organic thin-film transistorsstatic.sif.it/sif/resources/public/files/congr/mc2008/torsi_08.pdf ·...

SIF – XCIV Congresso Nazionale – Genova 23.09.08

Organic ThinOrganic Thin--Film Transistors Film Transistors with with

enhanced sensing capabilitiesenhanced sensing capabilities

L. TorsiL. Torsi, D. Angione, F. Marinelli and F. Palmisano, D. Angione, F. Marinelli and F. Palmisano

Dipartimento di Chimica - Università di Bari - (Italy)

[email protected]

analyte

A. Tsumura, H. A. Tsumura, H. KoezukaKoezuka and T. Ando, Appl. Phys. and T. Ando, Appl. Phys. LettLett., 49, 1210, 1986 (1., 49, 1210, 1986 (1°° OTFT)OTFT)H. H. LaursLaurs and G. and G. HeilandHeiland, , ThinThin SolidSolid FilmsFilms 149 (1987) 129149 (1987) 129--142 (142 (11°° OTFT sensor)OTFT 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.

Organic TFT sensorsOrganic TFT sensors

Ids

gategate

Vg

dielectricdielectric

Vds

⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕ ⊕sourcesource draindrain

conducting channel

organicorganic semiconductorsemiconductor


OTFT pressure sensor: toward OTFT pressure sensor: toward artificial skin artificial skin

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

Prof. T. Someya University of Tokyo

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)


DHDH--αα6T morphology6T morphologyDHα-6T

90 nm 200 nm 400 nm

500 nm 500 nm500 nm

100 nm100 nm100 nm

Organic Thin-Film Transistors with Enhanced Sensing Capabilities.M. Daniela Angione, Francesco Marinelli, Antonio Dell’Aquila, Alessandro Luzio, Bruno Pignataro and Luisa Torsi. Proceedings symposium e-MRS 2008 in press


Grain surface

EB

GBC μμμ111

+=

⎟⎠⎞

⎜⎝⎛−∝

kTEB

GB expμ

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 butanol

TransTrans--characteristicscharacteristicsin butanolin butanol

Tran-characterisics in N2

TranTran--characterisicscharacterisics in in NN22

Sensing measurements on OTFTSensing measurements on OTFT


0 1 2 3 4 5 6 7 8 9 10 11 12-18-17-16-15-14-13-12-11-10-9-8-7-6-5

ΔI(n

A)

# of replicates

ΔI(nA) (+)citronellolo

average =-8,58nA

StndStnd devdev < 2%< 2%

Response repeatabilityResponse repeatability


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


The role of grainThe role of grain boundaries boundaries

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

2D Field2D Field--induced conductance induced 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)

M.C. Tanese et al. , Thin Solid Films, 516, 3263–3269, (2008)

A. Dodabalapur, L. Torsi and H.E. Katz, Science 268, 270, 1995


SSiO2

DSOSOS

G


Device Operation regimesDevice Operation regimes

(a)

Gatecontact

GateDielectr.

p-typeactivelayer

LUMO

HOMO

VGS = 0

+ +

(c)

VGS> 0depletion mode

Ψs

+ +

(b)

VGS< 0accumulation mode

Ψs

+ + + + ++

2D-transport region

2D sensing response2D sensing response

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

•• EllipsometryEllipsometry: : no swellingno swelling•• QCM: QCM: mass upmass up--taketake

•• 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)


Sensing mechanism Sensing mechanism

Highly doped Si substrate2SiO2

S DG

Ids

t

Ids

Vgs

Vgs

Vds

Grain surface

EB

Vds & Vgs = const

Vds = const


0 -20 -40 -60 -800

-2

-4

-6

-8

-10

ΔI

N2

(S)(S)--((--))--ββ--citronellolcitronellol

0 -20 -40 -60 -80

10-11

1x10-10

1x10-9

1x10-8

|I (A

)|

Vg(V)

I ds(n

A)

| ΔI|

(A)

Vg (V)

(a)

(b)

