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Chip-based Ion Sensing Trends in Micro Nano Trends in Micro Nano 5. Dec. 2013 Christian Schönenberger Department of Physics, University of Basel, Klingelbergstr. 82, CH4056, Basel, Switzerland Schönenberger group www.nanoelectronics.ch Sensor wikipedia: “A sensor (also called detector) converts a measured physical quantity into a signal which can be read by an observer or by an instrument which can be read by an observer or by an instrument.

Trends inTrends in Micro Nano · 2013. 12. 6. · Chip-based Ion Sensing Trends inTrends in Micro Nano 5. Dec. 2013 Christian Schönenberger Department ofPhysics, University of Basel,

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Page 1: Trends inTrends in Micro Nano · 2013. 12. 6. · Chip-based Ion Sensing Trends inTrends in Micro Nano 5. Dec. 2013 Christian Schönenberger Department ofPhysics, University of Basel,

Chip-based Ion Sensing

Trends in Micro NanoTrends in Micro Nano5. Dec. 2013

Christian SchönenbergerDepartment of Physics, University of Basel, 

Klingelbergstr. 82, CH‐4056, Basel, Switzerland

Schönenberger group    www.nanoelectronics.ch

Sensor

wikipedia:“A sensor (also called detector) converts a measured physical quantity into a signal which can be read by an observer or by an instrument “which can be read by an observer or by an instrument. 

Page 2: Trends inTrends in Micro Nano · 2013. 12. 6. · Chip-based Ion Sensing Trends inTrends in Micro Nano 5. Dec. 2013 Christian Schönenberger Department ofPhysics, University of Basel,

Schönenberger group    www.nanoelectronics.ch

Sensor

wikipedia: A sensor (also called detector) converts a measured physical & chemical quantityinto a signal which can be read by an observer or by an instrumentinto a signal which can be read by an observer or by an instrument. 

GlucoWatch® Monitor

• fully integrated analytical systems

• portable diagnostic capabilities• portable diagnostic capabilities

(early detection)

• personalized medicine

Schönenberger group    www.nanoelectronics.ch

Sensor

human’s sensorics we can see  we can hear VIBE from we can hear we can smell we can taste

Philips

we can taste we can feel we may have pain we can think (sensor ?) we have emotions (sensor ?) we have intuition (sensor ?) we have intuition (sensor ?) we may be frightened (sensor ?)

Page 3: Trends inTrends in Micro Nano · 2013. 12. 6. · Chip-based Ion Sensing Trends inTrends in Micro Nano 5. Dec. 2013 Christian Schönenberger Department ofPhysics, University of Basel,

Schönenberger group    www.nanoelectronics.ch

Chip‐based sensing

Schönenberger group    www.nanoelectronics.ch

Bio‐ / chemical sensor

a device that can detect molecules with some specificity

Page 4: Trends inTrends in Micro Nano · 2013. 12. 6. · Chip-based Ion Sensing Trends inTrends in Micro Nano 5. Dec. 2013 Christian Schönenberger Department ofPhysics, University of Basel,

Schönenberger group    www.nanoelectronics.ch

Bio‐ / chemical sensor

a device that can detect molecules with some specificity

how can this information be read ?

Schönenberger group    www.nanoelectronics.ch

Bio‐ / chemical sensor

a device that can detect molecules with some specificity

how can this information be read ?

mechanically a) mass change (QCM)

www.q-sense.com

mechanically a) mass change (QCM)

b) strain (cantilever)

Page 5: Trends inTrends in Micro Nano · 2013. 12. 6. · Chip-based Ion Sensing Trends inTrends in Micro Nano 5. Dec. 2013 Christian Schönenberger Department ofPhysics, University of Basel,

Schönenberger group    www.nanoelectronics.ch

Bio‐ / chemical sensor

a device that can detect molecules with some specificity

Affymetrix

mechanically a) mass change (QCM)

y

mechanically a) mass change (QCM)

b) strain (cantilever)

optically a) labelled (DNA chip)p y ) ( p)

