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Richard P. Van Duyne

Research Seminar for New Graduate StudentsNano4003, 9:00 - 9:15 AM Thursday September 12, 2013

Molecular Plasmonics: Nanoscale Spectroscopy & Sensing

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

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What is the Mechanism?

μ = αE

EFCHEM ~ 101 EFEM ~ 108

EFSERS = 1 x 108

Ek

Benzenethiolhhννoo h(h(ννoo--ννvib)

Haes, Haynes, McFarland, Zou, Schatz, and Van Duyne, MRS Bulletin, 30, 368-375 (2005)P. Stiles, J. Dieringer, N. C. Shah, and R. P. Van Duyne, Ann. Rev. Anal. Chem., 1, 601-626 (2008)

Surface Enhanced Raman Spectroscopy (SERS)

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Van Duyne Group Research Portfolio #1Grand Challenge: Control light on the 1-100 nm Length Scale

Plasmonic Materials

MRS Bulletin, 30, 368 (2005)

Plasmonic Biosensors

Nature Materials, 7, 442 - 453 (2008)

Single Molecule Spectroscopy

JACS, 129, 16249-16256 (2007)

Single Particle Spectroscopy

JPCC, 116, 393-403 (2012)

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Van Duyne Group Research Portfolio #2Ultrafast Plasmonics

JPCL, 2, 1193-1203 (2011)

Single Molecule TERS

JPCC 116, 487-483 (2012)

Ultrafast Photoionization Microscopy

Nano. Lett. 12, 4823-4829 (2012)

UHV-TERS

Nano Lett. 12, 5061-5067 (2012)

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Ultrahigh Vacuum Tip-Enhanced Raman Spectroscopy

Ag tip is plasmonic amplifier

All external optics

< 2 x 10-11 torr

Cryostat: 7K; 19K

E. Foley, N. Jiang, A. McFarland, J. Klingsporn, M. Sonntag, J. Dieringer, M. Hersam, and R. P. Van Duyne, in preparation (2013)

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15Å

3Å

2nm

2nm

9.1Å

11.2Å 11.2Å

Cross Section

10pA

, 2.0

V

Single molecules and/or clusters observed on the Ag(111) surface

LT-UHV-STM R6G/Ag(111): 1 mW @ 532 nm Ag Tip

J. Klingsporn, N. Jiang, E. Pozzi, M. Sonntag, D. Chulhai, T. Seideman, L. Jensen, M. Hersam, and R. Van Duyne, submitted (2013)

7J. Klingsporn, N. Jiang, E. Pozzi, M. Sonntag, D. Chulhai, T. Seideman, L. Jensen, M. Hersam, and R. Van Duyne, submitted (2013)

Line Narrowing in LT-UHV-TERS: R6G/Ag(111)

14001450150015501600165017001750

1700 1600 1500 1400

Nor

mal

ized

Inte

nsity

Raman Shift (cm-1)

a

b

c

d

e

RT-SERSAverage peakwidth: 20 cm-1

RT-TERSAverage peakwidth: 17 cm-1

LT-SERSAverage peakwidth: 18 cm-1

LT-TERSAverage peakwidth: 9 cm-1

LT-TERS fitresiduals

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1310

19

16

14

21

13

26

16

9

22

16 24

22

22

231314

1921

17 12

(9)(18)

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1700 – 1400 cm-1 Region

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High Repetition Rate is Needed for SE-FSRS

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High Resolution Plasmonic Sensors

HR-LSPR Sensor: Calmodulin JACS, 130, 5836-5837 (2008)

Nano Lett,11,1098-1105 (2011)

Single Molecule LSPRNano Lett., 11, 1826-1830 (2011)

Van Duyne Group Research Portfolio #3

Super-Resolution LSPR MicroscopyJACS, 134, 15832–15839 (2012)

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SERS for Art Conservation ScienceVan Duyne Group Research Portfolio #4

TLC-SERS for Fiber AnalysisAnal. Chem. 81, 3056-3062 (2009)

SERS for Fiber AnalysisPCCP, 11, 7350-7359 (2009)

SERS to Identify of Color in Mary Cassatt’sPastels, Anal. Chem. 81, 7443-7447 (2009)

SERS to Identify Color in Winslow Homer’sWatercolors, JRS 42, 1305-1310 (2011)

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Van Duyne Group & Collaborators Summer 2013

InternationalMikael Käll (Chalmers)

Bill Barnes (Exeter)Besenbacher (Aarhus)

Pileni (Paris VI)Vallee (Lyon)

Liz-Marzan (Spain)

