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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luisa torsi Turku, August 27-28 2009
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
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luisa torsi Turku, August 27-28 2009
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
⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕
luisa torsi Turku, August 27-28 2009
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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
luisa torsi Turku, August 27-28 2009
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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.
luisa torsi Turku, August 27-28 2009
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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
luisa torsi Turku, August 27-28 2009
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luisa torsi Turku, August 27-28 2009
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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luisa torsi Turku, August 27-28 2009
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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luisa torsi Turku, August 27-28 2009
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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luisa torsi Turku, August 27-28 2009
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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luisa torsi Turku, August 27-28 2009
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)
⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕
luisa torsi Turku, August 27-28 2009
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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⊕ ⊕ ⊕ ⊕ ⊕ ⊕
luisa torsi Turku, August 27-28 2009
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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
luisa torsi Turku, August 27-28 2009
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luisa torsi Turku, August 27-28 2009
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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luisa torsi Turku, August 27-28 2009
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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luisa torsi Turku, August 27-28 2009
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
24
luisa torsi Turku, August 27-28 2009
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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luisa torsi Turku, August 27-28 2009
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
DHDH--αα6T / butanol6T / butanol
26
Low voltage operationLow voltage operation
Dr. M. Grell’s group at Shieffield University - Adv. Func. Mat. 2005, 15, 1017
luisa torsi Turku, August 27-28 2009
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The The BaoBao’’ss group @ Stanfordgroup @ Stanford
Prof, Zhenan Bao’s group at Stanford University – PNAS in press
luisa torsi Turku, August 27-28 2009
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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
luisa torsi Turku, August 27-28 2009
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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 !
luisa torsi Turku, August 27-28 2009
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