Covalent functionalization of GaP(110) surfaces via a staudinger-type reaction with perfluorophenyl azide

Miguel M. Ugeda; Aaron J. Bradley; Lucía Rodrigo; Min Yu; Wenjun Liu; Peter Doak; Alexander Riss; Jeffrey B. Neaton; T. Don Tilley; Rubén Pérez; Michael F. Crommie

doi:10.1021/acs.jpcc.6b10691

Covalent functionalization of GaP(110) surfaces via a staudinger-type reaction with perfluorophenyl azide

Miguel M. Ugeda, Aaron J. Bradley, Lucía Rodrigo, Min Yu, Wenjun Liu, Peter Doak, Alexander Riss, Jeffrey B. Neaton, T. Don Tilley, Rubén Pérez, Michael F. Crommie

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

3 Scopus citations

Abstract

Despite the markedly low chemical reactivity of the nonpolar (110) surfaces of III-V semiconductors, the covalent functionalization of GaP(110) surfaces with perfluorophenyl azide (PFPA) molecules by a Staudinger-type reaction occurs only slightly above room temperature (325 K). Scanning tunneling microscopy observations, combined with density functional theory calculations, support the formation of stable, covalent perfluorophenyl nitride (PFPN) molecule-surface bonds, which can be described as Lewis acidic Ga-stabilized phosphine imides. π-π stacking between aromatic, electron-deficient PFPN units results in compact, commensurate 2D molecular assembly at the surface. PFPA deposition on GaP(110) at room temperature with no additional annealing leads to an intermediate phase consistent with an alternating 1D array of physisorbed and chemisorbed molecular units. This work provides a new route for covalently bonding molecular linkages to the (110) surfaces of III-V semiconductors.

Original language	English
Pages (from-to)	26448-26452
Number of pages	5
Journal	Journal of Physical Chemistry C
Volume	120
Issue number	46
DOIs	https://doi.org/10.1021/acs.jpcc.6b10691
State	Published - Nov 23 2016
Externally published	Yes

Funding

This research was supported by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award No. DE-SC0004993 (PFPA chemical synthesis and theory) and by the DOE Nanomachine program Award no. DE-ACO2-05CH11231 (PFPA/GaP surface functionalization and STM imaging). L.R. and R.P. acknowledge the financial support of MINECO (projects CSD2010-00024, MAT2011-23627 and MAT2014-54484-P). Computer time was provided by the Lawrence Berkeley National Laboratory facilities and the Spanish Supercomputing Network (RES). Experimental and simulated STM images were rendered using WSxM software.23

Funders	Funder number
DOE Energy Innovation Hub
Joint Center for Artificial Photosynthesis
U.S. Department of Energy	DE-ACO2-05CH11231, DE-SC0004993
Office of Science
Ministerio de Economía y Competitividad	MAT2014-54484-P, MAT2011-23627, CSD2010-00024

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title = "Covalent functionalization of GaP(110) surfaces via a staudinger-type reaction with perfluorophenyl azide",

abstract = "Despite the markedly low chemical reactivity of the nonpolar (110) surfaces of III-V semiconductors, the covalent functionalization of GaP(110) surfaces with perfluorophenyl azide (PFPA) molecules by a Staudinger-type reaction occurs only slightly above room temperature (325 K). Scanning tunneling microscopy observations, combined with density functional theory calculations, support the formation of stable, covalent perfluorophenyl nitride (PFPN) molecule-surface bonds, which can be described as Lewis acidic Ga-stabilized phosphine imides. π-π stacking between aromatic, electron-deficient PFPN units results in compact, commensurate 2D molecular assembly at the surface. PFPA deposition on GaP(110) at room temperature with no additional annealing leads to an intermediate phase consistent with an alternating 1D array of physisorbed and chemisorbed molecular units. This work provides a new route for covalently bonding molecular linkages to the (110) surfaces of III-V semiconductors.",

author = "Ugeda, {Miguel M.} and Bradley, {Aaron J.} and Luc{\'i}a Rodrigo and Min Yu and Wenjun Liu and Peter Doak and Alexander Riss and Neaton, {Jeffrey B.} and Tilley, {T. Don} and Rub{\'e}n P{\'e}rez and Crommie, {Michael F.}",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

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doi = "10.1021/acs.jpcc.6b10691",

language = "English",

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AU - Ugeda, Miguel M.

AU - Bradley, Aaron J.

AU - Rodrigo, Lucía

AU - Yu, Min

AU - Liu, Wenjun

AU - Doak, Peter

AU - Riss, Alexander

AU - Neaton, Jeffrey B.

AU - Tilley, T. Don

AU - Pérez, Rubén

AU - Crommie, Michael F.

PY - 2016/11/23

Y1 - 2016/11/23

N2 - Despite the markedly low chemical reactivity of the nonpolar (110) surfaces of III-V semiconductors, the covalent functionalization of GaP(110) surfaces with perfluorophenyl azide (PFPA) molecules by a Staudinger-type reaction occurs only slightly above room temperature (325 K). Scanning tunneling microscopy observations, combined with density functional theory calculations, support the formation of stable, covalent perfluorophenyl nitride (PFPN) molecule-surface bonds, which can be described as Lewis acidic Ga-stabilized phosphine imides. π-π stacking between aromatic, electron-deficient PFPN units results in compact, commensurate 2D molecular assembly at the surface. PFPA deposition on GaP(110) at room temperature with no additional annealing leads to an intermediate phase consistent with an alternating 1D array of physisorbed and chemisorbed molecular units. This work provides a new route for covalently bonding molecular linkages to the (110) surfaces of III-V semiconductors.

AB - Despite the markedly low chemical reactivity of the nonpolar (110) surfaces of III-V semiconductors, the covalent functionalization of GaP(110) surfaces with perfluorophenyl azide (PFPA) molecules by a Staudinger-type reaction occurs only slightly above room temperature (325 K). Scanning tunneling microscopy observations, combined with density functional theory calculations, support the formation of stable, covalent perfluorophenyl nitride (PFPN) molecule-surface bonds, which can be described as Lewis acidic Ga-stabilized phosphine imides. π-π stacking between aromatic, electron-deficient PFPN units results in compact, commensurate 2D molecular assembly at the surface. PFPA deposition on GaP(110) at room temperature with no additional annealing leads to an intermediate phase consistent with an alternating 1D array of physisorbed and chemisorbed molecular units. This work provides a new route for covalently bonding molecular linkages to the (110) surfaces of III-V semiconductors.

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Covalent functionalization of GaP(110) surfaces via a staudinger-type reaction with perfluorophenyl azide

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