Post on 21-Mar-2018
Laser technology for sensors gyapplications
I. Zergioti
Physics DepartmentNational Technical University of Athens
“Mi S ”“MinaSens”Athens 7-8 March 2013
“MINASENS”, Athens 7-8 March 2013
Laser printing for sensors applicationsLaser printing for sensors applications
Microsystems(cantilevers, membranes, micro-electrodes, nano-wires)
ProteinsCells
Polymers materialsComposites Cells
Enzymes
DNA or aptamers
CompositesNanoparticles
CNTs, Graphene
Need for printing
technologies !
Chemical sensors Biological sensors
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LASER INDUCED FORWARD TRANSFER
Polymer layers Interdigitated Ag electrodes for organic thin film transistors
Ag linesthin film transistors
H Kim et al 2010 J. Phys. D: Appl. Phys. 43
J. Shaw-Stewart et al. Appl. Mater. & Interfaces 3, 309
Rapp et al., Optics Express ,19, 22, 21563
(2011) (2011)
N T K i l / O E 12 1152 1158
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N.T. Kattamis et al. / O. E., 12 1152–1158, (2011)
LASER INDUCED FORWARD TRANSFER
DNA microarrays
Solid phase bio printing Liquid phase bio printing
M. Colina et. al., Biosensors and Bioelectronics 20 1638 (2005)
Zergioti et al. Appl. Phys. Let. 86, 163902 (2005)Work at FORTH
Polymers for chemical sensors
C. Boutopoulos et al. Appl. Phys. Lett., 19 191109 (2008)Work at NTUA
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Work at NTUA
LASER INDUCED FORWARD TRANSFER266 nm, 355 nm, 532 nm, 1064 nmns or ps pulses
Microarrays
Capacitive chemical and bio sensors Biosensors
Thin Film Transistors (OTFT)(OTFT)
Resistivity chemical sensors
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AN OUTLINE
Analyte• Polymer/CNT resistivity sensorsPolymer/CNT resistivity sensors for humidity monitoring
Bio-receptor
• Aptamers based sensors for Pb detection on capacitive approach
• Photosynthetic amperometric environmental sensors for water
Transducer (electrochemical, optical or capacitive)
environmental sensors for water monitoring
• Mechanisms study of the laser direct immobilization
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Polymer/carbon nanotube (CNT) composites (P ti A li ti )(Properties – Applications)
• Mixture of CNT and polymer matrix form conductive composite with high electrical conductivity.• The composite CNT/polymer can be used as chemical sensor.
Polymer/carbonPolymer/carbon nanotube composite film
Polymer/CNT composites for sensors and electronics
"Polymer/carbon nanotube composite patterns via laser inducedforward transfer," C. Boutopoulos, C. Pandis, C. Giannakopoulos, P.Pi i I Z i ti A li d Ph i L tt 96 041104 (2010)
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for sensors and electronicsPissis, I. Zergioti, Applied Physics Letters 96, 041104 (2010).
Polymer/carbon nanotube (CNT) composites for chemical sensingsensing
•The electrical conductivity of the polymer/CNT composites depends
Polymer/CNT composites candidates for chemical
from the:
•CNT aspect ratiocandidates for chemical sensing through amperometric measurements
•Dispersion of the CNTs into the polymer matrices
•Polymer matrix
•CNT functionalization
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Polymer/carbon nanotube (CNT) composites for chemical sensing
f-CNTs
Nafion with functionalized and non functionalized CNTs 5% wt.f CNTs
CNTs
TEM
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More uniform distribution of the f-CNTs
Polymer/carbon nanotube (CNT) composites for chemical sensing
H2O
g
80
75% RH
78% RH
75% RH
75% RH
drydrydrydrydrydry
74% RH
Nafion/CNTs 5 wt.%
Gas output
60 TCEM=40oCN2=500 mls/min)
Consistent and reproducible change in
20
40 I=10-6A
R
/Ro (%
) reproducible change in resistance (70-100%)
Quick response time (sec)
0
(sec)
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20 30 40 50 60 70 80 90
t (min)
Direct laser printing of biomaterials
THE CAPACITIVE APPROACH FOR SENSOR DEVICES
Change of surface energy due to target binding on receptor
reference
sensor
