advanced materials synthesis for inkjet printed...

Advanced Materials Synthesis for Inkjet

Printed Electronic Applications

Dr. Samuele Porro, Dr. Sergio Bocchini, Dr. Alessandro Chiolerio

Istituto Italiano di Tecnologia (IIT) Center for Space Human Robotics C.so Trento 21, 10129 Torino, Italy

1 - 28th November 2013, PoliMI -

Smart Materials Energy Devices Artificial Physiology

2

Politecnico di Torino campus

Istituto Italiano di Tecnologia - CSHR

Torino


- 28th November 2013, PoliMI -

Outline

o Synthesis

o Morphological analysis

o Electrical properties

1. One pot synthesis of reduced graphene oxide / polyaniline composite ink

2. Hybrid systems based on Ag NPs and acrylic resin


Endurance

Sustainability

Low-cost

Easy manufacturing

Flexible substrates Devices printed on flexible substrates

Processing: Inkjet Direct Printing

INK REQUIREMENTS - Printability: adjustable viscosity (low), surface tension and solvent evaporation rate - Easy to prepare and process: nanoparticle fillers, fast polymerization of the matrix - Possibly absence of solvents (water-based) - A plus is the absence of post-curing (i.e. thermal). State of the art Metal nanoparticle-based inks: require thermal sintering.

1)

Introduction: aim of research


Additive Technique (no further steps of material removal are needed)‏ Safe for the substrate (lower substrate damage risk)‏ Material is used without any waste (spin-coating losses 95%)‏ A large variety of materials may be used

Piezoelectric heads: long lifetime with respect to thermal (bubble jet) Cheap compared to silicon technology, no wasted materials, easy to implement Resolution: depends on the head, substrate and ink.

Drop On Demand (DOD) technique

Inkjet Printing

IjP resistive test pattern

Real size of a piezoelectric nozzle (Microfab)


Endurance

Sustainability

Low-cost

Easy manufacturing

Flexible substrates Printed Electronics

Materials: Polymers and carbon-based 2) GRAPHENE OXIDE

- Large-scale production (oxidation + expansion of graphite)

- Strongly hydrophilic due to oxygenated functional groups Easy to disperse in water and functionalize

- Reduction to graphene by several methods: chemical reaction, thermally, radiation-induced, etc.

Introduction: aim of research


Synthesis of Polyaniline (PANI)

PANI can be considered as being derived from two different repeating units, which are alternatively reduced and oxidized (base form given in the figure).

The average oxidation state varies continuously: y = 1 is the completely reduced polymer, y = 0.5 is the “half-oxidized” polymer, y = 0 is the completely oxidized polymer.

J. Mater. Chem. C 1 (2013) 5101

Literature: use of ANYLINE monomer precursor Toxic, suspect carcinogenic, easily produces irregular non-linear polymer chains (orto addition), needs hazardous solvents (DMF, etc.), slow reaction, graphene does not disperse in presence of anyline.

This work: use of the anyline dimer (DANI) Non toxic, can be used in water-based emulsion, polymerizes more regularly than anyline. GO, which is a strong oxidant, participates in the complex set of redox reactions which lead to the polymerization of the matrix, and is reduced in-situ.

The polymer/graphene composite can be readily dispersed in a common solvent (DMSO) and inkjet printed.


GO water dispersion 1 mg/ml with PSS surfactant agent

+

Dianiline precursor in DMSO

Complete oxidation of dianiline to PANI (polymerization) and concurrent reduction of GO to RGO.

Printable ink

2%

Solv

en

t

(DM

SO)

J. Mater. Chem. C 1 (2013) 5101

Synthesis of RGO/PANI ink

IJP Inkjet printed samples on

flexible substrates (polyimide)

Patent n. TO2013A000561 - 28th November 2013, PoliMI -

UV-Vis absorbance at 481 nm is typical of PANI in the emeraldine salt (conductive) form. The saturation at about 300 nm is expected because of the presence of the graphene filler.

Characterization of RGO/PANI ink

XRD: GO amorphous band (2θ = 13°) disappears in the composite, which shows PANI band (20°) and a peak (38°) which can be ascribed to lamellar graphitic structures.

