organic electronic biological sensing: what are we up to? · 1 annual meeting of the centre of...

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Annual meeting of the Centre of ExcellenceAnnual meeting of the Centre of Excellenceon Functional Materialson Functional Materials

Organic electronic biological Organic electronic biological sensing: what are we up to?sensing: what are we up to?

Luisa TorsiLuisa TorsiDipartimento di Chimica

Università degli Studi di Bari

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luisa torsi Bari, april 21st- 2009

Goal of the Goal of the activityactivity

Fexible RFID-tag

Smart Cards

Wereable sensors

Portable sensor

Low cost

Large area

Flex plastic substrate

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luisa torsi Turku, August 27-28 2009

Goal of the Goal of the activityactivityAffymaxAffymax DNA chipDNA chip

http://http://bmel.korea.ac.kr/image/intro_fig_5_4.gifbmel.korea.ac.kr/image/intro_fig_5_4.gif

Low cost, low power, disposable electronic sensing system Low cost, low power, disposable electronic sensing system Implemented on flex substrate (plastic, fabric, paper)Implemented on flex substrate (plastic, fabric, paper)

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State of the artState of the art

UCLAUT

AustinCagliari

Tokyo

Nanyang

P&MCurie

JH Univ

PNNL

CNRBO

UCBerkeley

LINZCNRIMM

Trento UPENN

Philips

LinköpingAbo

IMECBARI

Cornell

Stanford

H. H. LaursLaurs and G. and G. HeilandHeiland, , ThinThin SolidSolid FilmsFilms 149 (1987) 129149 (1987) 129--142 (142 (11°° OFET sensor)OFET sensor)A. A. AssadiAssadi, G. , G. GustafssonGustafsson, M. , M. WillanderWillander, C. , C. SvenssonSvensson, O. , O. InganasInganas, , SynthSynth. Met. 37 (1990) 123. Met. 37 (1990) 123

L. Torsi, A. Dodabalapur, L. Sabbatini, P.G. Zambonin, L. Torsi, A. Dodabalapur, L. Sabbatini, P.G. Zambonin, Sensors and Actuators B., 67, 312, 2000.Sensors and Actuators B., 67, 312, 2000.

Sdielectric

DSorg org semsem

G

5


Young but Young but …… growing fieldgrowing field

Luisa Torsi and Ananth Dodabalapur, Analytical Chemistry, 70, 381A-387A (2005).Luisa Torsi, Analytical and Bioanalytical Chemistry, 384(2), 309 (2006).

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DeviceDevice fabricationfabrication

Highly doped Si substrate2SiO2

S DGVgs

Vds

20 0 -20 -40 -60 -80-1000

-10-20-30-40-50-60

ΔI

(a)

I ds(μ

A)

Vg(V)

N2

Butanol

0 -20 -40 -60 -80 -1000

-10

-20

-30

-40

-50

I ds (μ

A)

Vds (V)

Grain surface

EB

⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕


7

22

time (sec)time (sec)

-5-50055

55

00

700700600600500500400400300300

-1-1

00

VG (V)VG (V)

Analyte deliver

trigger pulse

Analyte deliver

trigger pulse(V)(V)

Ids(μA)Ids(μA)

0 10 20

Cyc

le n

umbe

r

time (sec)

-0.15

-0.10

-0.05

0.00

0.05

60

40

20

0

dDDα6T / 1-hexanol, on current

I ana

lyte

(μA

) -1.0

-0.5

0.020100

time (sec)

dDDα6T/1-hexanol, Vds = -5V

Vg = -5V

Vg = -4VVg = -3VVg = -2VVg = -1VVg = 0V

B. Crone, A. Dodabalapur, A. Gelperin, L. Torsi, H.E. Katz, A.J. Lovinger, and Z. Bao,Appl. Phys. Lett., 78, 2229, 2001.

@ Bell @ Bell LabsLabs


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OFET sensors are not OFET sensors are not ISFETsISFETs

• electrochemical (potentiometric) sensors, not really an electronic one

• they have been around for most then 30 years but the only commercial success is as hydrogenleakage sensor (S.Lundström et a.,l Appl. Phys. Lett. 26 (1975) 55.)

