surface enhanced raman scattering: substrate design and ... · r.f. aroca et al. / advances in...
TRANSCRIPT
![Page 1: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/1.jpg)
Surface Enhanced Raman Scattering:Substrate Design and Fabrication
Victor Ovchinnikov
Department of Aalto NanofabAalto UniversityEspoo, Finland
![Page 2: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/2.jpg)
Outline
• SERS principles and applications• SERS substrates
– Design– Fabrication methods
• Commercial SERS substrates– Specification– Understanding substrate design and processing– Proper substrate choice
July 24, 2016 ICQNM 2016 Nice, France 2
![Page 3: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/3.jpg)
Trace detection technologies
• Mass spectrometry and gas chromatography– Cost– Size
• Fluorescence spectroscopy– Excitation in visible range– Requires fluorophore
• SERS– Substrate price $10’s-$100– Sensitivity and repeatability issues
July 24, 2016 ICQNM 2016 Nice, France 3
![Page 4: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/4.jpg)
SERS measurements using a substrate
July 24, 2016 ICQNM 2016 Nice, France 4
P-SERS™ Technology Technical PaperDiagnostic anSERS https://www.diagnosticansers.com/technical/
![Page 5: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/5.jpg)
Trace chemical marker detection
July 24, 2016 ICQNM 2016 Nice, France 5
BPE (1,2-Bis(4-pyridyl)ethylene)
1207 cm-1
1207 cm-1
Diagnostic anSERS https://www.diagnosticansers.com/technical/
![Page 6: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/6.jpg)
SERS advantages• Can be used with solids, liquids or gases• No sample preparation needed (KBr, nujol)• Non-destructive, non-invasive• Works in-situ and in-vitro for biological samples• No vacuum needed• Works under a wide range of conditions (temperature, pressure)• Short time scale• Can work with aqueous solutions• Glass vials can be used• Can use down fiber optic cables for remote sampling• Very small analyzing volume – till single molecule• Extremely high spatial resolution• Inexpensive, portable equipment• Simultaneous detection of multiple sample constituents (multiplexing)
July 24, 2016 ICQNM 2016 Nice, France 6
![Page 7: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/7.jpg)
SERS disadvantages
• Cannot be used for metals or alloys
• Problems with quantitative analysis
• Can be swamped by fluorescence from somematerials
• Stability and repeatability issues
July 24, 2016 ICQNM 2016 Nice, France 7
![Page 8: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/8.jpg)
SERS applications
• Pharmaceutical industry• Biotech industry
– Bacteria, DNA and protein detection– Intracellular measurements (glucose measurement in vivo)
• Food industry– Melamine detection in milk– Pesticide detection
• Law enforcement and homeland security– Explosives detection (DNT)– Trace detection of narcotics such as cocaine and heroin
• Anti-counterfeiting (tags)– Weakened/inactive counterfeit drugs– Counterfeit petrol, perfumes and liquors
• Nanosensors
July 24, 2016 ICQNM 2016 Nice, France 8
![Page 9: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/9.jpg)
Scattered radiation
July 24, 2016 ICQNM 2016 Nice, France 9
Incident light (I0 , ν0)
Reflection
Transmission
Scattering
Scattering processesRayleigh Raman
particles molecular vibrations, phononsν0 ν0 ± ν
Is ~ 10-3 I0 Is ~ (10-6 – 10-9) I0ν <104 cm-1
a<<λ
![Page 10: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/10.jpg)
Energy levels
July 24, 2016 ICQNM 2016 Nice, France 10
Vibrationalstates
Excitedelectronstates
Virtualstates
FluorescenceRayleightIRStokesRaman
Anti-StokesRaman
E1
E0
E2
hν
ν0 - ν ν0+ ν
ν=0
ν=1
ν=2
ν=0
ν=1
ν=2
InRaman ν isinvariant toν0
![Page 11: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/11.jpg)
Cross-sections of the optical processes
July 24, 2016 ICQNM 2016 Nice, France 11
R. Aroca, Surface-Enhancend Vibrational Spectroscopy, J.Wiley & Sons Ltd, 2007
![Page 12: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/12.jpg)
Raman spectrum examples
July 24, 2016 ICQNM 2016 Nice, France 12
Bankapur A et all, (2010) .PLoS ONE 5(4): e10427.doi:10.1371/journal.pone.0010427.Laboratoire de Sciences de la Terre ENS-Lyon
Polysterene beadsLaser 785 nm
www.perkinelmer.com , Introduction to Raman SpectroscopyJ. Raman Spectrosc. 2004; 35: 82–86
GlassLaser 514 nm
Laser 514 nm
![Page 13: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/13.jpg)
Intermediate conclusion I
• Raman spectroscopy provides ‘fingerprint’ ofmolecular bonds and crystalline structure(phonons) in dependence on environmentconditions (temperature, pressure …) throughnon-resonance excitation of any vibrationaltransitions
• At the same time method applications in real lifeare hindered by very low cross-section ofRaman scattering
July 24, 2016 ICQNM 2016 Nice, France 13
![Page 14: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/14.jpg)
Bulk Raman versus SERS
July 24, 2016 ICQNM 2016 Nice, France 14
Bulk: 100 µM solution in a 13 µm3 scattering volume, × 100 immersion objective with 400 s integration time.SERS: signal from a single molecule under the same experimental conditions, but with 0.05 s integration time.