0 -20 -40 -60 -80

10-9

10-10

Trans-characteristics in

citronellol

TransTrans--characteristicscharacteristics in in

citronellolcitronellol

ΔΙ responseΔΙΔΙ responseresponse

Tran-characterisics in N2

TranTran--characterisicscharacterisics in in NN22

Vds = -40 V

Sensing measurements on OTFTSensing measurements on OTFT

30 ppm Citronellol


L. Torsi, G.M. Farinola et al, L. Torsi, G.M. Farinola, M.C. Tanese, O. Hassan Omar, L. Valli, F. Babudri, F. Palmisano, P.G. Zambonin & F. Naso. Nature Materials 7 (5), 412-417 (2008)

Patent Filed FT/TS/GV/ds/06578D53

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


Receptor: glucose

Analytes: Carvone

(+) (-)

PTG OTFT sensor for PTG OTFT sensor for carvonecarvone

PTG / PTG / carvonecarvone

Vg = -100 V

0 20 40 60 80 1000

-2-4-6-8

-10-12-14

carvone (ppm)

ΔI (

nA)

(S)-(+)-carvone(S)(S)--(+)(+)--carvonecarvone

(R)-(-)-carvone(R)(R)--((--))--carvonecarvone


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

(nA

)

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

L. Torsi, G.M. Farinola et al, Nature Materials 7 (5), 412-417 (2008)



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

L. Torsi F. Marinelli, M. D. Angione, A. Dell’Aquila, N. Cioffi, E. De Giglio and L. Sabbatini, submitted 2008


Role of contact resistanceRole of contact resistance

GG

SiOSiO22

SiSi

SS DD

RRchchRRcc

DHDH--αα6T6T


RRchch and and RRcc: transfer line method (N: transfer line method (N22))

GGS DS D

Si Si

SiOSiO22DHDH--a6Ta6T

0.0 0.2 0.4 0.6 0.8 1.00

2

4

6

8

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

RW

(MΩ

cm

)

Channel Lenght - (mm)


RRchch and and RRcc: transfer line method : transfer line method (Butanol)(Butanol)

DHDH--a6Ta6T

GGS DS D

Si Si

SiOSiO22

0.0 0.2 0.4 0.6 0.8 1.00

2

4

6

8

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

RW

(MΩ

cm

)Channel Lenght - (mm)



-20 -40 -60 -80 -100

0.1

1

L=0.2 mm L=0.6 mm L=1 mm ΔRc

ΔR(M

Ω)

Vg(V)SIF – XCIV Congresso Nazionale – Genova 23.09.08


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


L. Torsi F. Marinelli, M. D. Angione, A. Dell’Aquila, N. Cioffi, E. De Giglio and L. Sabbatini, submitted 2008

What will the future be like?What will the future be like?AffymaxAffymax 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)


••OTFT sensor are very sensitive devices: enantiomeric OTFT sensor are very sensitive devices: enantiomeric differential detection @ ppm differential detection @ ppm

•• Gate induced sensitivity enhancementGate induced sensitivity enhancement•• Excellent repeatability but reproducibility is still an Excellent repeatability but reproducibility is still an

issueissue•• Spurious effects are under controlSpurious effects are under control

•• Future is likely to be in allFuture is likely to be in all--electronic disposable bioelectronic disposable bio--systems on cheap & flex substratessystems on cheap & flex substrates

ConclusionsConclusions


RingraziamentiRingraziamenti

G.PG.P Suranna, G. Romanazzi, P. Suranna, G. Romanazzi, P. MastrorilliMastrorilli e C. F. Nobilee C. F. NobileDipartimento di Ingegneria delle Acque e di Chimica – Politecnico di Bari

A. LuzioA. Luzio11 and B. Pignataroand B. Pignataro221 PLAST_ICS - Superlab - Consorzio Catania Ricerche - Catania

2 Dipartimento di Chimica Fisica - Università degli Studi di Palermo - Palermo

G.M. Farinola, P. Iliade, H. G.M. Farinola, P. Iliade, H. HassanHassan Omar, F. Babudri, F. NasoOmar, F. Babudri, F. NasoDipartimento di Chimica - Università degli Studi di Bari

G. G. GiancaneGiancane and L. Valliand L. ValliUniversità del Salento. Lecce

MIUR MIUR -- PRIN 04 PRIN 04 -- 20040340212004034021


organic thin-film transistorsstatic.sif.it/sif/resources/public/files/congr/mc2008/torsi_08.pdf ·...

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