TGA in N2: two degradation peaks at 300 and 400°C are due to PSS e PANI. The 550°C peak is due to loss of oxygen from GO. The 31.3% weight residulal is graphene. TGA in air: absence of organic contaminations; complete carbonization due to oxidation with peak speed at 530°C.


TEM images show partially overfolding graphene flakes. The dark structures are PANI crystals, while the smaller spots are PSS surfactant agent, which allowed the separation of graphene lamellar flakes and their interaction with the polymer.

Characterization of RGO/PANI ink


Re

sist

ivit

y [W

cm

]

Width [mm]

RGO/PANI ink

Electrical characterization of RGO/PANI printed tracks

Optical microscope images of RGO/PANI tracks printed on commercial polyimide flexible substrates.

I-V curves in the -50 +50 V range, for different track width .

RGO/PANI 1 pass


Negative capacitance effects in (RGO) PANI printed tracks

AC measurements in the range 20 Hz – 2 MHz The modulus of complex impedance above 1 kHz is similar to that of an ideal capacitor, and the corresponding phase saturates at -90° (capacitive phase). At frequencies below 100 Hz there is evidence of inductive phase (in average +45°). Increasing AC signal amplitude from 1 to 10 V increases the probability of measuring an inductive phase at frequencies lower than 100 Hz, probably because of an easier charge transfer. This phenomenon is also known as negative capacitance effect.

[Solid-State Electron. 47 (2003) 1089]


Complex impedance represented as Nyquist plot: x = real part (resistance) y = imaginary part (reactance). Frequency is codified by colour. Spline fits to experimental points show the trajectory of complex impedance across the quadrants. Increasing AC amplitude to 10 V, it is possible to increase the probability of having a positive resistance keeping a negative reactance (equivalent to a negative capacitance effect).

This effect is clear also observing the capacitance versus signal frequency at 10 V AC signal amplitude. Negative capacitances up to some hundreds of µF were observed at very low frequencies, meaning that this material could be exploited in negative supercapacitors for devices running at commercial grid frequencies (50, 60 Hz).

Negative capacitance effects in (RGO) PANI printed tracks


PANI-EB before/after protonation

Doped Polyaniline (PANI)

Synthesis of PANI, doping with several agents and IJP after solution in DMSO. J. Mater. Chem. C 1 (2013) 5101

Graphene-polymer composites

PEGDA/RGO printable ink. J. Mater. Sci. 48 (2013) 1249

PANI/RGO composite ink. Patent n. TO2013A000561

Technology Transfer: ICP-based inks


Outline

o Synthesis

o Morphological analysis

o Electrical properties

1. One pot synthesis of reduced graphene oxide / polyaniline composite ink

2. Hybrid systems based on Ag NPs and acrylic resin


100

101

102

0

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FE-SEM NP diameter distribution

100

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1 10 100

100

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0

5

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1 10 500 1 10 100

Log(size)

Co

un

ts

8 x

A. Chiolerio et al., Microelectron. Eng. 88 (2011) 2481-2483


UV-vis spectroscopy and plasmonic properties Transmitted

Reflected A. Chiolerio et al., Microelectron. Eng. 97 (2012) 8-15

Optical plasmonic properties


Re

sist

ance

[Ω

]

3D trajectories describing the path towards electrical percolation during sintering

A. Chiolerio et al., Microelectron. Eng. 97 (2012) 8-15


Islands of residual solvents + Ag NPs

Sintered Ag sponge

Si substrate

Uniform Non-uniform

Residual solvent droplets

Ag / copolymer Uniform zone

Si substrate

Post-annealing nanocomposite section

Post-annealing metal section

A. Chiolerio et al., RSC Advances 3 (2013) 3446


IjP 4 point probe

HAZ

Beam path

A. Chiolerio et al., Microelectron. Eng. 88 (2011) 2481


0 5 10 15 20 25 30 35 40 45 500

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AgSbF6

Thick-film resistivity for aged and electroaged samples; NP diameter distributions


Percolation theory: universal model for disordered systems. At criticality, percolation occurs and the system becomes conductive. The critical concentration only depends on the lattice properties.

