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© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP Confidential.
Implement taste and smell with nanosensors
Zhiyong Li HP Labs, Palo Alto, CA, USA zhiyong.li@hp.com
© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
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Microtechnology and semiconductor industry have revolutionalized modern life
Smell
Taste ?
Sight Hearing Touch
© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
3
San Bruno Fire
© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
4 Milk adulteration with melamine
© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
5
Pesticide residue?
© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
Analysis of food contaminants in Lab
Extraction Analysis (GCLC-MS)
Time-consuming: several hours (exclude sample shipping) Expensive tools: hundreds of thousands dollar Complicated: need professional operator (labor cost)
Sample concentrator
© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
7
Safe, secure, sustainable world and people’s well-being demand more sensors
© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
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Nanosensor is the solution to implement smell and taste (chemical sensing or chemosensation)
© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
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Food and agriculture: food contaminant test and monitoring, $1.6billion market Healthcare: Disease diagnostic, patient monitoring, multi-function test strips $53billion IVD market Drug regulations: supply monitoring, anti-counterfeiting, 5-10% of WW pharmaceutical annual sales of $800billion is believed to be counterfeit Chemical industry: industrial chemical monitoring Government: environmental monitoring, security and defense applications, food, agriculture and drug regulations R&D organizations: developing new apps
Potential application of smell and taste nanosensors
© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
Silicon ChemFET Nanosensor
Circuitry at nanoscale
Selective surface functionalization
Specificity and sensitivity
Bio-compatibility
Stability & reliability Power
I/O interfacing
Low-cost high-value sensor technology for parallel detection of 100s – 1000s of bio-molecular species.
© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
Sensing proton to DNA
3000 4000 5000 6000 7000 8000-5.0-4.5-4.0-3.5-3.0-2.5-2.0-1.5-1.0-0.50.00.51.01.52.02.5
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Micro-wire Nano-wire
C:\Documents and Settings\SVMO\My Documents\Projects\Calder\Details\13_05_r4c2_RIE_A1100_pHscl_1x ph micro nano - 27/22/2005 11:50:51
pH pH 5 4 5 6
pH 7 8 9 10 9 8
25 pM
n-SiNW
p-SiNW
Control
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Z. Li, et al, Nanoletter, 2004, 4, 245
pH sensing DNA sensing
© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
12
I. Park, Z. Li et al, Nano Letters, 2007 and 2011
Smelling the hydrosulfide gas
© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
Surface Enhanced Raman Spectroscopy (SERS) – enabling “molecular fingerprinting”
SERS Enhancement Factor ∝ |E(ω)|2 |E(ω’)|2
also approx. to ~ |E|4
Localized surface plasmon on nanostructure can enhance the Raman scattering process -- SERS
Electromagnetic field induced EF: 106 - 1012
SERS
No SERS
DNT
106-1012
Gain
Ag NP
hν
hν’
hν’ hν
© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
Surface Enhanced Raman Scattering (SERS)
1974 – M. Fleischman studied pyridine on roughened silver with increased surface area.
1977 – Rick Van Duyne and Alan Creighton reported enhancement of ~105 - 106 -- much too large to account for, by the increased surface area alone.
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Num
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f pub
licat
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Year
Publications in SERS area
© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
HP’s SERS Technology Evolution
Black Silicon (Etched Silicon Cones)
Polymer Cones (nanoimprinted)
Periodic Cones (nanoimprinted)
500nm
Periodic Gold Fingers
(nanoimprinted)
Deterministic Gold Fingers
(nanoimprinted)
2008
2009
2010
2011
© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
Molecular Trapped in SERS “hot-spots”
Top view of nanofingers
Field map of closed nanofingers
Cartoon of molecular Trapping
Hu, M. et. al. J. Am. Chem. Soc. 2010, 132, 12820.
© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
Top-down meets self-assembly the leap from stochastic to deterministic SERS structures
© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
• Leverage advantages from both top-down and bottom-up approaches – No need of costly critical dimension control. • Easy scale-up for large area uniformity and reliable hot spots – Roll-to-roll plastic fab. • Micro-capillary driven “finger” closing – Easy for fluidic interface, no power nor complicated controls needed. • Molecule self-limiting of the gap sizes, as small as sub-nm – Physical limit of the smallest separation manufacturable, hence strongest coupling effect. • Active molecule trapping by the fingers – Molecular tweezer with build-in sensing functionality.
Advantages of nanofinger structures
© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
CAN WE DESIGN FINGER SYMMETRY? 2 3 4 5 7
200 nm
Ou, F. S. et. al. Nano Letters, 2011, 11, 2538–2542.
© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
SERS of nanofinger of different symmetry
Ou, F. S. et. al. Nano Letters, 2011, 11, 2538–2542.
BPE
© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
100f 1p 10p 100p 1n 10n 100n 1μ 10μ 100μ 1m
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50000 Data: Data2_BModel: HillEquation: y=Vmax*x^n/(k n+x^n)Weighting: y Statistical Chi 2/DoF = 248.95693R^2 = 0.98792 Vmax 46682.94086 ±2689.4077k 3.1412E-7 ±1.1879E-7n 0.55525 ±0.04936
Ram
an In
tens
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rb. u
nit)
BPE concentration [mol/L]
BPE sensing
NN
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Ethanol solution
Detection limit of 0.02 parts per trillion
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© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
Demonstration A:
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Raman shift (cm-1)
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Concentration of melamine (mol/L)
max. amount in infant formula (FDA):
1 mg/kg (1part per million)
Melamine contamination in milk, 300,000 victims in China 2008
Melamine sensing with HP nanofinger SERS: >10,000× better than competitors
Detection limit of 100 parts per trillion
© Copyright 2011 Hewlett-Packard Development Company, L.P. The information contained herein is subject to change without notice. HP confidential.
Demonstration B:
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EPA regulation: 0.1 parts per million
on citrus fruits
Chlropyrifos sensing with HP nanofinger SERS: >1,000× lower than EPA regulation
Detection limit of 35 parts per trillion
Chlropyrifos, is a neurotoxin, carcinogen, once popular pesticide used worldwide, and the residue can be found in vegetables, fruits, etc.
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