Nitroxyl free radical binding to Si(1 0 0): A combined scanning tunneling microscopy and computational modeling study

Mark E. Greene; Nathan P. Guisinger; Rajiv Basu; Andrew S. Baluch; Mark C. Hersam

doi:10.1016/j.susc.2004.04.012

Nitroxyl free radical binding to Si(1 0 0): A combined scanning tunneling microscopy and computational modeling study

Mark E. Greene^*, Nathan P. Guisinger, Rajiv Basu, Andrew S. Baluch, Mark C. Hersam

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

23 Scopus citations

Abstract

The ultra-high vacuum scanning tunneling microscope (UHV-STM) was used to investigate the addition of the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) radical to the Si(1 0 0) surface. Room temperature studies performed on clean Si(1 0 0)-2×1 confirm the proposed binding of the unpaired valence electron associated with the singly occupied molecular orbital (SOMO) of the molecule with a Si dangling bond. A strong bias dependence in the topography of isolated molecules was observed in the range of -2.0 to +2.5 V. Semiempirical and density functional calculations of TEMPO bound to a three-dimer silicon cluster model yield occupied state density isosurfaces below the highest occupied (HOMO) and unoccupied state densities isosurfaces above the lowest unoccupied molecular orbital (LUMO) which trend in qualitative agreement with the bias dependent STM topography. Furthermore, the placement of TEMPO molecules on dangling bonds was controlled with atomic precision on the monohydride Si(1 0 0) surface via electron stimulated desorption of H, demonstrating the compatibility of nitroxyl free radical binding chemistries with nanopatterning techniques such as feedback controlled lithography.

Original language	English (US)
Pages (from-to)	16-28
Number of pages	13
Journal	Surface Science
Volume	559
Issue number	1
DOIs	https://doi.org/10.1016/j.susc.2004.04.012
State	Published - Jun 10 2004

Funding

The authors would like to acknowledge J. Michl for advice on free radical molecules. This work was supported by an Arnold and Mabel Beckman Young Investigator Award, the NASA Institute for Nanoelectronics and Computing under Award Number NCC 2-3163, the Nanoscale Science and Engineering Initiative of the National Science Foundation under NSF Award Numbers EEC-0118025 and DMR-0134706, and the Defense University Research Initiative in Nanotechnology of the United States Army Research Office under grant number DAAD 19-01-1-0521.

Keywords

Density functional calculations
Molecule-solid reactions
Scanning tunneling microscopy
Silicon
Surface electronic phenomena (work function, surface potential, surface states, etc.)

ASJC Scopus subject areas

Condensed Matter Physics
Surfaces and Interfaces
Surfaces, Coatings and Films
Materials Chemistry

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10.1016/j.susc.2004.04.012

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@article{219c52bd476d4e838cfb4958a82f6be4,

title = "Nitroxyl free radical binding to Si(1 0 0): A combined scanning tunneling microscopy and computational modeling study",

abstract = "The ultra-high vacuum scanning tunneling microscope (UHV-STM) was used to investigate the addition of the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) radical to the Si(1 0 0) surface. Room temperature studies performed on clean Si(1 0 0)-2×1 confirm the proposed binding of the unpaired valence electron associated with the singly occupied molecular orbital (SOMO) of the molecule with a Si dangling bond. A strong bias dependence in the topography of isolated molecules was observed in the range of -2.0 to +2.5 V. Semiempirical and density functional calculations of TEMPO bound to a three-dimer silicon cluster model yield occupied state density isosurfaces below the highest occupied (HOMO) and unoccupied state densities isosurfaces above the lowest unoccupied molecular orbital (LUMO) which trend in qualitative agreement with the bias dependent STM topography. Furthermore, the placement of TEMPO molecules on dangling bonds was controlled with atomic precision on the monohydride Si(1 0 0) surface via electron stimulated desorption of H, demonstrating the compatibility of nitroxyl free radical binding chemistries with nanopatterning techniques such as feedback controlled lithography.",

keywords = "Density functional calculations, Molecule-solid reactions, Scanning tunneling microscopy, Silicon, Surface electronic phenomena (work function, surface potential, surface states, etc.)",