• they need reference electrode but It has not yet found a stable reference integrated in an electronic circuit (B.A. McKinley, Chem. Rev. 108, (2008) 826)

P. Bergveld, IEEE Trans. Biomed. Eng. BME-19, 342, 1972.J. Janata, M. Josowicz, Nature Materials 2, 19, 2003.


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OFET sensing arraysOFET sensing arrays

T. Someya, T. Sekitani, S. Iba, Y. Kato, H. Kawaguki, T. Sakurai, PNAS, 101, 9966, 2004.

Artificial skinwith

temperature and pressure

sensor


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DHDH--αα6T OTFT6T OTFT

0 -20 -40 -60 -80 -1000

-20

-40

-60

-80

Vg = - 0VVg = - 40V

Vg = - 60V

Vg = - 80V

Vg = - 100VI ds

(μA)

Vds(V)20 0 -20 -40 -60 -80-100

0,000

0,002

0,004

0,006

0,008

0,010

0,012

squa

re ro

ot -

I ds (A

)

Vg (V)

Vt= -1.72 Vμ= 0.095 cm2/V s

(b)(a)

0 -20 -40 -60 -80 -1000

-20

-40

-60

-80

Vg = - 0VVg = - 40V

Vg = - 60V

Vg = - 80V

Vg = - 100VI ds

(μA)

Vds(V)20 0 -20 -40 -60 -80-100

0,000

0,002

0,004

0,006

0,008

0,010

0,012

squa

re ro

ot -

I ds (A

)

Vg (V)

Vt= -1.72 Vμ= 0.095 cm2/V s

(b)(a)

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20 0 -20 -40 -60 -80 -1000

-10-20-30-40-50-60

ΔI

(a)

I ds(μ

A)

Vg(V)

N2 Butanol

20 0 -20 -40 -60 -80 -100

10-8

10-7

10-6

1x10-5

1x10-4

(b)

|I ds(A

)|

Vg(V)

N2 Butanol

0 -20 -40 -60 -80 -1000

-10

-20

-30

-40

-50

(c)

N2

I ds (μ

A)

Vds (V) 0 -20 -40 -60 -80 -1000

-10

-20

-30

-40

-50(d)Butanol

I ds (μ

A)

Vds (V)

DHDH--αα6T / butanol6T / butanol

Trans-characteristicsin citronellol

TransTrans--characteristicscharacteristicsin citronellolin citronellol

Tran-characterisics in N2

TranTran--characterisicscharacterisics in in NN22

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The role of grainThe role of grain boundaries boundaries

•• EllipsometryEllipsometry: : no swellingno swelling•• QCM: QCM: mass mass incresesincreses

•• EEaa increases upon exposure to analyteincreases upon exposure to analyte(A. Dodabalapur.(A. Dodabalapur. et al. et al. SPIE Optics and PhotonicsSPIE Optics and Photonics 2007 2007 -- 2626--30 August, San Diego, CA)30 August, San Diego, CA)Correlation between Correlation between OligothiopheneOligothiophene Thin Film Transistor Morphology and Vapor Responses L. Torsi, AThin Film Transistor Morphology and Vapor Responses L. Torsi, A. J. . J.

Lovinger, B. Crone, T. Someya, A. Dodabalapur, E. Katz, A. GelpeLovinger, B. Crone, T. Someya, A. Dodabalapur, E. Katz, A. Gelperin, Journal of Phys. Chem. B, 2002, 106, 12563rin, Journal of Phys. Chem. B, 2002, 106, 12563

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PTO OTFTPTO OTFTPTO: Phenylene-thiophene oligomer

GG

SiOSiO22

SiSi

SS DDPTOPTO

0 -20 -40 -60 -80 -100

0

-20

-40

-60

-80

-100

I ds (n

A)

Vds(V)0 -20 -40 -60 -80 -100

0,0

5,0x10-5

1,0x10-4

1,5x10-4

2,0x10-4

2,5x10-4

3,0x10-4

(I dsS

AT )1/

2 (A)1/

2Vg (V)

