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Research Seminar for New Graduate StudentsRyan 4003, 11:05 AM - 11:20 AM Friday September 08, 2017Surface Enhanced Raman Spectroscopy (SERS)

Departments of Chemistry and Biomedical Engineering & The Applied Physics ProgramTECH K124, (847)-491-3561, vanduyne@northwestern.edu

Richard P. Van Duyne

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Single Particle and Single Molecule SERS

Single Particle Surface Enhanced Raman Excitation SpectroscopyJ. Am. Chem. Soc., 135, 301-308 (2013)

Single Molecule SERS: Bianalyte vs. Isotopologue ProofJ. Phys. Chem. C, 120, 5133-5142 (2016)

Single Molecule SERS: Isotopologue ProofJ. Am. Chem. Soc., 129,16249-16256 (2007)

Ultrafast SERS #1

Surface Enhanced FemtosecondStimulated Raman Spectroscopy (SE-FSRS)J. Phys. Chem. Letters, 2, 1199-1203 (2011)

Fano-like resonances in SE-FSRSNano Letters, 12, 5989-5994 (2012)

SE-FSRS at 1 MHz Repetition RateJ. Phys. Chem. Letters, 7, 4629−4634 (2016)

Coupled wave equations theory of SE-FSRSJ. Chem. Phys., 145, 094106 (2016) 3

Ultrafast SERS #2

Wavelength-scanned excitation in SE-FSRSJ. Phys. Chem. Letters, 8, 3328-3333 (2017)Balancing the Effects of Extinction and

Enhancement for Optimal SE-FSRSJ. Phys. Chem. C., 120, 29449-29454 (2016)

Quantum mechanical theory of SE-FSRSJ. Chem. Phys., in preparation (2017) Single-aggregate µSE-FSRS

J. Phys. Chem. C, in preparation (2017) 4

Plasmon Driven Electron Transfer

28E. Sprague-Klein, M. O. McAnally, D. Zhdanov, A. Zrimsek, V. A. Apkarian,T. Seideman, G. C. Schatz, and R. P. Van Duyne, submitted (2017)

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e-

Plasmon-Driven Electron Transfer: BPE/Au Nanoparticle Assemblies

JACS, submitted (2017)

Plasmon-Driven Re-CO Bond Breaking Re(bpy)(CO)3Cl/Au Nanoparticle Assemblies

to be submitted (2017)

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Plasmon-Driven Electron Transfer: BPY-h8,d8/Au Nanoparticle Assemblies

JACS, submitted (2017)

Plasmon-Driven Electron Transfer N-719/Au Nanoparticle Assemblies

to be submitted (2017)

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SERS for Catalysis #1

Probing the Chemistry of Alumina Atomic Layer Deposition Using SERSJ. Phys. Chem. C, 120, 3822-3833 (2016)

High-Resolution Distance Dependence of SERS Nano Letters, 16, 4251-4259 (2016)

Aluminum: Deep-UV SERS Nano Letters, 16, 7968-7973 (2016)

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SERS for Catalysis #2

Identification of Dimeric Methylalumina Surface Species during AtomicLayer Deposition using Operando Surface-Enhanced Raman Spectroscopy

J. Am. Chem. Soc., 139, 2456-2463 (2017)

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SERS Biosensing #1

SERS Biosensing: In Vivo Diagnostics and Multimodal ImagingAnal. Chem., 88, 6638-6647 (2016)

SERS Detection of Ricin B Chain in Human BloodJ. Phys. Chem. C, 120, 20961−20969 (2016)

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SERS Biosensing #2

In Vivo, Transcutaneous Glucose Sensing Using SERSAnal. Chem., 83, 9146-9152 (2011)

Bisboronic Acids for Selective, Physiologically Relevant Direct Glucose Sensing with SERSJ. Am. Chem. Soc., 138, 13952-13959 (2016)

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Nanoscale Imaging with LightNo – the wavelength of light is too large

2014 Nobel Prize in ChemistryE. Betzig, S. Hell, W. E. Moerner

ConventionalFluorescenceMicroscopy

Super-ResolutionFluorescenceMicroscopy

Super-Resolution Fluorescence: ~ 10 nm resolution & single molecule detection

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Tip-Enhanced Raman Spectroscopy (TERS)Nanoscale Imaging with Light – Another Way

Raman + STM + Plasmonics

E. Pozzi, G. Goubert, N. Chiang, N. Jiang, C. Chapman, M. McAnally, A-I. T. Seideman, G. Schatz, M. Hersam, and RPVD, Chem. Rev., (2016), DOI: 10.1021/acs.chemrev.6b00552