Schönenberger group    www.nanoelectronics.ch

Bio‐ / chemical sensor

OWLS

a device that can detect molecules with some specificity

OWLS

mechanically a) mass change (QCM)mechanically a) mass change (QCM)

b) strain (cantilever)

optically a) labelled (DNA chip) BIACOREp y ) ( p)

b) refractive index

c) Plasmonics

BIACORE

Page 6: Trends inTrends in Micro Nano · 2013. 12. 6. · Chip-based Ion Sensing Trends inTrends in Micro Nano 5. Dec. 2013 Christian Schönenberger Department ofPhysics, University of Basel,

Schönenberger group    www.nanoelectronics.ch

Bio‐ / chemical sensor

a device that can detect molecules with some specificity

how can this information be read ?

mechanically a) mass change (QCM)mechanically a) mass change (QCM)

b) strain (cantilever)

optically a) labelled (DNA chip)p y ) ( p)

b) refractive index

c) Plasmonics

electrically a) impedance spectroscopy

b) CV spectroscopy

c) potentiometric (e g zeta potential)c) potentiometric (e.g. zeta potential)

Schönenberger group    www.nanoelectronics.ch

Potentiometric sensing

FET

Page 7: Trends inTrends in Micro Nano · 2013. 12. 6. · Chip-based Ion Sensing Trends inTrends in Micro Nano 5. Dec. 2013 Christian Schönenberger Department ofPhysics, University of Basel,

Schönenberger group    www.nanoelectronics.ch

Potentiometric sensing

IS-FET

P B ld / S d A t t B 88 1 20 (2003)P. Bergveld / Sensors and Actuators B 88 1–20 (2003)

Schönenberger group    www.nanoelectronics.ch

Ion Sensitive FET (IS‐FET)

channel conductance (i.e. threshold) ( )depends on gate charge

h l b th h ld ip-channel, sub-threshold regime-

- -

-

rain

cur

rent

)

-source drain

(sou

rce-

d-

( t t ti l)(gate potential)

Page 8: Trends inTrends in Micro Nano · 2013. 12. 6. · Chip-based Ion Sensing Trends inTrends in Micro Nano 5. Dec. 2013 Christian Schönenberger Department ofPhysics, University of Basel,

Schönenberger group    www.nanoelectronics.ch

Ion Sensitive FET (IS‐FET)

channel conductance (i.e. threshold) ( )depends on gate charge

h l b th h ld ip-channel, sub-threshold regime-

--

rain

cur

rent

)

-

source drain

(sou

rce-

d

- -

( t t ti l)(gate potential)

Schönenberger group    www.nanoelectronics.ch

Ion Sensitive FET (IS‐FET)

channel conductance (i.e. threshold) ( )depends on gate charge

h l b th h ld ie.g. heparime binding on protamie

p-channel, sub-threshold regime

--

rain

cur

rent

)

-

-

SHIFT

source drain

(sou

rce-

d

-- -

( t t ti l)(gate potential)

Page 9: Trends inTrends in Micro Nano · 2013. 12. 6. · Chip-based Ion Sensing Trends inTrends in Micro Nano 5. Dec. 2013 Christian Schönenberger Department ofPhysics, University of Basel,

Schönenberger group    www.nanoelectronics.ch

IS FET for pH sensing

Honeywell: Durafet III pH sensors

Endress+Hauser :CPS441 and CPS441D

p

taken from an application note

P. Bergveld / Sensors and Actuators B 88 1–20 (2003)

Schönenberger group    www.nanoelectronics.ch

Dental Application

• Food components that lower pH of dental plaque cause caries

pH  recording of dental plaquep g p qP =  paraffin chewingS =  rinse with sucrose 10%U = rinse with urea 3 %

H. H. van den Vlekkert, Sensors and Actuators, Vol 14, p. 165 (1988)

U    rinse with urea 3 %

Page 10: Trends inTrends in Micro Nano · 2013. 12. 6. · Chip-based Ion Sensing Trends inTrends in Micro Nano 5. Dec. 2013 Christian Schönenberger Department ofPhysics, University of Basel,

