Gold Nanoparticle Monolayers with Tunable Optical and Electrical Properties.

Centimeter-scale gold nanoparticle (Au NP) monolayer films have been fabricated using a water/organic solvent self-assembly strategy. A recently developed approach, drain to deposit, is demonstrated to be most effective in transferring the Au NP films from the water/organic solvent interface to various solid substrates while maintaining their integrity. The interparticle spacing was tuned from 1.4 to 3.1 nm using alkylamine ligands of different lengths. The ordering of the films increased with increasing ligand length. The surface plasmon resonance and the in-plane electrical conductivity of the Au NP films both exhibit an exponential dependence on the interparticle spacing. These findings show great potential in scaling up the manufacturing of high-performance optical and electronic devices based on two-dimensional metallic nanoparticle superlattices.

[1]  R. Marcus,et al.  Electron transfers in chemistry and biology , 1985 .

[2]  C D Frisbie,et al.  Fabrication and characterization of metal-molecule-metal junctions by conducting probe atomic force microscopy. , 2001, Journal of the American Chemical Society.

[3]  K. B. Blodgett.  Films Built by Depositing Successive Monomolecular Layers on a Solid Surface , 1935 .

[4]  J. Crocker,et al.  Nanoparticles at fluid interfaces: exploiting capping ligands to control adsorption, stability and dynamics. , 2012, Journal of colloid and interface science.

[5]  Raffaella Buonsanti,et al.  Exceptionally mild reactive stripping of native ligands from nanocrystal surfaces by using Meerwein's salt. , 2012, Angewandte Chemie.

[6]  Linfeng Hu,et al.  Oil-water interfacial self-assembly: a novel strategy for nanofilm and nanodevice fabrication. , 2012, Chemical Society reviews.

[7]  Yaochun Shen,et al.  SURFACE-ENHANCED SECOND-HARMONIC GENERATION AND RAMAN SCATTERING , 1983 .

[8]  D. Boda,et al.  The effect of concentration- and temperature-dependent dielectric constant on the activity coefficient of NaCl electrolyte solutions. , 2014, The Journal of chemical physics.

[9]  Shaowei Chen.  Discrete charge transfer in nanoparticle solid films , 2007 .

[10]  James R. Heath,et al.  Synthesis and Characterization of Hydrophobic, Organically-Soluble Gold Nanocrystals Functionalized with Primary Amines , 1996 .

[11]  R. Nuzzo,et al.  Synthesis, Structure, and Properties of Model Organic Surfaces , 1992 .

[12]  Y. Zu,et al.  Gold nanoparticle-modified ITO electrode for electrogenerated chemiluminescence: well-preserved transparency and highly enhanced activity. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[13]  A Paul Alivisatos,et al.  Localized surface plasmon resonances arising from free carriers in doped quantum dots. , 2011, Nature materials.

[14]  M. Reed,et al.  Microfabrication of a Mechanically Controllable Break Junction in Silicon , 1995 .

[15]  C. Frisbie,et al.  Length-dependent transport in molecular junctions based on SAMs of alkanethiols and alkanedithiols: effect of metal work function and applied bias on tunneling efficiency and contact resistance. , 2004, Journal of the American Chemical Society.

[16]  D. Allara,et al.  Spontaneously organized molecular assemblies. 4. Structural characterization of n-alkyl thiol monolayers on gold by optical ellipsometry, infrared spectroscopy, and electrochemistry , 1987 .

[17]  G. Schatz,et al.  Confined plasmons in nanofabricated single silver particle pairs: experimental observations of strong interparticle interactions. , 2005, The journal of physical chemistry. B.

[18]  Larry A. Nagahara,et al.  Electron Transport Properties of a Carotene Molecule in a Metal−(Single Molecule)−Metal Junction , 2003 .

[19]  George Chumanov,et al.  Light-induced coherent interactions between silver nanoparticles in two-dimensional arrays. , 2003, Journal of the American Chemical Society.

[20]  E. Kumacheva,et al.  Properties and emerging applications of self-assembled structures made from inorganic nanoparticles. , 2010, Nature nanotechnology.

[21]  G. Whitesides,et al.  Formation of monolayer films by the spontaneous assembly of organic thiols from solution onto gold , 1989 .

[22]  Sang-Kee Eah,et al.  Charged gold nanoparticles in non-polar solvents: 10-min synthesis and 2D self-assembly. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[23]  E. Lörtscher,et al.  Break-junctions for investigating transport at the molecular scale , 2014, Journal of physics. Condensed matter : an Institute of Physics journal.

[24]  J. R. Sambles,et al.  Optical characterisation of gold using surface plasmon-polaritons , 1987 .

[25]  R. Murray,et al.  Electronic conductivity of solid-state, mixed-valent, monolayer-protected Au clusters , 2000 .

[26]  C. Chidsey,et al.  Submicrosecond Electron Transfer to Monolayer-Bound Redox Species on Gold Electrodes at Large Overpotentials , 2002 .