E. C. Le Ru et al., J. Phys. Chem. C, 111, 2007, p.13794–803
633 nm, 3 mW,rhodamine RH6G
![Page 15: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/15.jpg)
Steps of Raman development
• Laser application– dramatically improved power of excitation and Raman
signal• SERS effect
– Enhanced method sensitivity up to 1014
• Raman microscope– Decreased probe volume (light spot diameter below 1 μm)
• Portable SERS– Mobility of analyses
July 24, 2016 ICQNM 2016 Nice, France 15
C. Douketis et al., J. Chem. Phys. 2000, 113, 11315-23
![Page 16: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/16.jpg)
SERS discovery
• M. Fleischmann, P. J. Hendra, and A. J. McQuillan.“Raman spectra of pyridine adsorbed at a silverelectrode.”Chem. Phys. Lett., 26, 1974, p.163–66
• Jeanmaire D.L. and Van Duyne R.P., “Surface Ramanspectroelectrochemistry, part 1: heterocyclic, aromatic,and aliphatic amines adsorbed on the anodized silverelectrode.” J. Electroanal. Chem., 84, 1977, p.120
• Albrecht and Creighton, ”Anomalously intense Ramanspectra of pyridine at a silver electrode.” J. Am. Chem.Soc., 99, 1977, p.5215-17
July 24, 2016 ICQNM 2016 Nice, France 16
![Page 17: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/17.jpg)
SERS experiment with pyridineadsorbed on silver
McQuillan A J Notes Rec. R. Soc. 2009;63:105-109
©2009 by The Royal Society
KCl in water
July 24, 2016 ICQNM 2016 Nice, France 17
![Page 18: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/18.jpg)
SERS definitions• SERS is a phenomenon associated with the
enhancement of the electromagnetic field surroundingsmall objects optically excited near an intense and sharpplasmon resonance. The enhanced fields excite theadsorbate (probe) and the scattered radiation will againbe enhanced.
• Surface-enhanced Raman scattering (SERS) consists inusing the large local field enhancements that can exist atmetallic surfaces (under the right conditions, typically byprofiting from localized surface plasmon resonances) toboost the Raman scattering signal of molecules at (orclose to) the surface.