Schönenberger group    www.nanoelectronics.ch

ISFET pH catheter

chips

K. Bedner et al.

Page 11: Trends inTrends in Micro Nano · 2013. 12. 6. · Chip-based Ion Sensing Trends inTrends in Micro Nano 5. Dec. 2013 Christian Schönenberger Department ofPhysics, University of Basel,

chip

48 silicon nanowires/sampletop width: 100nm – 1µm

NW

DRAIN

3 SOURCECONTACTS

SU-8microchannel

S

microchannel

HfO2, Al2O3

Wtop

5

DS

85nm

top

silicon

SiO2

5µm

K. Bedner et al.

Schönenberger group    www.nanoelectronics.ch

electrode fabrication1 2 3

80nm145nm

~10nm

p-type (100) SOI

SiO2

Si

step 1. step 2.+3. Weff = Wtop + 2Wwalls

145nmSiO2

Si handle wafer

wire length:6umwidth: 100nm‐1um

100nm

step 4.+5. step 6.+7.

metal

width: 100nm‐1um

PMMA

step 11.to14.

SU-8

silicon

silicon oxide

ALD oxide

resist

metal

ALD oxide

70 300epoxy

Kristine Bedner et al.

70 nm 300 nm

Page 12: Trends inTrends in Micro Nano · 2013. 12. 6. · Chip-based Ion Sensing Trends inTrends in Micro Nano 5. Dec. 2013 Christian Schönenberger Department ofPhysics, University of Basel,

up-scaling

SiO2 mask ~ 180nm

NW

180nm

SiSi

Si

Si

Si

K. Bedner et al.

Microfluidics

Devices location in µ-fluidic channels

Page 13: Trends inTrends in Micro Nano · 2013. 12. 6. · Chip-based Ion Sensing Trends inTrends in Micro Nano 5. Dec. 2013 Christian Schönenberger Department ofPhysics, University of Basel,

in the lab in operation

NW-ISFET “quality”

(low p‐doped wires in accumulation withp+‐implanted and alloyed contacts)

pH response & sensitivity

9.0 10-5

6.0

7.5

120mV/decpH 3, 5, 7, 9

10-7

10-6

)) )

8

NW 1NW 2

10-5

width =1m

reproducibility

3.0

4.5

Vsd

=0.1V

G (S

)

Vbg

=-6V

10-9

10-8 G (

S)

G (S

)

G (

S

4

6

NW 2

(S

)

8

10-7

10-6

(S)

120mV/dec

(S

)

(S) -0.5 0.0 0.5 1.0 1.5 2.0

0.0

1.5sd

V (V)

width =1m

10-10

10

Vref (V)

2

4

Vsd

=0.1V

G

Vbg

=-6V

pH 7

10-10

10-9

10-8 G

G ( G V

ref (V)Vref (V)

with good ALD oxides, HfO2 and Al2O3

always reach maximum sensitivity of

-0.5 0.0 0.5 1.0 1.5 2.00

Vref

(V)

10

Vref (V)

~ 60 mV/pH

Page 14: Trends inTrends in Micro Nano · 2013. 12. 6. · Chip-based Ion Sensing Trends inTrends in Micro Nano 5. Dec. 2013 Christian Schönenberger Department ofPhysics, University of Basel,

NW-ISFET “quality”

0.235

Stability measurements 5.5 days

0.225

0.230

HfO2 gate oxide

pH 6 buffer solution

0.215

0.220

Vth [V

]

pH 6 buffer solution

8

NW 1NW 2

10-5

width =1m

reproducibility0.205

0.210

4

6

NW 2

(S

)

8

10-7

10-6

(S)

120mV/dec

(S

)

(S)

0 24 48 72 96 1200.200

Time (h)

FinFET sample (EPFL) 8nm HfO2 gate ox

2

4

Vsd

=0.1V

G

Vbg

=-6V

pH 7

10-10

10-9

10-8 G

G ( G p ( ) 2 g

pH6 buffer solution• 4 different nanowires• Max. Drift ~2mV/day

-0.5 0.0 0.5 1.0 1.5 2.00

Vref

(V)

