STM and DFT investigations of isolated porphyrin on a silicon-based semiconductor at room temperature.

Metalloporphyrins represent a class of flexible molecules with a nearly square planar core conformation and a two dimensional conjugated p-electron delocalization. Due to their interesting physicochemical properties, metalloporphyrins adsorbed on a surface can be used in many technological applications such as molecular electronics, light-harvesting arrays for solar energy generation, catalysts, sensors, etc. The fine determination of the conformation and arrangement of adsorbed molecules on a surface are key points, since they are strongly related to the physical and chemical properties of the final organic–inorganic interfaces. They are changed by the subtle balance of internal deformation and substrate–molecule interactions, leading to a conformational adaptation of the molecule on the substrate lattice. These features are even more relevant in semiconductors than in metals because the moleculesemiconductor interactions are usually greater than molecule– metal interactions. Although scanning tunneling microscopy (STM) is a remarkable tool to investigate individual adsorbed molecules on semiconductors, experimental STM images of metalloporphyrins were achieved only on metals and only an unique very recent article investigates theoretically the adsorption of a metalloporphyrin on a Si(111)-H surface. Herein, we report the first experimental investigation at room temperature of the adsorption of Cu-5,10,15,20-tetrakis(3,5-di-tert-butylphenyl) porphyrin (Cu-TBPP) as a model of metalloporphyrin on a passivated silicon based surface (Si(111)-B) using STM and by theoretical calculations in order to fully understand the conformational adaptation of the Cu-TBPP on a Si(111)-B surface.

[1]  D. Bowler,et al.  Density functional theory study of the iron-based porphyrin haem(b) on the Si(111):H surface , 2009 .

[2]  P. Sonnet,et al.  SiC(0001) 3 x 3 heterochirality revealed by single-molecule STM imaging. , 2009, Journal of the American Chemical Society.

[3]  J. Barth,et al.  Temperature dependence of conformation, chemical state, and metal-directed assembly of tetrapyridyl-porphyrin on Cu(111). , 2008, The Journal of chemical physics.

[4]  Stefan Hecht,et al.  Spatial periodicity in molecular switching. , 2008, Nature nanotechnology.

[5]  E. Duverger,et al.  Complete supramolecular self-assembled adlayer on a silicon surface at room temperature. , 2008, Journal of the American Chemical Society.

[6]  W. Hofer,et al.  Dipole-directed assembly of lines of 1,5-dichloropentane on silicon substrates by displacement of surface charge. , 2008, Nature nanotechnology.

[7]  K. Miki,et al.  A scanning tunnelling microscopy investigation into the initial stages of copper phthalocyanine growth on passivated silicon surfaces , 2008 .

[8]  E. Duverger,et al.  A stable room-temperature molecular assembly of zwitterionic organic dipoles guided by a Si(111)-7x7 template effect. , 2007, Angewandte Chemie.

[9]  Y. Pennec,et al.  Conformational adaptation and selective adatom capturing of tetrapyridyl-porphyrin molecules on a copper (111) surface. , 2007, Journal of the American Chemical Society.

[10]  W. Hofer,et al.  Ab-initio calculations and STM observations on tetrapyridyl and Fe(II)-tetrapyridyl-porphyrin molecules on Ag(111) , 2007 .

[11]  V. Batista,et al.  Density functional theory and DFT+U study of transition metal porphines adsorbed on Au(111) surfaces and effects of applied electric fields. , 2006, Journal of the American Chemical Society.

[12]  Adrienn Ruzsinszky,et al.  Binding energy curves from nonempirical density functionals II. van der Waals bonds in rare-gas and alkaline-earth diatomics. , 2005, The journal of physical chemistry. A.

[13]  K. Kern,et al.  Engineering atomic and molecular nanostructures at surfaces , 2005, Nature.

[14]  Robert A. Wolkow,et al.  Field regulation of single-molecule conductivity by a charged surface atom , 2005, Nature.

[15]  R. E. Palmer,et al.  Two-electron dissociation of single molecules by atomic manipulation at room temperature , 2005, Nature.

[16]  S. Mashiko,et al.  Conformation selective assembly of carboxyphenyl substituted porphyrins on Au (111). , 2004, The Journal of chemical physics.

[17]  Jiang Ping,et al.  TBPP molecules on copper surfaces: a low temperature scanning tunneling microscope investigation , 2002 .

[18]  K. W. Hipps,et al.  A self-organized 2-dimensional bifunctional structure formed by supramolecular design. , 2002, Journal of the American Chemical Society.

[19]  Akihiko Tsuda,et al.  Fully Conjugated Porphyrin Tapes with Electronic Absorption Bands That Reach into Infrared , 2001, Science.

[20]  C Joachim,et al.  Conformational changes of single molecules induced by scanning tunneling microscopy manipulation: a route to molecular switching. , 2001, Physical review letters.

[21]  J. N. Russell,et al.  Cycloaddition chemistry of organic molecules with semiconductor surfaces. , 2000, Accounts of chemical research.

[22]  J. Lyding,et al.  Silicon-based molecular nanotechnology , 2000 .

[23]  J. Lyding,et al.  Implications of atomic-level manipulation on the Si(100) surface: From enhanced CMOS reliability to molecular nanoelectronics , 2000 .

[24]  J. K. Gimzewski,et al.  Conformational identification of individual adsorbed molecules with the STM , 1997, Nature.

[25]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[26]  Hafner,et al.  Ab initio molecular dynamics for liquid metals. , 1995, Physical review. B, Condensed matter.

[27]  N. Papageorgiou,et al.  Physics of ultra-thin phthalocyanine films on semiconductors , 2004 .