July 24, 2016 ICQNM 2016 Nice, France 18
E.C. Le Ru and P. G. Etchegoin, Principles of Surface-Enhanced Raman Spectroscopy and related plasmonic effects, Elsevier , 2009
![Page 19: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/19.jpg)
Lolcalized surface plazmon resonance(SPR) in metal sphere
July 24, 2016 ICQNM 2016 Nice, France 19
E.C. Le Ru and P. G. Etchegoin, Principles of Surface-Enhanced Raman Spectroscopy and related plasmonic effects, Elsevier , 2009.Stiles P.L. et all, Annual Review of Analytical Chemistry, 1, 2008, p.601-26
=3
ω + 2 0
The (complex) electric field inside the sphere is constant
εM - relative dielectric constant of medium
Ag sphere (r = 35nm) in vacuum,at resonance wavelength 370 nm
Max 85
= Plasmon
E in
![Page 20: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/20.jpg)
Electric field outside of metal sphere
July 24, 2016 ICQNM 2016 Nice, France 20
, , = 0 − α 0 −3
+ +
α =
=ω − εω + 2ε
, , – Cartesian coordinates,– radial distanse from sphere to the point ( , , ), , – Cartesian unit vectors
– radius of the sphere
Bθ
a
r
K. Kneipp, Physic Tody, 60(11), 2007, p. 40-46Stiles P.L. et all, Annual Review of Analytical Chemistry, 1, 2008, p.601-26
Ag nanosphere on glass
![Page 21: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/21.jpg)
E4 enchancement of outside field
July 24, 2016 ICQNM 2016 Nice, France 21
= 0 1 − + 3cos 2Re +
= 4 0
Maximum Eout at θ=0°
Electric field at the surface of nanosphere
=′
= 4 ′
Enhancement factor:
Stiles P.L. et all, Annual Review of Analytical Chemistry, 1, 2008, p.601-26
(in theory 1011 and 103, for field and chemical, respectively)
![Page 22: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/22.jpg)
Electromagnetic enhancement in near-field
July 24, 2016 ICQNM 2016 Nice, France 22
K. Kneipp, Physic Tody, 60(11), 2007, p. 40-46
Molecule
Metalnanoparticle
Adenine on Ag nanoclusters
Raman cross-section
Scattered field enhancementLaser excitation enhancement
IL – laser intensity
![Page 23: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/23.jpg)
Distance dependence
July 24, 2016 ICQNM 2016 Nice, France 23
=+
Stiles P.L. et all, Annual Review of Analytical Chemistry, 1, 2008, p.601-26
Pyridine, Ag over nanosphereAl2O3, 532 nm
![Page 24: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/24.jpg)
Ag dimer enhancement
July 24, 2016 ICQNM 2016 Nice, France 24
E. Hao and G. C. Schatz, J. Chem. Phys., Vol. 120, No. 1, 1 January 2004
36 nm spheres separated by 2 nm gap.
For sphere enhancement is 85 (slide 19)
![Page 25: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/25.jpg)
Plasmonic welding
July 24, 2016 ICQNM 2016 Nice, France 25
E. C. Garnett, Nature Materials 11, 241–249 (2012)
Suspended Si3N4 membrane
Gaps due to the presenceof surface ligands HOT SPOTS
Beforeillumination
W halogen lamp welding
200 nm 500 nm
500 nm
15–60 s heating at 200–300 °C
500 nm
![Page 26: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/26.jpg)
Wavelength dependence
July 24, 2016 ICQNM 2016 Nice, France 26
J. Phys. Chem. B 2005, 109, 11279-11285
benzenethiol,620 nm
NSL with 450nm spheres, 55 nm Ag on glass
SERES – suraface enhanced ecxitation spectroscopy
SERS is maximum when laser excitation is between SPRand the analized specturm line
λmax=(λex+ λvib)/2
![Page 27: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/27.jpg)
Inetrmediate conclusion II
• High local electromagnetic field near theplasmon nanostructures provides very highenhancement of Raman scattering (SERS)
• SERS effect depends on metal-molecule affinityand resonance conditions in molecule
• The highest EF is reached in random ’hot spots’,if the probe molecule has got at this ’spot’
July 24, 2016 ICQNM 2016 Nice, France 27
![Page 28: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/28.jpg)
Main types of SERS substrates
• A SERS substrate is any metallic(?) structure(nano-structure) that produces SERSenhancement:– Metal electrodes in electrochemistry (roughed
electrodes)– Metal nano-particles in solution ( colloids)– ‘Planar’ metal structures or arrays of metal nano-
particles supported on a planar substrate (glass,silicon)
