laser technology for sensors applications - · pdf filelaser technology for sensors...

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


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


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


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


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


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)


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


Polymer/carbon nanotube (CNT) composites for chemical sensing

f-CNTs

Nafion with functionalized and non functionalized CNTs 5% wt.f CNTs

CNTs

TEM


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)


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)


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,


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


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)


Photosynthetic Biosensors for environmental applications


Photosynthetic reactionLight Harvesting complex II

LED at 625 nm on for 5 sec

A)

Herbicide inhibition

Cur

rent

(nA

CTime (min)


( )Herbicide insertion

Bio-receptors and Electrodes

Bio-receptors Electrodes

DropSens Screen Printed Electrodes

MicroElectrodeArraysArrays

Indium Tin Oxide

Silicon


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


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


- 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


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


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


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 = 534 μmTime= 1,82 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


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


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.


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


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


Th k f tt ti !Thank you for your attention!


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