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Tip-Enhanced Raman Spectroscopy (TERS)

2focus

TERS 2tip

I rEF =I r

engaged

retracted

4 8TERSEF = 10 -10

Single Molecule Identification & < 1 nm Spatial Resolution

Nanoscale Imaging with Light – Another Way

All external optics

< 2 x 10-11 Torr

Cryostat: 7K; 19K

Ultrahigh Vacuum Tip-Enhanced Raman Spectroscopy

E. Foley, N. Jiang, A. McFarland, J. Klingsporn, M. Sonntag, J. Dieringer, M. Hersam, and RVD, in preparation (2016) 10

OPTICSSAMPLEPREPARATION

STM

Van Duyne Group LT-UHV-STMAg Tip/FePc/Ag(111)

10nm x 10nm+1V, 0.1nA 

7K

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Van Duyne Group LT-UHV-STMAg Tip/TCNQ/Au(111)

‐1.2V, 0.32nA  ‐1.2V, 0.8nA 12

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UHV-TERS Combined with Molecular-Resolution STM Nano Lett.,12, 5061-5067 (2012)

LT(19K)-UHV-TERSJACS, 136, 3881-3887 (2014)

UHV-TERS/TEF of PorphyrinNano. Lett., 15, 4114-4120 (2015)

Picosecond TERS in UHVJPCL, 5, 2657-2661 (2014)

UHV Tip Enhanced Raman Spectroscopy

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Imaging a Dynamic Phase Boundary with UHV-TERSNano Letters, 16, 3898-3904 (2016)

Plasmon Mediated Electron Transport in UHV-TERSJPCL, 6, 4210−4218 (2015)

Picosecond and Femtosecond Pulse-Excited UHV-SERSJPCL, 7, 2971−2976 (2016)

2.6 Å Resolution UHV-TERSNano Letters, 16, 7774-7778 (2016)

UHV Tip Enhanced Raman Spectroscopy

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4.3 nm Resolution in RT-UHV-TERS: Ag Tip/PPDI/Ag(111)

PPDI

1.0V, 0.3nA, Ag Tip

DiffusingPPDI

PPDI Island

5 nm

0 5 10 15 20

Raman Intensity

(nm)

1350 cm-1 TERS Line Scan1350 cm-1 TERS Map, Ag TipCurrent Image, Ag Tip

20 x 16 nm

Line Spread Function Gaussian Fit of LSF

FWHM: 4.34 nm

N. Jiang, N. Chiang, L. R. Madison, E. A. Pozzi, M. R. Wasielewski, T. Seideman, M. A. Ratner, M. C. Hersam, G. C. Schatz, and R. P. Van Duyne. Nano Letters, 16, 3898-3904 (2016)

Stronger molecule-substrate interaction on Cu(111)

STM conditions: Vb = 0.8 V, I = 100 pA

Two different molecular conformation (t-butylphenylgroups up/down)

H. Marbach et al., JACS. 136, 1609 (2014)

13 nm 4.8 nm

RT-UHV-TERS: Ag Tip/H2TBPP/Cu(111)

34N. Chiang, D. Chulhai, G. Goubert, X. Chen, E. Pozzi, N. Jiang, M. Hersam, T. Seideman,

L. Jensen, and R. P. Van Duyne, Nano Letters, 16, 7774-7778 (2016)

H2TBPP

+++ +++++ +++++ +++++ +++++ +++++ +++++ +++++ ++

TER

S In

tens

ity

(a.u

.)

0.05 nm

STM

Top

ogra

phic

H

eigh

t

Lateral Resolution:0.256 nm

1502 cm-1

4.0 nm

STM before/after does NOT represent the system since the molecules might flip during the scan. TERS and STM line scan need to be taken simultaneously!

Down DownUp Up

2.6 Å Resolution in UHV-TERS: Ag Tip/H2TBPP/Cu(111)

N. Chiang, D. Chulhai, G. Goubert, X. Chen, E. Pozzi, N. Jiang, M. Hersam, T. Seideman, L. Jensen, and R. P. Van Duyne, Nano Letters, 16, 7774-7778 (2016) 35

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Scientific Objective: In-Situ structure-activityrelationships for electrochemistry on 1-10 nm scale

New sites/

Defects

Crystal faces Surface sites Multi-component system

Each surface site will have a different standard potential,E0, and heterogeneous rate constant, k0. Nanoscaleelectrochemical tools are required to achieve this objective.