July 24, 2016 ICQNM 2016 Nice, France 28
![Page 29: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/29.jpg)
Metal electrodes
• Surface protrusions 25-500 nm• Ag in KCl electrolyte• Oxidation-reduction cycles
July 24, 2016 ICQNM 2016 Nice, France 29
MethylviolegenLaser 1064 nm
bulk Raman
SERS
Zheng et al., J. Phys. Chem. B, Vol. 106, No. 5, 2002, p.1019-23
![Page 30: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/30.jpg)
Metal colloids for plasmonics• Mainly Au, Ag or Cu nanoparticles (diameter 10 – 80 nm) in water• Produced by:
– Chemical reduction (co-precipitation and reducing). Process depends on:• Kind of metal• Reducing reagent
– AgNO3 in sodium citrate (Lee and Meisel, 1982). Average 60 nm– HAuCl4 (Frens, 1973 and Natan 1995). Range 16 – 150 nm
• Temperature (boiling 1 h)• Stabilizing agents• Metal ion concentration
– Laser ablation– Photoreduction
• The best SERS is provided by highly aggregated colloids (dimers etc.)• Enhancement up to 1014 (SMD possible)
July 24, 2016 ICQNM 2016 Nice, France 30
![Page 31: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/31.jpg)
Images of metal colloids
July 24, 2016 ICQNM 2016 Nice, France 31
R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61
TEM of Ag citrate colloidλmax= 406 nm
TEM of Au borohydride colloid,Au particles 20-70 nm,
λmax= 535 nm
TEM of Au nanorods,λmax= 525 nm and 885 nm TEM of Au nanosquares
AFM of Au nanospheres embeddedin film of biopoymer chitosan
(inert organic matrix)
AFM of Ag nanowiresin dendrimer matrix
![Page 32: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/32.jpg)
Variety of geometric morphologies
July 24, 2016 ICQNM 2016 Nice, France 32
nanoprismsnanocubes
nanostarsnanosheets
A. X. Wang, and X. Kongl., Materials 2015, 8, 3024-3052
![Page 33: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/33.jpg)
Material and size effect in plasmonresonance
July 24, 2016 ICQNM 2016 Nice, France 33
Materials Today, Feb 2004, p. 26-31
AuAg alloy nanoparticles with increasing Au concentration
Au nanorods of increasing aspect ratio
![Page 34: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/34.jpg)
Material dependent features
• Ag – the highest EF, up to 1014
• Au - bio-compatibility• Mixture of Au and Ag nanoparticles – immuno-
gold colloids• Core-shell Ag@SiO2, Au@Al2O3–
– stability in all environments– better spreading on different surfaces– agglomeration protect
• Magnetic core for particle position controle
July 24, 2016 ICQNM 2016 Nice, France 34
![Page 35: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/35.jpg)
Detection of insecticide
July 24, 2016 ICQNM 2016 Nice, France 35
methyl parathion
contaminatedby parathion
contaminatedby parathion,
SERS
clean pericarp
Li, J.F. Et al., Nature 2010, 464, pp.392–395
![Page 36: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/36.jpg)
Gold lace nanoshells
July 24, 2016 ICQNM 2016 Nice, France 36
50 nm
M. Yang et al., SERS-Active Gold Lace Nanoshells with Built-in Hotspots, Nano Lett. 2010, 10, 4013-–4019
1-naphthalenethiol
PU means amphiphilic polyurethane template
![Page 37: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/37.jpg)
Nanoshell (core-shell)
• additional degree of tunability of SPR bychanging the thickness d of shells
• more uniform signal (less fluctuations)
July 24, 2016 ICQNM 2016 Nice, France 37
M. Gellner et al. / Vibrational Spectroscopy 50 (2009) 43–47
d = (ra - ri)
d variations
4-mercaptobenzoic acid (MBA)
633 nm
![Page 38: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/38.jpg)
Ag nanowires
July 24, 2016 ICQNM 2016 Nice, France 38
Tao et al., Nano Lett. 2003, 3, 1229–1233
45 nm x 2-3 um
1-hexadecanethiol
EF 2x105
EF 2x109
![Page 39: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/39.jpg)
Colloid disadvantages
• Storage – usually are used fresh prepared• Using in portable spectrometers• Reproducibility• Cost• Limited range of materials
July 24, 2016 ICQNM 2016 Nice, France 39
![Page 40: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/40.jpg)
Fabrication of planar SERS substrates
• Deposited films (self-organized metal islands)• Beam lithography (ring, crescent, dimer...)