g g pmolecules results in membrane bending and therefore a change in the capacitance value of the device
VCx
sensor device
118,0p
120,0p
122,0p
ce (
F)
150um OD0.5um thickness
VOUTVCx
25 30 35 40 45 50 55 60 65 70 75 80 85 90108,0p
110,0p
112,0p
114,0p
116,0p
x25 biotin21nM streptavidin
Cap
acita
nc
Time (min)
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Aptamers baser Capacitive sensors for Pb detectionfor Pb detection
G
C17Ec
/
S S
/
S
AU/ GOPTS on LTO AU/ GOPTS on LTOAU/ GOPTS on LTO
Immobilization of oligo 1 Hybridization with oligo 2Cleavage of the
hybridized DS) aptamer,
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in the presence of Pb
Capacitive sensors
L i i f i i f h d i f Pb i
Fluorescent microscopy image Optical microscopy image
Laser printing of aptamers on capacitive sensors for the detection of Pb ions
8
LIFT conditions: 10μM on donor, 300 mJ/cm2, Spot size: 50μm, 266 nm
4
6
ores
cenc
e
2
Fluo
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0After Pb-SS aptamerDS aptamerSS aptamer
Capacitive sensors
L i i f i i f h d i f Pb i
1 82,0
Laser printing of aptamers on capacitive sensors for the detection of Pb ions
1,01,21,41,61,8
pF)
pb target
• Reference capacitors: oligomer probes
0 00,20,40,60,8
Cap
acita
nce(
p
• Measuring capacitors: hybridized oligomer probes with target
-0,8-0,6-0,4-0,20,0C
0,5 1,0 1,5 2,0 2,5 3,0
Time(hours)
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Photosynthetic Biosensors for environmental applications
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Photosynthetic reactionLight Harvesting complex II
LED at 625 nm on for 5 sec
A)
Herbicide inhibition
Cur
rent
(nA
CTime (min)
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( )Herbicide insertion
Bio-receptors and Electrodes
Bio-receptors Electrodes
DropSens Screen Printed Electrodes
MicroElectrodeArraysArrays
Indium Tin Oxide
Silicon
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SiliconNanoWires
Laser Direct Printing - Immobilisation
LIFT Pipette
200
300
Light on
Light on
LIFT Pipette
ent (
nA)
Light on
4 6 8 10 12 14 16
0
100
Cur
re
x3
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Time (min)
LIFT for Photosynthetic Biosensors : Direct Immobilization
300Light on
LIFT PipetteLight on • Direct immobilization of the thylakoid
l i t d t i l ith t th f
200
300
Light on
nA)
laser printed material without the use of any functionalization layer• High activity and high signal to noise ratio
100
Cur
rent
(n ratio
• Conventional technology: Use of chemical linkers and polymer hydrogels
0
x3
chemical linkers and polymer hydrogels as immobilization matrices which harm photosynthetic materials
4 6 8 10 12 14 16
Time (min) LIFT eliminates the functionalization step of the sensor
-C. Boutopoulos, E. Touloupakis, M. Giardi, I. Zergioti, Appl. Phys. Lett.,98 093703 (2011)
C B t l E T l ki G R di I Z i ti P t t
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- C. Boutopoulos, E. Touloupakis, G. Rodio, I. Zergioti, PatentApplication number : 20120100368 , 11-07-2012
LIFT for Photosynthetic Biosensors : Calibration Sensitivity curves
100
100
y
50
75
al a
ctiv
ity (%
)
50
75
al a
ctiv
ity (%
)
25
Res
idua
25Res
idua
1E-10 1E-9 1E-8 1E-7 1E-60
Linuron herbicide concentration (M)
1E-9 1E-8 1E-7 1E-6
0
Diuron herbicide concentration(M)
E. Touloupakis, C. Boutopoulos, I. Zergioti, M. Giardi, Analytical and Bioanalytical Ch i t 402 (10) 3237 3244 (2012)
Pesticide LOD (IUPAC]
Li 8 10 9 M Chemistry, 402 (10), pp. 3237-3244 (2012).Linuron 8 x 10‐9 MDiuron 4 x 10‐9 M
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Mechanisms of Direct Laser Immobilization of bi l lbiomolecules
Li id ti ( f t i i it• Liquid properties (surface tension, viscosity, thickness)
• Wetting and roughness of the sensor surface
•Impact Velocity
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Shadowgraphic imaging setup
CCD camera
beam expander10x objective lens Rhodamine
Nd:YAG laser532 10CCD camera
oscilloscope
532 nm, 10 ns
photodiode
1mask
d l t Nd:YAG laser
attenuator
delay generator Nd:YAG laser266 nm, 10 ns
Pump laser trigger