Single Molecule & Nanoscale Electrochemistry

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Single Molecule Electrochemistry

Probing Nanoscale Redox Reactions with EC-AFM-TERSNano Letters, 15, 7956-7962 (2015)

Nano Letters, 17, 590-596 (2017)Observing Single, Heterogeneous, 1 e- Reactions

J. Phys. Chem. C, 119, 28226-28234 (2015)

Nanoscale Electrochemistry with SERS & TERSAcc. Chem. Res., 49, 2023–2030 (2016)

2 Color SMSERS: The R6G Neutral RadicalJ. Phys. Chem. C, 120, 24982-24991 (2016)

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Van Duyne Group & Collaborators Summer 2016

Back row: Kevin Kang, Yinsheng Guo, Naihao Chiang, Ryan Hackler, Tyler Ueltschi, Meaghan Bruening, Guillaume Goubert, Jennifer Park, Michael Mattei, Cassie George, Larry Soboleski, Michael McAnally, Xu Chen,Song Jiang. Front row: Alyssa Zrimsek, Toby Singer, Emma Vander Ende, Betty Peng, Anne-Isabelle Henry, Hannah Mayhew, Richard Van Duyne, Emily Sprague-Klein, Nolan Wong, Fernanda Cardinal, Adie Slaton,Anam Furrukh

InternationalMikael Käll (Chalmers)

Bill Barnes (Exeter)Besenbacher (Aarhus)

Pileni (Paris VI)Vallee (Lyon)

Liz-Marzan (San Sebastian)Pineider (Pisa)

NU, ChemistryHarris, Hupp, Mirkin,

Mrksich, Ratner, Schatz, Scheidt

Seideman, Stair, WeitzPSU, Chemistry

Jensen

AIC, Art Conserv.Casadio

NU, MS&EHersam, Marks

UCI, CaSTLApkarian, Ho

AFOSR MURIBard (UT), White (Utah), Willets (Temple), Zhang (U Wash.)

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Christy L. Haynes 1998-2003 Ph.D.(2003) University of Minnesota (Faculty)

Amanda J. Haes 1999-2004 Ph.D.(2003) University of Iowa (Faculty)

Adam D. McFarland 1999-2004 Ph.D.(2004) Res. Scientist, Eli Lily

Xiaoyu Zhang 2001-2006 Ph.D.(2006) Res. Scientist, Eli Lily

Chanda Ranjit Yonzon 2001-2006 Ph.D.(2006) Res. Scientist, Schering Plough

Alyson V. Whitney 2002-2007 Ph.D.(2007) Chemist, British Petroleum

Leif J. Sherry 2002-2007 Ph.D.(2007) Chemistry Instructor, Bossier Parish Community College (Faculty)

Matthew A. Young 2002-2007 Ph.D.(2007) Hillsdale College (Faculty)

Erin C. McLellan 2002-2007 Ph.D.(2007) IBM, Albany, NY (Scientist)

Jiha Sung

Jing Zhao

David Q. Andrews

Jenny Roden

Kevin Biggs

Paige Hall

Kathryn Kosuda

Julia Bingham

2002-2007

2003-2008

2003-2008

2006-2008

2004-2009

2005-2010

2005-2010

2005-2010

Ph.D.(2007)

Ph.D.(2008)

Ph.D.(2008)

M.S.(2008)

Ph.D.(2009)

Ph.D. (2010)

Ph.D. (2010)

Ph.D. (2010)

Dongkuk University (Faculty)

University of Connecticut (Faculty)

Senior Scientist, EWG

Teacher, Chicago Public Schools

Scientist III, US Pharmocpieal

University of Portland (Faculty)

Vaxess Technologies

Postdoc, NU (Van Duyne Group)

Van Duyne Group: PlacementGraduate Students #1

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Emilie Ringe 2008-2012 Ph.D.(2012) Cambridge University (Faculty)

Samuel Kleinman

Matt Sonntag

Lauren Kreno

Nathan Greeneltch

Natalie Ray

Ke Ma

Jordan Klingsporn

Laura Ruvuna

Alex Peroff

2007-2012

2009-2013

2009-2013

2009-2013

2009-2013

2009-2013

2010-2014

2008-2013

2009-2014

Ph.D.(2012)

Ph.D.(2013)

Ph.D.(2013)

Ph.D.(2013)

Ph.D.(2013)

Ph.D.(2013)

Ph.D.(2014)

Ph.D.(2013)