– EBL– FIB
• Interference lithography• Nanoimprint• Template assisted lithography
– Porous polymers (polycarbonate membranes)– Porous anodic alumina Al2O3– Nanosphere lithography (NSL)
July 24, 2016 ICQNM 2016 Nice, France 40
![Page 41: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/41.jpg)
As deposited silver films
July 24, 2016 ICQNM 2016 Nice, France 41
4 nm0.2 Å/s
5.5 nm0.5 Å/s
10 nm2.0 Å/s
12 nm0.2 Å/s
Room temperature
![Page 42: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/42.jpg)
’Planar’ substrates - metal island films
• Prepared by PVD – physical vapor deposition
• Applicability to any substrate• High purity• Structure can be controlled by
– deposition rate (0.1 – 10 Å/s)– substrate roughness and temperature– mass thickness (4 - 8 nm)– Annealing (200 – 400°C)
July 24, 2016 ICQNM 2016 Nice, France 42
![Page 43: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/43.jpg)
EBL
July 24, 2016 ICQNM 2016 Nice, France 43
M. Kahl et al., Sensors and Actuators B-Chemical, 51 (1998), p. 285
![Page 44: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/44.jpg)
Nanohole array by lift-off
July 24, 2016 ICQNM 2016 Nice, France 44
100 nm thick Au200 nm holes
M. Najiminaini et al., Opt. Express 19, 26186-26197 (2011)
![Page 45: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/45.jpg)
FIB
• FIB lithography is superior to EBL:– Higher resolution– Higher resist sensitivity
• Additionally to EBL:– Local ion beam etching (subtractive lithography)
• 3D patterning
– Local deposition of materials (additive lithography)– Direct patterning of hard mask layers
• Multi-beam systems
July 24, 2016 ICQNM 2016 Nice, France 45
![Page 46: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/46.jpg)
FIB, Au, thickness 60 nm
July 24, 2016 ICQNM 2016 Nice, France 46
Nanofabrication, InTech, 2011, p. 247
![Page 47: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/47.jpg)
Lloyd’s mirror interference lithography
July 24, 2016 ICQNM 2016 Nice, France 47
Nanofabrication, InTech, 2011, p. 256
![Page 48: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/48.jpg)
Pillar based substrate
July 24, 2016 ICQNM 2016 Nice, France 48
M. R Gartia et al., Rigorous surface enhanced Raman spectral characterization of large-area high-uniformity silver-coatedtapered silica nanopillar arrays, Nanotechnology, 21(2010) 395701 (9pp)
benzenethiol
SiO2d=150nmgap 350 nmh=500nmAg 80nmEF=5·107
785 nm
![Page 49: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/49.jpg)
Nanoimprint lithography (NIL)
• Thermal assisted (T-NIL), 50 nm pitch, 100°Cabove Tg, 50-100 bar, 1995
• UV-NIL, 5 nm features, 0-5 bar
• Soft UV nanoimprint lithography (Soft UV-NIL),sub-50 nm range
July 24, 2016 ICQNM 2016 Nice, France 49
![Page 50: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/50.jpg)
Nanoimprint
July 24, 2016 ICQNM 2016 Nice, France 50
Recent Advances in Nanofabrication Techniques and Applications, InTech, 2011, p. 140
Limited application
Steppers
Reduced cost of master fabrication
![Page 51: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/51.jpg)
Plasmonic nanocavities200 nm, pitch 400 nm
July 24, 2016 ICQNM 2016 Nice, France 51
A. Cattoni et al., Nanoletters, 2011, pp. 3557-3563
Glass substrate, large surface < 1cm2,Au/dielectric/Au islandsGe -10 nm thick to improve theselectivity Amonil/PMMAAmonil (NIL resist) is not soluble insolvents
![Page 52: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/52.jpg)
NSL
July 24, 2016 ICQNM 2016 Nice, France 52
Recent Advances in Nanofabrication Techniques and Applications, InTech, 2011, p. 508
Dip-coating,drop-coatin, spinon.Problems for <100 nm spheres:surfaceroughness
![Page 53: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/53.jpg)
Nanocrescents fabricated bynanosphere lithography
July 24, 2016 ICQNM 2016 Nice, France 53
H. Rochholz et al., New Journal of Physics, 9 (2007) 53
![Page 54: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/54.jpg)
