Nanoscale chemical imaging of a dynamic molecular phase boundary with ultrahigh vacuum tip-enhanced raman spectroscopy

Nan Jiang; Naihao Chiang; Lindsey R. Madison; Eric A. Pozzi; Michael R. Wasielewski; Tamar Seideman; Mark A. Ratner; Mark C. Hersam; George C. Schatz; Richard P. Van Duyne

doi:10.1021/acs.nanolett.6b01405

Nanoscale chemical imaging of a dynamic molecular phase boundary with ultrahigh vacuum tip-enhanced raman spectroscopy

Nan Jiang^*, Naihao Chiang, Lindsey R. Madison, Eric A. Pozzi, Michael R. Wasielewski, Tamar Seideman, Mark A. Ratner, Mark C. Hersam, George C. Schatz, Richard P. Van Duyne

^*Corresponding author for this work

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

87 Scopus citations

Abstract

Nanoscale chemical imaging of a dynamic molecular phase boundary has broad implications for a range of problems in catalysis, surface science, and molecular electronics. While scanning probe microscopy (SPM) is commonly used to study molecular phase boundaries, its information content can be severely compromised by surface diffusion, irregular packing, or three-dimensional adsorbate geometry. Here, we demonstrate the simultaneous chemical and structural analysis of N-N′-bis(2,6-diisopropylphenyl)-1,7-(4′-t-butylphenoxy)perylene-3,4:9,10-bis(dicarboximide) (PPDI) molecules by UHV tip-enhanced Raman spectroscopy. Both condensed and diffusing domains of PPDI coexist on Ag(100) at room temperature. Through comparison with time-dependent density functional theory simulations, we unravel the orientation of PPDI molecules at the dynamic molecular domain boundary with unprecedented ∼4 nm spatial resolution.

Original language	English (US)
Pages (from-to)	3898-3904
Number of pages	7
Journal	Nano letters
Volume	16
Issue number	6
DOIs	https://doi.org/10.1021/acs.nanolett.6b01405
State	Published - Jun 8 2016

Funding

N.J., N.C., T.S., M.C.H., and R.P.V.D. acknowledge support from the Department of Energy Office of Basic Energy Sciences (SISGR Grant DE-FG02-09ER16109). L.R.M. and E.A.P. acknowledges support from the National Science Foundation Graduate Research Fellowship under Grant DGE-1324585 and the National Science Foundation Materials Research Science and Engineering Center (DMR-1121262). L.R.M., G.C.S., and R.P.V.D. acknowledge support from the National Science Foundation Center for Chemical Innovation dedicated to Chemistry at the Space-Time Limit (CaSTL) Grant CHE- 1414466. Additional support for facilities and instrumentation was provided by the National Science Foundation (CHE- 1414466, DMR-1121262) and the Department of Energy (DEFG02- 09ER16109). M.R.W. acknowledges the support of the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Department of Energy under Grant DE-FG02-99ER14999.

Keywords

Tip-enhanced Raman spectroscopy (TERS)
dynamic molecular phase boundary
time-dependent density functional theory (TDDFT)
ultrahigh vacuum scanning tunneling microscopy (UHV-STM)

ASJC Scopus subject areas

Bioengineering
General Chemistry
General Materials Science
Condensed Matter Physics
Mechanical Engineering

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10.1021/acs.nanolett.6b01405

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title = "Nanoscale chemical imaging of a dynamic molecular phase boundary with ultrahigh vacuum tip-enhanced raman spectroscopy",

abstract = "Nanoscale chemical imaging of a dynamic molecular phase boundary has broad implications for a range of problems in catalysis, surface science, and molecular electronics. While scanning probe microscopy (SPM) is commonly used to study molecular phase boundaries, its information content can be severely compromised by surface diffusion, irregular packing, or three-dimensional adsorbate geometry. Here, we demonstrate the simultaneous chemical and structural analysis of N-N′-bis(2,6-diisopropylphenyl)-1,7-(4′-t-butylphenoxy)perylene-3,4:9,10-bis(dicarboximide) (PPDI) molecules by UHV tip-enhanced Raman spectroscopy. Both condensed and diffusing domains of PPDI coexist on Ag(100) at room temperature. Through comparison with time-dependent density functional theory simulations, we unravel the orientation of PPDI molecules at the dynamic molecular domain boundary with unprecedented ∼4 nm spatial resolution.",

keywords = "Tip-enhanced Raman spectroscopy (TERS), dynamic molecular phase boundary, time-dependent density functional theory (TDDFT), ultrahigh vacuum scanning tunneling microscopy (UHV-STM)",

author = "Nan Jiang and Naihao Chiang and Madison, {Lindsey R.} and Pozzi, {Eric A.} and Wasielewski, {Michael R.} and Tamar Seideman and Ratner, {Mark A.} and Hersam, {Mark C.} and Schatz, {George C.} and {Van Duyne}, {Richard P.}",

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doi = "10.1021/acs.nanolett.6b01405",

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AU - Wasielewski, Michael R.

AU - Seideman, Tamar

AU - Ratner, Mark A.

AU - Hersam, Mark C.

AU - Schatz, George C.

AU - Van Duyne, Richard P.

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N2 - Nanoscale chemical imaging of a dynamic molecular phase boundary has broad implications for a range of problems in catalysis, surface science, and molecular electronics. While scanning probe microscopy (SPM) is commonly used to study molecular phase boundaries, its information content can be severely compromised by surface diffusion, irregular packing, or three-dimensional adsorbate geometry. Here, we demonstrate the simultaneous chemical and structural analysis of N-N′-bis(2,6-diisopropylphenyl)-1,7-(4′-t-butylphenoxy)perylene-3,4:9,10-bis(dicarboximide) (PPDI) molecules by UHV tip-enhanced Raman spectroscopy. Both condensed and diffusing domains of PPDI coexist on Ag(100) at room temperature. Through comparison with time-dependent density functional theory simulations, we unravel the orientation of PPDI molecules at the dynamic molecular domain boundary with unprecedented ∼4 nm spatial resolution.

AB - Nanoscale chemical imaging of a dynamic molecular phase boundary has broad implications for a range of problems in catalysis, surface science, and molecular electronics. While scanning probe microscopy (SPM) is commonly used to study molecular phase boundaries, its information content can be severely compromised by surface diffusion, irregular packing, or three-dimensional adsorbate geometry. Here, we demonstrate the simultaneous chemical and structural analysis of N-N′-bis(2,6-diisopropylphenyl)-1,7-(4′-t-butylphenoxy)perylene-3,4:9,10-bis(dicarboximide) (PPDI) molecules by UHV tip-enhanced Raman spectroscopy. Both condensed and diffusing domains of PPDI coexist on Ag(100) at room temperature. Through comparison with time-dependent density functional theory simulations, we unravel the orientation of PPDI molecules at the dynamic molecular domain boundary with unprecedented ∼4 nm spatial resolution.

KW - Tip-enhanced Raman spectroscopy (TERS)

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Nanoscale chemical imaging of a dynamic molecular phase boundary with ultrahigh vacuum tip-enhanced raman spectroscopy

Abstract

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Keywords

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