10

Vref (V)• differential drift ~ 0mV

S. Rigante et al.

Genome sequencing

ion-torrent

Page 15: Trends inTrends in Micro Nano · 2013. 12. 6. · Chip-based Ion Sensing Trends inTrends in Micro Nano 5. Dec. 2013 Christian Schönenberger Department ofPhysics, University of Basel,

can one measure something else ?

oxide surface highly sensitive to protons Nernst limit

iti it t th i i ll ll !sensitivity to other ions is usually very small !

if there are other reactions on the surface that can compete with the de protonation and proton addition at OH sites the pH sensitivity may bede-protonation and proton addition at OH sites, the pH sensitivity may be reduced

NW with floating gate

purple = Au on top

6µm

M. Wipf et al. ACS Nano 2013

Page 16: Trends inTrends in Micro Nano · 2013. 12. 6. · Chip-based Ion Sensing Trends inTrends in Micro Nano 5. Dec. 2013 Christian Schönenberger Department ofPhysics, University of Basel,

Au coated NW: Selective Sodium SensingSensing

M. Wipf et al. ACS Nano 2013

Results

1. maximum sensitivity (Nernst limit) can be achieved (Al2O3 and HfO2)

2. oxide surfaces (Al2O3 and HfO2) can be highly selective to protons( ld d l b ff f )(yielding ideal pH sensor up to buffer conc. of 10 mM) 

3. maximum sensitivity also for the narrowest nanowires

4. highest resolution in concentration best for wide wires

5. differntial measurement greatly improves stability

6. full passivation possible  “ideal” reference electrode

7. good sensitivity with high selectivity to other ions can be h dachieved 

8. multi‐ion sensing is promissing

Page 17: Trends inTrends in Micro Nano · 2013. 12. 6. · Chip-based Ion Sensing Trends inTrends in Micro Nano 5. Dec. 2013 Christian Schönenberger Department ofPhysics, University of Basel,

System Architecture

• 16 nanowires can be interfaced in parallel• voltage across each nanowire is kept constant, and the current flowing through is measured•Two different analog‐to‐digital converter architectures are used (12 bits resolution)

33

Paolo Livi et al.• Current range: 1 nA to 5 μA

CMOS readout

• Power consumption: 35 mW

• I2F resolution:• 8 bits (50 pA -1 μA range)• 10 bits (10 nA - 400 nA range)( g )

• Sigma-Delta resolution:• 12 bits in the range ±2 μA

34

Paolo Livi et al.34

Page 18: Trends inTrends in Micro Nano · 2013. 12. 6. · Chip-based Ion Sensing Trends inTrends in Micro Nano 5. Dec. 2013 Christian Schönenberger Department ofPhysics, University of Basel,

System Architecture

VDS = 200 mV

Nanowire Sensor Chip

CMOS Readout Chip

sigma‐delta modulator read‐out of 4 Si‐NW, 9.‐10. Nov. 2011

35

pPaolo Livi et al.

Thanks to....

Uni Baselphysics

Michel CalameOren

KnopfmacherWangyang Fu

Alexey TarasovChristian

SchönenbergerEPFL

PSI

Mathias WipfRalph Stoop

Adrian Ionescu Kristine BednerSara RiganteMohammad N j d h

BirgitPäi ä t

VitaliyG k

ChristianD id

Jens Gobrecht

PSI

RenatoMi i

Adrian Ionescu Kristine BednerSara RiganteNajmzadeh Päivänranta Guzenko David

ETHZ UniBaspharma

Jens GobrechtMinamisawa

Beat ErnstBernd Dielacher

Jolanta KurzUwe PielesArjan OdedraJanos VörösRobert

MacKenzie

pharma

FHNW

Floriian Binder

D-BSSEFHNW

Sensirion

36

Andreas Hierlemann

Paolo Livi Yihui Chen Matthias Sreiff