Vt= - 12.8 Vμ= 1.3 10-4cm2/Vs

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LoD =3.6 + 1.5 ppm

Sensitivity enhancementSensitivity enhancement

0 5 10 15 20 25 30 350.0

-0.5

-1.0

-1.5

-2.0

-2.5 (R)-(+)-β-citronellol (S)-(-)-β-citronellol

ΔI (n

A)

β-citronellol [ppm]

responses @ fixed gate bias

20 0 -20 -40 -60 -80 -1001E-14

1E-13

1E-12

1E-11

1E-10

(R)-(+)-β-citronellol(S)-(-)-β-citronellol

m (A

/ppm

)

Vg (V)

sensitivity vs. gate bias

three order of magnitude enhancement !!!

m

15

2D 2D sensingsensing responseresponse

0 5 10 15 20 25 30 35012345678

ΔI(n

A)

β-Citronellol [ppm]

95 nm 290 nm 470 nm 950 nm

Vgs = -50 V

GG

SiOSiO22

SiSi

SS DD

L. Torsi, G.M. Farinola, M.C. Tanese, O. Hassan Omar, L. L. Torsi, G.M. Farinola, M.C. Tanese, O. Hassan Omar, L. ValliValli, F. Babudri, F. Palmisano, P.G. , F. Babudri, F. Palmisano, P.G. Zambonin & F. Zambonin & F. NasoNaso. , . , Nature Materials Nature Materials 77 (5), 412(5), 412--417 (2008)417 (2008)

⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕


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2D Field2D Field--induced conductanceinduced conductance

0 -20 -40 -60 -80 -100

10-11

10-10

10-9

10-8 5 10 15 20 40 45 50

Fiel

d-ef

fect

Con

dutta

nce

(S)

Vg(V)

A. Dodabalapur, L. Torsi and H.E. Katz, A. Dodabalapur, L. Torsi and H.E. Katz, ScienceScience 268, 270, 1995268, 270, 1995M.C. Tanese M.C. Tanese etet al. , al. , ThinThin SolidSolid FilmsFilms, 516, 3263 2008, 516, 3263 2008

S

dielectric

org org semsem

GG

SS DD⊕ ⊕ ⊕ ⊕ ⊕ ⊕


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Bilayer OTFTBilayer OTFT

A. Dodabalapur, H.E. Katz and L. Torsi, A. Dodabalapur, H.E. Katz and L. Torsi, ScienceScience 269, 1560, 1995269, 1560, 1995


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OTFT gas OTFT gas sensorssensors

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PTA OTFT sensor for citronellolPTA OTFT sensor for citronellol

0 5 10 15 20 25 30 350,0

-0,5

-1,0

-1,5

-2,0

-2,5

-3,0

ΔI (n

A)

β-citronellol [ppm]

PTA / citronellolPTA / citronellol

Vg = -100 V

Analytes: Citronellolenantiomers

OH OH

(+) (-)

Receptor: amino acid

(R)-(+)-β-citronellol(R)(R)--(+)(+)--ββ--citronellolcitronellol

(S)-(-)-β-citronellol(S)(S)--((--))--ββ--citronellolcitronellol

RacemateRacemateRacemate

(+)LOD 2.5 ±1.0 ppm(-)LOD 3.6 ±1.5 ppm

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Role of contact resistanceRole of contact resistance

GG

SiOSiO22

SiSi

SS DDPTOPTO

β-citronellol ((R)R)--(+) / (+) / (S)(S)--((--))or carvone (R)R)--((--)) / (S)/ (S)--(+)(+)

RRcc RRchch

Contact Effects in Organic Thin-Film Transistor Sensors

Luisa Torsi et al. Organic Electronics 10, 233–239 (2009).

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104 W cm, but more often, in the 105 W cm are typical for thiophene based materials contacted with gold electrodes

0,0 0,2 0,4 0,6 0,8 1,00123456789

Vg = -20V Vg = -40V Vg = -60V Vg = -80V Vg = -100V

R W

( MΩ

cm

)

Channel Lenght - L (mA)

RRchch and and RRcc: transfer line : transfer line metodmetod

22


RRcc < < RRchch

23



24


Nano pentacene OTFTNano pentacene OTFT

0 1 0 2 0 3 0 4 0 5 0 6 00

2

4

6

8

1 0 V g = -2 5 V -1 5 V -5 V 0 V + 5 V

Nor

mal

ized

Sou

rce-

Dra

in C

urre

nt

T im e (s e c )

