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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.
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 ?)
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
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)
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
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
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)
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)
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 %
Schönenberger group www.nanoelectronics.ch
ISFET pH catheter
chips
K. Bedner et al.
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
up-scaling
SiO2 mask ~ 180nm
NW
180nm
SiSi
Si
Si
Si
K. Bedner et al.
Microfluidics
Devices location in µ-fluidic channels
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
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
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
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
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
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