NU, ChemistryHupp, Mirkin, Mrksich,

Ratner, Schatz, Seideman, Stair, Weitz

NU, Neuro.Bill Klein

UIUC, ChemistrySligar

AIC, Art Conserv.Casadio

NU, MS&EHersam, Marks

NU, BMEGlucksberg, Walsh, Zhang

UCI, CaSTLApkarian, Ho

3rd Row: Jon Dieringer, Matt Sonntag, Bogdan Nehru, Jordan Klingsporn, Eric Pozzi, Cassie George, Mike McAnally, James Brooks, Sicelo Manango, Dmitri Kurouski

2nd Row: Nan Jiang, Naihao Chaing, Alex Peroff, Natalie Gruenke, Natalie Ray, Sanaiya Khatwani, Laura Ruvuna, Alyssa Zrimsek, Huayi Wang,David Pawletki

1st Row: Nilam Shah,, Stephanie Zaleski, Bhavya Sharma, Fernanda Cardinal, Emily Sprague, Nathan Greeneltch, Anne-Isabelle Henry, Nolan Wong

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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)

Ph.D.(2007)

Ph.D.(2008)

Ph.D.(2008)

M.S.(2008)

Ph.D.(2009)

Ph.D. (2010)

Ph.D. (2010)

Ph.D. (2010)

2002-2007

2003-2008

2003-2008

2006-2008

2004-2009

2005-2010

2005-2010

2005-2010

Jiha Sung

Jing Zhao

David Q. Andrews

Jenny Roden

Kevin Biggs

Paige Hall

Kathryn Kosuda

Julia Bingham

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

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

Chemistry Instructor, Bossier Parish Community College (Faculty)

Ph.D.(2007)2002-2007Leif J. Sherry

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

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

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

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

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

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

Van Duyne Group: PlacementGraduate Students

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Postdoc, NU (Van Duyne Group)

Postdoc, NU (Van Duyne Group)

ExxonMobil (Research Scientist)

Enhanced Plasmonics, LLC (Founder)

British Petroleum (Chemist)

MedSphere Corp. (Biomed. Engineer)

Ph.D.(2012)

Ph.D.(2013)

Ph.D.(2013)

Ph.D.(2013)

Ph.D.(2013)

Ph.D.(2013)

2007-2012

2009-2013

2009-2013

2009-2013

2009-2013

2009-2013

Samuel Kleinman

Matt Sonntag

Lauren Kreno

Nathan Greeneltch

Natalie Ray

Ke Ma

Rice University (Faculty, Mat. Sci.)Ph.D.(2012)2008-2012Emilie Ringe

Van Duyne Group: PlacementGraduate Students #2

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Van Duyne Group: Placement

University of West Georgia (Faculty)

University of Texas, Austin (Faculty)

ZEV Capital Research (Analysis & Design)

Avon (Program Manager)

Clemson University (Faculty)

University of Tennessee (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 (Research Scientist)

Washington University, St. Louis (Postdoc)

Northwestern University (Res. Faculty)

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

Douglas 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

Postdoctoral Fellows

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Van Duyne Group: Placement

University of Cincinnati (Faculty)

University of Minnesota (Faculty)

Research Scientist, (OndaVia, Inc.)

2009-2012

2010-2013

2012-2013

Laura Sagle

Renee Frontiera

Samuel Kleinman

Postdoctoral Fellows #2

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Group Meetings:

Open House:Date: 10/16/13Time: 4:00 – 6:00 pmPlace: Pancoe 2nd Floor near Einstein’s

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

Time: Thursdays 4-5 pmPlace: TECH K140

Van Duyne Group

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Van Duyne Travel ScheduleSeptember - November

09/30/13 – 10/03/13: SciX

10/28/13 – 10/29/13: Osaka, Japan

10/21/13 – 10/23/13: ARO Workshop

11/05/13 – 11/07/13: Singapore

11/18/13 – 11/22/13: Nanjing, China

10/30/13 – 10/31/13: DARPA

09/14/13 – 09/27/13: Vacation

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Van Duyne Group Project Summary (2013-2014)New Students = (2 full or 1 full & 2 joint)

NSF (MRSEC): Plasmonics, Ultrafast Plasmon Switching, HRTEM

NSF (CHE): Single Nanoparticle & Ultrafast Spectroscopy

SERS/TERS in Art Conservation (Renewal Pending)Mellon Foundation:

DOE (SISGR): Ultrafast TERS, Photocatalysis, Solar

DARPA (IVN:Dx): in vivo Nanosensors

NSF (CCI): Ultrafast TERS, Ultrafast Raman, electron transfer

NSF (SCIART): NIR-SERS in Art Conservation (Renewal Pending)

SERS Sensors – Critical Care AnalytesBaxter:

ARO SBIR (Phase II): SERS Gas Sensing

AFOSR: Mechanism of CO2 Electrocatalysis (Pending)

AFOSR MURI: Nanoscale Electrochemistry – SECM/TERS (New)