[27]  S. Pratsinis,et al.  Dispersed nanoelectrode devices. , 2010, Nature nanotechnology.

[28]  Vincent J. Schaefer,et al.  Activities of Urease and Pepsin Monolayers , 1938 .

[29]  Byung-Ryool Hyun,et al.  Photogenerated exciton dissociation in highly coupled lead salt nanocrystal assemblies. , 2010, Nano letters.

[30]  J. M. Kikkawa,et al.  A generalized ligand-exchange strategy enabling sequential surface functionalization of colloidal nanocrystals. , 2011, Journal of the American Chemical Society.

[31]  James E. Martin,et al.  Control of the Interparticle Spacing in Gold Nanoparticle Superlattices , 2000 .

[32]  D. Hallinan,et al.  A convenient phase transfer protocol to functionalize gold nanoparticles with short alkylamine ligands. , 2015, Journal of colloid and interface science.

[33]  W. Kegel,et al.  Spontaneous assembly of a monolayer of charged gold nanocrystals at the water/oil interface. , 2004, Angewandte Chemie.

[34]  Chad A. Mirkin,et al.  One-Pot Colorimetric Differentiation of Polynucleotides with Single Base Imperfections Using Gold Nanoparticle Probes , 1998 .

[35]  Yong-Kyun Park,et al.  Directing Close-Packing of Midnanosized Gold Nanoparticles at a Water/Hexane Interface , 2008 .

[36]  C. Daniel Frisbie,et al.  Distance Dependence of Electron Tunneling through Self-Assembled Monolayers Measured by Conducting Probe Atomic Force Microscopy: Unsaturated versus Saturated Molecular Junctions , 2002 .

[37]  Paul L. McEuen,et al.  Fabrication of metallic electrodes with nanometer separation by electromigration , 1999 .

[38]  Louis E. Brus,et al.  Ag Nanocrystal Junctions as the Site for Surface-Enhanced Raman Scattering of Single Rhodamine 6G Molecules , 2000 .

[39]  Royce W Murray,et al.  Nanoelectrochemistry: metal nanoparticles, nanoelectrodes, and nanopores. , 2008, Chemical reviews.

[40]  Richard J. Saykally,et al.  Reversible Tuning of Silver Quantum Dot Monolayers Through the Metal-Insulator Transition , 1997 .

[41]  Prashant K. Jain,et al.  On the Universal Scaling Behavior of the Distance Decay of Plasmon Coupling in Metal Nanoparticle Pairs: A Plasmon Ruler Equation , 2007 .

[42]  Sarit S. Agasti,et al.  Gold nanoparticles in chemical and biological sensing. , 2012, Chemical reviews.

[43]  D. Fernig,et al.  Determination of size and concentration of gold nanoparticles from UV-vis spectra. , 2007, Analytical chemistry.

[44]  Shaowei Chen,et al.  Langmuir−Blodgett Fabrication of Two-Dimensional Robust Cross-Linked Nanoparticle Assemblies , 2001 .

[45]  R L Sandstrom,et al.  Spin-dependent tunneling in self-assembled cobalt-nanocrystal superlattices. , 2000, Science.

[46]  T. Vlugt,et al.  Understanding interactions between capped nanocrystals: three-body and chain packing effects. , 2009, The Journal of chemical physics.

[47]  Ralph G. Nuzzo,et al.  Fundamental studies of microscopic wetting on organic surfaces. 1. Formation and structural characterization of a self-consistent series of polyfunctional organic monolayers , 1990 .

[48]  J. Heath,et al.  Reversible Metal-Insulator Transition in Ordered Metal Nanocrystal Monolayers Observed by Impedance Spectroscopy , 1998 .

[49]  A. A. Maryott,et al.  Dielectric constant of water from 0 to 100 C , 1956 .

[50]  M. Kovalenko,et al.  Prospects of colloidal nanocrystals for electronic and optoelectronic applications. , 2010, Chemical reviews.

[51]  S. Louie,et al.  Amine-gold linked single-molecule circuits: experiment and theory. , 2007, Nano letters.

[52]  Z. Lu,et al.  Adjusting the inter-particle spacing of a nanoparticle array at the sub-nanometre scale by thermal annealing. , 2014, Chemical communications.

[53]  Stephen Z. D. Cheng,et al.  Molecular Nanoparticles Are Unique Elements for Macromolecular Science: From “Nanoatoms” to Giant Molecules , 2014 .

[54]  M. Pileni,et al.  Nanocrystal Self-Assemblies: Fabrication and Collective Properties , 2001 .

[55]  Mark K. Debe,et al.  High voltage stability of nanostructured thin film catalysts for PEM fuel cells , 2006 .

[56]  K. Leifer,et al.  Nanoparticle bridges for studying electrical properties of organic molecules. , 2012, Methods in molecular biology.

[57]  L. Liz‐Marzán,et al.  Optical Properties of Thin Films of Au@SiO2 Particles , 2001 .

[58]  M. Kovalenko,et al.  Colloidal Nanocrystals with Molecular Metal Chalcogenide Surface Ligands , 2009, Science.

