Implement taste and smell with nanosensors - IEEE€¦ · 22 . 600 700 800 900 1000 1100 1200 1300...

© 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 [email protected]

© 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

http://en.wikipedia.org/wiki/File:Hearing_aid_20080620.jpg�


3

San Bruno Fire

http://nationalpostnews.files.wordpress.com/2010/09/0910cali7.jpg�


4 Milk adulteration with melamine


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Pesticide residue?


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


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Safe, secure, sustainable world and people’s well-being demand more sensors


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Nanosensor is the solution to implement smell and taste (chemical sensing or chemosensation)


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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


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.


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

4 5 6 7 8 9 10

-3

-2

-1

0

1

2

∆ID

S /

I DS (%

)

Time (s)

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

T A

C A

A A

T A A

T

C C

SiNW I

T A

C A

A A

T A A

T

C C

- - - - - -

I T A

C A

A A

T A A

T

C C

- - - - - -

I

Z. Li, et al, Nanoletter, 2004, 4, 245

pH sensing DNA sensing


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I. Park, Z. Li et al, Nano Letters, 2007 and 2011

Smelling the hydrosulfide gas


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


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.

0

100

200

300

400

500

600

700

800

Num

ber o

f pub

licat

ions

Year

Publications in SERS area


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


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.


Top-down meets self-assembly the leap from stochastic to deterministic SERS structures


• 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


CAN WE DESIGN FINGER SYMMETRY? 2 3 4 5 7

200 nm

Ou, F. S. et. al. Nano Letters, 2011, 11, 2538–2542.


SERS of nanofinger of different symmetry

Ou, F. S. et. al. Nano Letters, 2011, 11, 2538–2542.

BPE


100f 1p 10p 100p 1n 10n 100n 1μ 10μ 100μ 1m

0

10000

20000

30000

40000

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

ity (a

rb. u

nit)

BPE concentration [mol/L]

BPE sensing

NN

1000 1100 1200 1300 1400 1500 1600 17000

500

1000

1500

2000

2500

3000

3500 1 nM (182 ppt) 100 pM (18.2 ppt) 10 pM (1.82 ppt) 1 pM (0.182 ppt) 100 fM (0.0182 ppt)

Ram

an in

tens

ity (a

.u.)

Raman shift (cm-1)

100f 1p 10p 100p 1n

0

500

1000

1500

2000

BPE concentration (mol/L)

Ram

an in

tens

ity (a

rb. u

nit)

Ethanol solution

Detection limit of 0.02 parts per trillion

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Demonstration A:

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600 700 800 900 1000 1100 1200 1300

0

5000

10000

15000

20000

Ram

an in

tens

ity (a

.u.)

Raman shift (cm-1)

1 mM

100 uM

10 uM

1 uM 100 nM 10 nM 1 nM 1E-9 1E-8 1E-7 1E-6 1E-5 1E-4 1E-3

0

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10000

Ram

an in

tens

ity (a

.u.)

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


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.

900 1000 1100 1200 1300 1400 1500 1600

0

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9000

100 pM

1 µM10 µM

100 µM

Ram

an in

tens

ity (a

.u.)

Raman shift (cm-1)

1 mM

100 nM

10 nM1 nM

Implement taste and smell with nanosensors - IEEE€¦ · 22 . 600 700 800 900 1000 1100 1200 1300...

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