1 5 n m c h a n n e l

o n o ff

0 10 20 30 40 50 600,0

0,2

0,4

0,6

0,8

1,0

1,2

Nor

mal

ized

Dra

in C

urre

nt

T im e (sec)

Vg = -30V -20V -10V 0V +5V

25 um channelon

off

L. Wang, D. Fine, A. Dodabalapur, Appl. Phys. L. Wang, D. Fine, A. Dodabalapur, Appl. Phys. LettLett. 85, 6386, 2004, Liang Wang, Daniel Fine, Luisa Torsi and . 85, 6386, 2004, Liang Wang, Daniel Fine, Luisa Torsi and Ananth Dodabalapur Analytical and Ananth Dodabalapur Analytical and BioanalyticalBioanalytical Chemistry, 384(2), 310Chemistry, 384(2), 310--321 (2006).321 (2006).

Journal list TopJournal list Top--ten in 2006 ten in 2006

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20 0 -20 -40 -60 -80 -100

1E-13

1E-12

1E-11

1E-10

1E-9

m (A

/ppm

)

Vg (V)

L = 0.2 mm L = 1 mm


26

Low voltage operationLow voltage operation

Dr. M. Grell’s group at Shieffield University - Adv. Func. Mat. 2005, 15, 1017


27

The The BaoBao’’ss group @ Stanfordgroup @ Stanford

Prof, Zhenan Bao’s group at Stanford University – PNAS in press


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Future developments @ UNIBAFuture developments @ UNIBA

= Phospholipidic Bilayer

= Protein receptor

= Analyte

2D electronic transport

Plastic / Paper substrate

Au (S)Organic Semiconductor

Ti (G)

Au (D)TiO2 (ultra-thin dielectric)

Aqueous sample analyte

M. D. Angione, A. Mallardi , G. Romanazzi, G. P. Suranna, P. Mastrorilli, D. Cafagna, E. De Giglio, G. Palazzo and L. Torsi*

3rd IEEE International Workshop on Advances in Sensors and Interfaces

Martin Andersson, Henk M. Keizer, Chenyu Zhu, Daniel Fine, Ananth Dodabalapur, and Randolph S. Duran* Langmuir 23(6), 2924 (2007)

0 -20 -40 -60 -80 -1000

-4

-8

-12

I ds(μ

A)

Vds(V)

Membrane Proteins Embedded in Supported Lipid Bilayers Employed in Field Effect Electronic Devices


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luisa torsi Bari, april 21st- 2009

Gas Sensors on Flexible Substrates for Wireless ApplicationsGas Sensors on Flexible Substrates for Wireless Applications

Hybrid very low-cost, ultra low-power olfaction system based on bioolfaction system based on bio--receptorreceptor and

implemented on a flexible substrate.system is to be compatible with wireless is to be compatible with wireless readread--outout, setting the ground for the future development of smart sensing RFID tags.

Applications in the field of logistics for the monitoring of perishable goods along their

transport and storing, though smart packaging solutions.

UNIBA coordinates the effortUNIBA coordinates the effort that involves 9 9 full partnersfull partners (two companies) to train 2121young researchersresearchers. Total grant: ca. 4M€

The FlexSMELL projectThe FlexSMELL project

Marie Curie Actions—Networks for Initial Training

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CalvanoCalvano

I. van der WerfI. van der Werf

D. D. LonganoLongano

S. S. LoperfidoLoperfido

V. V. DeGiorgio

DeGiorgioD. D. CafagnaCafagna

S. S. CotroneCotrone

M.C. TaneseM.C. Tanese

M. D. AngioneM. D. Angione

L. TorsiL. Torsi

N. N. CioffiCioffi

I. I. LositoLosito

E. De E. De GiglioGiglio

F. PalmisanoF. Palmisano

P.G. ZamboninP.G. Zambonin

N. DitarantoN. Ditaranto

L. SabbatiniL. Sabbatini

R. PilolliR. Pilolli

T. T. CataldiCataldi

Thanks !Thanks !


organic electronic biological sensing: what are we up to? · 1 annual meeting of the centre of...

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