Ph.D.(2014)

Postdoc, NU (Van Duyne Group)

Albright College, (Faculty)

ExxonMobil (Research Scientist)

Intel

British Petroleum (Chemist)

MedSphere Corp. (Biomed. Engineer)

Intel

Abbott

Postdoc, SUNY Albany (Lednev Group)

Natalie Gruenke 2010-2015 Ph.D.(2015) Postdoc, UC Berkeley (Fleming Group)

Eric Pozzi 2011-2016 Ph.D.(2016) Intel

Sicelo Masango 2011-2016 Ph.D.(2016) Intel

Stephanie Zaleski 2011-2016 Ph.D.(2016) Postdoc, Met. Museum (Leona Group)

Alyssa Zrimsek 2011-2016 Ph.D.(2016) Postdoc, U Pitt (Asher Group)

Lingxuan Peng 2011-2016 Ph.D.(2016) Intel

Naihao Chiang 2012-2017 Ph.D.(2017) Postdoc, UCLA (Weiss Group)

Michael McAnally 2012-2017 Ph.D.(2017) IDA (Scientist)

Van Duyne Group: PlacementGraduate Students #2

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Van Duyne Group: PlacementDouglas A. Stuart

Katherine A. Willets

Paul L. Stiles

Rebecca L. Stiles

Jeffrey N. Anker

Jon P. Camden

Christa Brosseau

Nilam Shah

Kristin Wustholz

Faith Boman

Julia Ruemelle

Julia Bingham

Dragos Seghete

Jon Yuen

Jon Dieringer

2003-2006

2005-2007

2005-2007

2007-2008

2006-2008

2006-2008

2007-2009

2008-2010

2007-2010

2009-2011

2009-2011

2010-2011

2010-2011

2010-2012

2008-2011

University of West Georgia (Faculty)

Temple University, Austin (Faculty)

ZEV Capital Research (Analysis & Design)

BASF (Senior Manager)

Clemson University (Faculty)

Notre Dame (Faculty)

Saint Mary’s University (Faculty)

Northwestern University (Res. Faculty)

College of William & Mary (Faculty)

Stepan Company (Research Scientist)

Illinois Toolworks (Research Scientist)

St. Xavier College (Faculty)

Intel

Washington University, St. Louis (Postdoc)

Eli Lily, Research Scientist

Postdoctoral Fellows #1

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Van Duyne Group: PlacementLaura Sagle

Renee Frontiera

Samuel Kleinman

Bhavya Sharma

Nan Jiang

Nilam Shah

2009-2012

2010-2013

2012-2013

2011-2015

2010-2015

2009-2015

University of Cincinnati (Faculty)

University of Minnesota (Faculty)

Research Scientist, (OndaVia, Inc.)

University of Tennessee (Faculty)

University of Illinois, Chicago (Faculty)

Lake Forest College (Faculty)

Lauren Buchanan 2013-2016 Vanderbilt University (Faculty)

Dmitry Kurouski 2013-2015 Texas A&M (Faculty)

Bogdan Negru 2013-2016 Sonoma State (Faculty)

M. Fernanda Cardinal 2012-2017 U of San Martin, Argentina (Faculty)

Guillaume Goubert 2014-2017 ETH Zurich (Senior Scientist)

Postdoctoral Fellows #2

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Group Meetings:

Subgroup Meetings

Time: Thursdays 4-5 pmPlace: TECH K140

Van Duyne Group

SERS: Monday

Time: 11 am-12 noonPlace: K126

TERS: TuesdayUltrafast: Wednesday

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Open House:Date: September 17, 2017Time: 4-6pmPlace: Pancoe Café (2nd floor next to Einstein’s)

Meet the group, see our work, enjoyfree FOOD and DRINKS

Van Duyne Group

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Van Duyne Group Project Summary (2017-2018)New Students = 2 (either full or joint)

NSF (CHE): Single Molecule & Ultrafast Spectroscopy

DOD PRMRP: SERS Glucose Sensing

NSF (CCI): Ultrafast TERS, Ultrafast Raman, Plasmonic Chem.

NSF (PIRE): TERS in Art Conservation

AFOSR MURI: Nanoscale Electrochemistry: EC-TERS

AFOSR COE: Bioprogrammable plasmonic sensors for humanperformance biomarkers

DOE (SISGR): TERS, 2D Materials (Pending)

DOE (ICEP): SERS, ALD, Catalysis

DOD VBFF: Strong Light-Matter Coupling

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Questions