Exotic SERS substrates
• On-wire lithography (segmented structures)• Nano-capsules• Nano-antennas (Bowtie, Yagi-Uda)• Gratings and periodic structures (SPP)
Nanoporous gold• Hybrid SERS substrates (optical waveguide in
leaky mode and nanoparticles• Bio-enabled materials• Optical fibersJuly 24, 2016 ICQNM 2016 Nice, France 54
![Page 55: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/55.jpg)
Ideal SERS substrate
• High EF• No fluorescence background• Broad wavelength range• Unlimited laser power• Long shelf life• Reproducibility• Different environments• Different available sizes• Homogenity through the substrate area
July 24, 2016 ICQNM 2016 Nice, France 55
![Page 56: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/56.jpg)
Saleable SERS substrate (Klarite)
July 24, 2016 ICQNM 2016 Nice, France 56
www.d3technologies.co.uk - www.renishawdiagnostics.com/en/klarite-sers-substratesZHIDA XU, Master Thesis, University of Illinois at Urbana-Champaign, 2011
785 nm
c-Si
E/E0
Very high enhancement is ‘sacrificed’ in favor of homogeneity and reproducibility
75 EUR/pc 4x4 mm
1500 nm
![Page 57: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/57.jpg)
Diagnostic anSERS Inc, USA
July 24, 2016 ICQNM 2016 Nice, France 57
https://www.diagnosticansers.com/
Metal purityTemperature and humidity effect
Ink jet printing
![Page 58: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/58.jpg)
Ocean Optics Inc, USA
July 24, 2016 ICQNM 2016 Nice, France 58
Special nanoparticle ink onto a flexible substrate
Gold paper-based
Gold sponge on glass
Metal purityTemperature and humidity effect
http://oceanoptics.com/product/sers/
![Page 59: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/59.jpg)
Silmeco ApS, Denmark
July 24, 2016 ICQNM 2016 Nice, France 59
http://www.silmeco.com/
Self organized polymer mask and RIE
Cost
![Page 60: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/60.jpg)
Leaning Si pillars
July 24, 2016 ICQNM 2016 Nice, France 60
M.S. Schmidt et al., Adv. Mater. 2012, 24, OP11–OP18 no leaning leaning
![Page 61: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/61.jpg)
HORIBA, Ltd., Japan
July 24, 2016 ICQNM 2016 Nice, France 61
Dynamic oblique anglevacuum evaporation
http://www.horiba.com
High cost
![Page 62: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/62.jpg)
Enhanced Spectrometry, Inc., USA
July 24, 2016 ICQNM 2016 Nice, France 62
http://enspectr.com/sers-substates/
Low EFHigh costOnly silver
As deposited silver nanoparticlesAdditional amplification due to Ag layer
![Page 63: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/63.jpg)
Nanova Inc., USA
July 24, 2016 ICQNM 2016 Nice, France 63
Bimodal gold particle distribution 60 nm and 15 nmExcitation 785 nm
$25http://www.q-sers.com
Large particles from colloid?Small particles by evaporation
![Page 64: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/64.jpg)
July 24, 2016 ICQNM 2016 Nice, France 64
Summary
• Metal nanostructures provide huge EF of the Ramanscattering, making possible single molecule detection
• High informativity and sensitivity of SERS burstedmultiple applications of the method in different areas
• SERS substrate fabrication, distribution andreproducibility are still main problems for SERS
• Desing and fabrication of SERS substrate provideadditional information about substrate functionality
![Page 65: Surface Enhanced Raman Scattering: Substrate Design and ... · R.F. Aroca et al. / Advances in Colloid and Interface Science 116 (2005) 45–61 TEM of Ag citrate colloid λ max= 406](https://reader036.vdocument.in/reader036/viewer/2022062414/5ee076d3ad6a402d666ba457/html5/thumbnails/65.jpg)
SERS future
• Commercial production of reproducible andcheap SERS substrate
• Cheap and functional portable Ramanspectrometers
• Application of new plasmonic materials(graphene, semiconductors)
• Standartization and data bases for spectruminterpetation
July 24, 2016 ICQNM 2016 Nice, France 65