[59]  W. Kegel,et al.  Understanding the self-assembly of charged nanoparticles at the water/oil interface. , 2006, Physical chemistry chemical physics : PCCP.

[60]  James R. Heath,et al.  PRESSURE/TEMPERATURE PHASE DIAGRAMS AND SUPERLATTICES OF ORGANICALLY FUNCTIONALIZED METAL NANOCRYSTAL MONOLAYERS: THE INFLUENCE OF PARTICLE SIZE, SIZE DISTRIBUTION, AND SURFACE PASSIVANT , 1997 .

[61]  Dmitri V Talapin,et al.  PbSe Nanocrystal Solids for n- and p-Channel Thin Film Field-Effect Transistors , 2005, Science.

[62]  S. Majetich,et al.  Ultra-large-area self-assembled monolayers of nanoparticles. , 2011, ACS nano.

[63]  Shangjr Gwo,et al.  Tunable plasmonic response from alkanethiolate-stabilized gold nanoparticle superlattices: evidence of near-field coupling. , 2008, Journal of the American Chemical Society.

[64]  L. Liz‐Marzán,et al.  A General Method for Solvent Exchange of Plasmonic Nanoparticles and Self-Assembly into SERS-Active Monolayers , 2015, Langmuir : the ACS journal of surfaces and colloids.

[65]  Jan Ilavsky,et al.  Nika : software for two-dimensional data reduction , 2012 .

[66]  J. Coates.  Interpretation of Infrared Spectra, A Practical Approach , 2006 .

[67]  H. Möhwald,et al.  Directing self-assembly of nanoparticles at water/oil interfaces. , 2004, Angewandte Chemie.

[68]  Amine-linked single-molecule circuits: systematic trends across molecular families. , 2008, Journal of physics. Condensed matter : an Institute of Physics journal.

[69]  D. Milliron,et al.  Electronically coupled nanocrystal superlattice films by in situ ligand exchange at the liquid-air interface. , 2013, ACS nano.

[70]  John Wang,et al.  Ordered mesoporous alpha-MoO3 with iso-oriented nanocrystalline walls for thin-film pseudocapacitors. , 2010, Nature materials.

[71]  C. Mirkin,et al.  Nanoparticles with Raman spectroscopic fingerprints for DNA and RNA detection. , 2002, Science.

[72]  Shi-Gang Sun,et al.  A universal approach for the self-assembly of hydrophilic nanoparticles into ordered monolayer films at a toluene/water interface. , 2006, Angewandte Chemie.

[73]  Lechner,et al.  Metal nanoparticle gratings: influence of dipolar particle interaction on the plasmon resonance , 2000, Physical review letters.

[74]  M. Brust,et al.  Spontaneous ordering of bimodal ensembles of nanoscopic gold clusters , 1998, Nature.

[75]  G. U. Kulkarni,et al.  Films of Metal Nanocrystals Formed at Aqueous-Organic Interfaces † , 2003 .

[76]  J. Brédas,et al.  Molecular electronics: Reflections on charge transport. , 2013, Nature nanotechnology.

[77]  Cherie R. Kagan,et al.  Thiocyanate-capped nanocrystal colloids: vibrational reporter of surface chemistry and solution-based route to enhanced coupling in nanocrystal solids. , 2011, Journal of the American Chemical Society.

[78]  C. Haynes,et al.  Nanoparticle Optics: The Importance of Radiative Dipole Coupling in Two-Dimensional Nanoparticle Arrays † , 2003 .

[79]  Al-Amin Dhirani,et al.  Charge transport in nanoparticle assemblies. , 2008, Chemical reviews.

[80]  Sungho V. Park,et al.  Assembly of highly ordered nanoparticle monolayers at a water/hexane interface. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[81]  Kevin W Eliceiri,et al.  NIH Image to ImageJ: 25 years of image analysis , 2012, Nature Methods.

[82]  R. Murray,et al.  Gold nanoelectrodes of varied size: transition to molecule-like charging , 1998, Science.

[83]  Thermal annealing: a facile way of conferring responsivity to inert alkyl-chain-passivated nanoparticle arrays. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[84]  D. B. Robinson,et al.  Controlled fabrication of metallic electrodes with atomic separation , 1999 .

[85]  Jianguo Wang,et al.  Correlation between nanostructural parameters and conductivity properties for molecularly-mediated thin film assemblies of gold nanoparticles , 2007 .

[86]  Shannon K. Yee,et al.  Fundamentals of energy transport, energy conversion, and thermal properties in organic-inorganic heterojunctions , 2010 .

[87]  Alex K.-Y. Jen,et al.  Air-stable inverted flexible polymer solar cells using zinc oxide nanoparticles as an electron selective layer , 2008 .

[88]  Matt Law,et al.  Schottky solar cells based on colloidal nanocrystal films. , 2008, Nano letters.

[89]  D. Astruc,et al.  Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology. , 2004, Chemical reviews.