Probe laser trigger
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Effect of laser energy density on surface wetting‐hydrophilic surfaces
Reference pipette spotting (θ 89 4ο) E (mJ/cm2)= 89.4ο) ( / )
125 150 175 200 225 250 275 300
89.1ο ± 2.6ο 88.2ο ± 8.6ο 93.1ο ± 5.2ο 71.1ο ± 11.7ο 59.6ο ± 7.1ο 33.8ο ± 5.5ο 27.5ο ± 12.2ο 18.5ο ± 3.5ο
“MINASENS”, Athens 7-8 March 2013Contact angle
180 mJ/ cm2/ 2 454 mJ/ cm2 890 mJ/ cm2 1430 mJ/ cm2
Laser Induced Forward Transfer Shadowgraphy study180 mJ/ cm 263 mJ/ cm2 454 mJ/ cm 890 mJ/ cm 1430 mJ/ cm
8 ate bu
ffer pH8
1M pho
spha
800
Distance = 467 μmTime= 14,8 μs
Distance = 506,8 μmTime= 10,3 μs
Distance = 412,9 μmTime= 6,36 μs
Distance = 534 μmTime= 1,82 μs
Distance = 470,3 μmTime= 1,84 μs
400
500
600
700
e (u
m)
Chosen Laser energy fluence for deposition
180 mJ/ cm2 33 m/s Pim= 0,61 MPa
263 mJ/ cm2 47 m/s Pim= 1,17 MPa
100
200
300
400
1430 mJ/ cm^2 890 mJ/ cm^2 454 mJ/ cm^2 263 mJ/ cm^2 185 mJ/ cm^2
Dis
tanc
e263 mJ/ cm 47 m/s Pim 1,17 MPa
454 mJ/ cm2 70 m/s Pim= 2,73 MPa
890 mJ/ cm2 255 m/s Pim= 36,78 MPa
1430 J/ 2 263 / Pi 39 18 MP
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0 2000 4000 6000 8000 10000 12000 14000 160000
Time (ns)
1430 mJ/ cm2 263 m/s Pim= 39,18 MPa
Wetting states transition due to high velocity impact
P = ½ ρ V 2
4 min
Pd= ½∙ρ∙Vim2
160
180
Pipette-deposited drop CA ~ 157o
120
140
160
gle,
deg
10
sure
, MP
a
80
100
120
cont
act a
ng
0.1
1
mpa
ct p
ress
4 min oxygen plasma etched
0 300 600 900 120060
80
laser fluence mJ / cm2
im nanotexture PMMA resulting at600 nm roughness
Transition from partial to complete wetting
laser fluence, mJ / cmSticking of droplets on slippery superhydrophobic surfaces by Laser Induced Forward Transfer (LIFT) , Christos Boutopoulos, Dimitrios P. Papageorgiou, Ioanna Zergioti, Athanasios G. Papathanasiou, Submitted Appl. Phys. Let., 2013.
“MINASENS”, Athens 7-8 March 201330 μL phosphate buffer on Ti coated quartz target (60 μm thickness), 130 μm spot size
LIFT immobilization of thylakoids on various substrates: fluorescence resultsfluorescence results
1000 mJ/cm2 800 mJ/cm2 700 mJ/cm2 600 mJ/cm2
500 mJ/cm2 400 mJ/cm2 300 mJ/cm2 200 mJ/cm2
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500 mJ/cm 400 mJ/cm 300 mJ/cm 200 mJ/cm
Conclusions
• Laser can print high spatial resolution biomediators and polymers for sensors applicationspolymers for sensors applications
• Laser can eliminate the functionalisation of a biosensor
• Transit from Cassie-like to Wenzel state. Physical adsorption of th d l t lti i th di t i bili ti f ththe droplet resulting in the direct immobilization of the photosynthetic material.
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PeopleNTUA, Phyiscs Department
Christos Boutopoulos Post Doc
NTUA, Chemical Engineering Department
Christos Boutopoulos, Post DocMarianneza Chatzipetrou, PhD
I Z i i A i P f
Dimitris Papageorgiou, PhDAthanassios Papathannasiou, Assist. P fIoanna Zergioti, Assist. Professor
http://zergioti. physics.ntua.gr/
Professor
NCSRD/IMELDr. V. TsoutiDr S Chatzandroulis
BIOSENSOR srl, RomeG Rodio Eng Dr. S. ChatzandroulisG. Rodio, EngProf. M. T. Giardi
BRFAADr. G. Tsekenis
University of CreteDr. E. Touloupakis
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ACKNOLOWDMENTS
• Corallia, “Labonchip” 2010-2012
• ICT-2009 3.3 a: ee--LIFT: LIFT: Laser printing of organic/inorganic material p g g gfor the fabrication of electronic devices (2010-2012)
• MARIE CURIE IAPP: FP7-PEOPLE-2012-IAPP-Industry-AcademiaMARIE CURIE IAPP: FP7 PEOPLE 2012 IAPP Industry Academia Partnerships and Pathways (IAPP)“Laser Digital Micro-Nano fabrication for Organic Electronics and Sensor applications” (2013-2017)Sensor applications (2013-2017)
• COST Action TD1102 Photosynthetic proteins for technological applications: biosensors and biochips (PHOTOTECH) 2011 2015applications: biosensors and biochips (PHOTOTECH) 2011-2015
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Th k f tt ti !Thank you for your attention!
“MINASENS”, Athens 7-8 March 2013