author = "Greene, {Mark E.} and Guisinger, {Nathan P.} and Rajiv Basu and Baluch, {Andrew S.} and Hersam, {Mark C.}",

note = "Funding Information: The authors would like to acknowledge J. Michl for advice on free radical molecules. This work was supported by an Arnold and Mabel Beckman Young Investigator Award, the NASA Institute for Nanoelectronics and Computing under Award Number NCC 2-3163, the Nanoscale Science and Engineering Initiative of the National Science Foundation under NSF Award Numbers EEC-0118025 and DMR-0134706, and the Defense University Research Initiative in Nanotechnology of the United States Army Research Office under grant number DAAD 19-01-1-0521.",

year = "2004",

month = jun,

day = "10",

doi = "10.1016/j.susc.2004.04.012",

language = "English (US)",

volume = "559",

pages = "16--28",

journal = "Surface Science",

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AU - Greene, Mark E.

AU - Guisinger, Nathan P.

AU - Basu, Rajiv

AU - Baluch, Andrew S.

AU - Hersam, Mark C.

N1 - Funding Information: The authors would like to acknowledge J. Michl for advice on free radical molecules. This work was supported by an Arnold and Mabel Beckman Young Investigator Award, the NASA Institute for Nanoelectronics and Computing under Award Number NCC 2-3163, the Nanoscale Science and Engineering Initiative of the National Science Foundation under NSF Award Numbers EEC-0118025 and DMR-0134706, and the Defense University Research Initiative in Nanotechnology of the United States Army Research Office under grant number DAAD 19-01-1-0521.

PY - 2004/6/10

Y1 - 2004/6/10

N2 - The ultra-high vacuum scanning tunneling microscope (UHV-STM) was used to investigate the addition of the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) radical to the Si(1 0 0) surface. Room temperature studies performed on clean Si(1 0 0)-2×1 confirm the proposed binding of the unpaired valence electron associated with the singly occupied molecular orbital (SOMO) of the molecule with a Si dangling bond. A strong bias dependence in the topography of isolated molecules was observed in the range of -2.0 to +2.5 V. Semiempirical and density functional calculations of TEMPO bound to a three-dimer silicon cluster model yield occupied state density isosurfaces below the highest occupied (HOMO) and unoccupied state densities isosurfaces above the lowest unoccupied molecular orbital (LUMO) which trend in qualitative agreement with the bias dependent STM topography. Furthermore, the placement of TEMPO molecules on dangling bonds was controlled with atomic precision on the monohydride Si(1 0 0) surface via electron stimulated desorption of H, demonstrating the compatibility of nitroxyl free radical binding chemistries with nanopatterning techniques such as feedback controlled lithography.

AB - The ultra-high vacuum scanning tunneling microscope (UHV-STM) was used to investigate the addition of the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) radical to the Si(1 0 0) surface. Room temperature studies performed on clean Si(1 0 0)-2×1 confirm the proposed binding of the unpaired valence electron associated with the singly occupied molecular orbital (SOMO) of the molecule with a Si dangling bond. A strong bias dependence in the topography of isolated molecules was observed in the range of -2.0 to +2.5 V. Semiempirical and density functional calculations of TEMPO bound to a three-dimer silicon cluster model yield occupied state density isosurfaces below the highest occupied (HOMO) and unoccupied state densities isosurfaces above the lowest unoccupied molecular orbital (LUMO) which trend in qualitative agreement with the bias dependent STM topography. Furthermore, the placement of TEMPO molecules on dangling bonds was controlled with atomic precision on the monohydride Si(1 0 0) surface via electron stimulated desorption of H, demonstrating the compatibility of nitroxyl free radical binding chemistries with nanopatterning techniques such as feedback controlled lithography.

KW - Density functional calculations

KW - Molecule-solid reactions

KW - Scanning tunneling microscopy

KW - Silicon

KW - Surface electronic phenomena (work function, surface potential, surface states, etc.)

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DO - 10.1016/j.susc.2004.04.012

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JO - Surface Science

JF - Surface Science

IS - 1

ER -

Nitroxyl free radical binding to Si(1 0 0): A combined scanning tunneling microscopy and computational modeling study

Abstract

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