Research Seminar for New Graduate Students Ryan 4003, 11 ......18 4.3 nm Resolution in RT-UHV-TERS:...
Transcript of Research Seminar for New Graduate Students Ryan 4003, 11 ......18 4.3 nm Resolution in RT-UHV-TERS:...
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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, [email protected]
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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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