Nanoscale shape and size control of cubic, cuboctahedral, and octahedral Cu-Cu2O core-shell nanoparticles on Si(100) by one-step, templateless, capping-agent-free electrodeposition.

Cu-Cu2O core-shell nanoparticles (NPs) of different shapes over an extended nanosize regime of 5-400 nm have been deposited on a H-terminated Si(100) substrate by using a simple, one-step, templateless, and capping-agent-free electrochemical method. By precisely controlling the electrolyte concentration [CuSO4 x 5H2O] below their respective critical values, we can obtain cubic, cuboctahedral, and octahedral NPs of different average size and number density by varying the deposition time under a few seconds (<6 s). Combined glancing-incidence X-ray diffraction and depth-profiling X-ray photoelectron spectroscopy studies show that these NPs have a crystalline core-shell structure, with a face-centered cubic metallic Cu core and a simple cubic Cu2O shell with a CuO outerlayer. The shape control of Cu-Cu2O core-shell NPs can be understood in terms of a diffusion-limited progressive growth model under different kinetic conditions as dictated by different [CuSO4 x 5H2O] concentration regimes.

[1]  Youngil Lee,et al.  Large-scale synthesis of copper nanoparticles by chemically controlled reduction for applications of inkjet-printed electronics , 2008, Nanotechnology.

[2]  J. Geus,et al.  The sol—gel preparation of porous catalyst spheres , 1991 .

[3]  A. Kirfel,et al.  Accurate structure analysis with synchrotron radiation. The electron density in Al2O3 and Cu2O , 1990 .

[4]  A. Gedanken,et al.  Synthesis, Characterization, and Properties of Metallic Copper Nanoparticles. , 1998 .

[5]  S. Ishizuka,et al.  Thin film deposition of Cu2O and application for solar cells , 2006 .

[6]  Jae Kwang Lee,et al.  Influence of copper oxide modification of a platinum cathode on the activity of direct methanol fuel cell , 2007 .

[7]  D. Sarkar,et al.  Growth Mechanisms of Copper Nanocrystals on Thin Polypyrrole Films by Electrochemistry , 2003 .

[8]  Peter C. Searson,et al.  Electrodeposition of Copper on Silicon from Sulfate Solution , 2001 .

[9]  L. Tjeng,et al.  Electronic structure of Cu2O and CuO. , 1988, Physical review. B, Condensed matter.

[10]  Ko Kang Ning,et al.  SYNTHESIS AND CHARACTERIZATION OF , 2011 .

[11]  Masakazu Higuchi,et al.  Preparation of CuO thin films on porous BaTiO3 by self-assembled multibilayer film formation and application as a CO2 sensor , 1998 .

[12]  A. Sahari,et al.  Electrochemical nucleation and growth of copper deposition onto FTO and n-Si(1 0 0) electrodes , 2009 .

[13]  S. Gwo,et al.  Synthesis of Pyramidal Copper Nanoparticles on Gold Substrate , 2006 .

[14]  C. Foss,et al.  Metal Nanoparticles: Synthesis, Characterization, and Applications , 2001 .

[15]  P. D. Jongh,et al.  Cu2O: a catalyst for the photochemical decomposition of water? , 1999 .

[16]  Humberto H. Lara-Villegas,et al.  Neutralizing Viruses in Suspensions by Copper Oxide-Based Filters , 2007, Antimicrobial Agents and Chemotherapy.

[17]  T. Fleisch,et al.  Reduction of copper oxides by UV radiation and atomic hydrogen studied by XPS , 1982 .

[18]  Hiroshi Nakatsuji,et al.  Mechanism of Methanol Synthesis on Cu(100) and Zn/Cu(100) Surfaces: Comparative Dipped Adcluster Model Study , 2000 .

[19]  Lingyan Wang,et al.  Synthesis of size-controlled and shaped copper nanoparticles. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[20]  Jinghui Zeng,et al.  Hydrothermal Synthesis of Uniform Cuprous Oxide Microcrystals with Controlled Morphology , 2008 .

[21]  B. Pešić,et al.  Electrodeposition of copper: the nucleation mechanisms , 2002 .

[22]  M. S. El-shall,et al.  Synthesis and characterization of nanoparticle Co3O4, CuO and NiO catalysts prepared by physical and chemical methods to minimize air pollution , 2007 .

[23]  D. Barreca,et al.  CVD of Copper Oxides from a β-Diketonate Diamine Precursor: Tailoring the Nano-Organization , 2009 .

[24]  P. Ostoja,et al.  Lattice parameter study of silicon uniformly doped with boron and phosphorus , 1974 .

[25]  I. Losito,et al.  Electrosynthesis and analytical characterisation of polypyrrole thin films modified with copper nanoparticles , 2001 .

[26]  H. Schmidt,et al.  The stability of CuO and Cu2O surfaces during argon sputtering studied by XPS and AES , 1985 .