s

c pp

MN

bap

ni

i ii

1

LATTICE pc

s

d=2 z=3 0.3116±0.0001 1.30±0.02

d=3 z=6 0.6962±0.0001 0.74±0.03

M. Sahimi, Application of Percolation Theory, Taylor & Francis, London 1994

25


Ag

s

cSbFPEGDAtw

banp

tw

ban

tw

ban

6

1

The new model takes into account the real 3-D

Distribution of NPs within the FESEM image

And the resistivity contribution

Due to SbF6- counter-ion

26


A specific composition, chosen to express radical-diffusion-engineering, gave

GF > 4

A. Chiolerio et al., Macr. Chem. Phys. 211 (2010) 2008; A. Chiolerio et al., Mater. Sci. Eng. B 177 (2012) 373; A. Chiolerio et al., RSC Advances 3 (2013) 3446


InkA-C100 uncured Unannealed G.F. >> 2.0

0 2 4 6 8 10 12 14

2

4

6

8

10

12

14

R

/R

l/l (%)

G.F.= 61

G.F.= 40

28 - A. Chiolerio, 26th October 2013, Rho Milanofiere, Mecha – Tronika -


A. Chiolerio et al., Microelec. Eng. 97 (2012) 8; V. Camarchia et al., Org. Elec. DOI: 10.1016/j.orgel.2013.10.018

30

Development of a conductive ink

Based on silver microparticles in polar solvent

RFID printed directly on BOPP packaging for food

Low thicknesses (5-10 µm ) high flexibility

Insulator based on functional nanoparticles (Al2O3, TiO2, BaTiO3, SiO2) and polymer-based with UV-curing capabilities

Development of an insulating ink


Electrodes realized on flexible copper metalized Kapton® (polyimide) film 50 µm thick by photolithography process and etching in iron chloride

Composite tactile sensor ready for characterization

Device under test in a real-time acquisition experiment


Filler: smooth conductive particles Matrix: elastometric, polymer matrix Connectivity: 0-3, 1-3 in function of AR and amount of filler. (Contact between conductive particles) Electrical resistance: is pressure dependent (variation about 6 orders of magnitude) Conduction mechanism: Percolation models

Filler: conductive spiky metal particles Matrix: elastometric, polymer matrix Connectivity: 0-3 (no contact among conductive particles) Electrical resistance: pressure dependent (from 1010 Ω‏to‏1‏Ω)‏exponential dependence with gap between particles Conduction mechanism: electrical field assisted Fowler- Nordheim tunneling model (enhancement factor up to 1000)

Quantum tunneling hybrid materials

Pressure conductive rubbers

Piezoresistive composite materials

Spiky particles QTC® material from Peratech©

Conventional composite Spherical particles

polymer matrix

connectivity = 0 : particles randomly distributed into the polymer matrix without being connected to each others

connectivity = 3 : continuous network

conductive metal particles

0 - 3 composites

Connectivity of composite

Images from Peratech© website www.peratech.com


AIM Multi-layered sensing coating monitoring environmental parameters (temperature, pressure, stresses...) and integrating circuits, antennas for data transmission and an energy source.

REQUIREMENTS AND DESIGN GUIDELINES Innovative and highly-performing sensing materials High flexibility Low energy consumption and small payload Large working condition range

A large-area, flexible pressure sensor matrix with organic field-effect

transistors for artificial skin applications, PNAS, 2004

A Rubberlike Stretchable Active Matrix Using Elastic Conductors. Science,

2008, Vol. 321, pp. 1468-1472

An Embedded Artificial Skin for Humanoid Robots G. Cannata, M. Maggiali, G. Metta and G. andini

Proceedings of IEEE

Human skin section

Low density modular sensors


http://4.bp.blogspot.com/_1PWGvz_Jlfs/S8x_m2XuoNI/AAAAAAAAFEo/4jgE2voULmk/s1600/mg20627566.800-1_300.jpg

Politronica Inkjet Printing www.politronica.eu

Acknowledgments

http://www.politronica.eu/

Contacts: http://shr.iit.it www.iit.it [email protected] [email protected] [email protected]

Thanks for your kind attention!

Istituto Italiano di Tecnologia (IIT), Center for Space Human Robotics, Turin, Italy

mailto:[email protected]



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