molecular detection , 2007 .

[34]  Hugh J. Byrne,et al.  A Comparative Study of the Interaction of Different Polycyclic Aromatic Hydrocarbons on Different Types of Single Walled Carbon Nanotubes , 2010 .

[35]  Sabine Szunerits,et al.  Silicon nanowires coated with silver nanostructures as ultrasensitive interfaces for surface-enhanced Raman spectroscopy. , 2009, ACS applied materials & interfaces.

[36]  Ramasamy Manoharan,et al.  Extremely Large Enhancement Factors in Surface-Enhanced Raman Scattering for Molecules on Colloidal Gold Clusters , 1998 .

[37]  Barnett F. Dodge,et al.  Chemical engineering thermodynamics , 1944 .

[38]  R. V. Van Duyne,et al.  Localized surface plasmon resonance spectroscopy and sensing. , 2007, Annual review of physical chemistry.

[39]  K. Arai,et al.  Hydrothermal Synthesis of Metal Oxide Nanoparticles at Supercritical Conditions , 2000 .