[27]  M. Pileni,et al.  Anisotropic copper nanocrystals synthesized in a supersaturated medium: nanocrystal growth. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[28]  Wenzhong Wang,et al.  Shape evolution and size-controllable synthesis of Cu2O octahedra and their morphology-dependent photocatalytic properties. , 2006, The journal of physical chemistry. B.

[29]  Yoshio Waseda,et al.  High-temperature thermal expansion of six metallic elements measured by dilatation method and X-ray diffraction , 1988 .

[30]  Z. Pászti,et al.  Laser ablation induced formation of nanoparticles and nanocrystal networks , 2000 .

[31]  Yong Wang,et al.  One‐Pot Synthesis and Hierarchical Assembly of Hollow Cu2O Microspheres with Nanocrystals‐Composed Porous Multishell and Their Gas‐Sensing Properties , 2007 .

[32]  B. Saidani,et al.  Preparation on iron of a polypyrrole (PPy) electrode modified with copper by the electrochemical cementation process , 2000 .

[33]  J. Schultze,et al.  Electrochemical incorporation of copper in polyaniline layers , 2001 .

[34]  Catherine J. Murphy,et al.  Solution-phase synthesis of Cu2O nanocubes , 2003 .

[35]  T. Matsuoka,et al.  Improvement of copper plating adhesion of PPE printed wiring board by plasma treatment , 2008 .

[36]  P. Stefanov,et al.  Adsorption of oxygen and formation of an oxide phase on a Cu(100) surface , 1988 .

[37]  B. Mehta,et al.  Surface-modified CuO layer in size-stabilized single-phase Cu2O nanoparticles , 2001 .

[38]  J. Forrester,et al.  A crystallographic contribution to the mechanism of a mechanically induced solid state reaction , 1996 .

[39]  V. Tsakova,et al.  Electrochemical deposition of copper in polyaniline films — number density and spatial distribution of deposited metal clusters , 2000 .

[40]  Claude R. Henry,et al.  Morphology of supported nanoparticles , 2005 .

[41]  P. Searson,et al.  Electrochemical nucleation and growth of copper on Si(111) , 2001 .

[42]  M. Ger,et al.  Mechanism of underpotential deposition of metal on conducting polymers , 2002 .

[43]  A. Harmer,et al.  Parametric study on electrochemical deposition of copper nanoparticles on an ultrathin polypyrrole film deposited on a gold film electrode. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[44]  A. Nyamathi,et al.  Deactivation of Human Immunodeficiency Virus Type 1 in Medium by Copper Oxide-Containing Filters , 2008, Antimicrobial Agents and Chemotherapy.

[45]  H. Chiu,et al.  Convergent electron beam induced growth of copper nanostructures: evidence of the importance of a soft template. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[46]  Formation and valence band density of states of nonspherical Cu nanoparticles deposited on Si(100) substrate , 1997 .

[47]  Zhaohui Li,et al.  Photochemical synthesis of submicron- and nano-scale Cu2O particles. , 2009, Journal of colloid and interface science.

[48]  G. Zangari,et al.  Electrochemical Nucleation and Growth of Copper from Acidic Sulfate Electrolytes on n-Si ( 001 ) Effect of Chloride Ions , 2007 .

[49]  C. Murphy,et al.  Controlling the size of Cu2O nanocubes from 200 to 25 nm , 2004 .

[50]  C. Malitesta,et al.  Conducting polymer electrodes modified by metallic species for electrocatalytic purposes—spectroscopic and microscopic characterization , 1996 .

[51]  S. Vongehr,et al.  An additive-free electrochemical route to rapid synthesis of large-area copper nano-octahedra on gold film substrates , 2009 .

[52]  Yunsoo Kim,et al.  Self-Assembled Monolayers of Alkanethiols on Oxidized Copper Surfaces , 2000 .

[53]  Arun Natarajan,et al.  Electrochemical deposition of metals onto silicon , 1998 .

[54]  Norio Miura,et al.  Dilute hydrogen sulfide sensing properties of CuO–SnO2 thin film prepared by low-pressure evaporation method , 1998 .

[55]  A. West,et al.  Influence of Additives on Nucleation and Growth of Copper on n-Si(111) from Acidic Sulfate Solutions , 2002 .

[56]  D. Sarkar,et al.  Growth of self-assembled copper nanostructure on conducting polymer by electrodeposition , 2003 .

[57]  Ying Dai,et al.  Crystal Faces of Cu2O and Their Stabilities in Photocatalytic Reactions , 2009 .

[58]  A. Barron,et al.  Ultrasmall copper nanoparticles from a hydrophobically immobilized surfactant template. , 2009, Nano letters.

[59]  M. Pileni,et al.  Control of the shape of copper metallic particles by using a colloidal system as template , 1997 .

[60]  W. Kern Cleaning solutions based on hydrogen peroxide for use in silicon semiconductor technology , 1970 .

[61]  H. Zhang,et al.  Solution-phase synthesis of smaller cuprous oxide nanocubes , 2008 .