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Paper Electronics

Martti ToivakkaLaboratory of Paper Coating and Converting

Center for Functional MaterialsÅbo Akademi University

Paper as Substrate for Printed Electronics and Functionality

Martti Toivakka 2013

Co-operative Research

www.funmat.fi www.abo.fi/lpcc

Roger Bollström1, Daniel Tobjörk3, Anni Määttänen2, Petri Ihalainen2, Jouko Peltonen2, Ronald Österbacka3 and Martti Toivakka1

1Paper Coating and Converting2Physical Chemistry

3Physics/Organic Electronics

• D. Tobjörk & R. Österbacka, Paper Electronics, Adv Mater. 23(17):1935‐61, 2011.• R. Bollström, Paper for printed electronics and functionality, PhD‐thesis, Åbo

Akademi, submitted, 2013.


Paper Electronics for Pre-school!

Scientific Tuesdays, http://www.youtube.com/watch?v=BwKQ9Idq9FM


Paper Electronics = Disposable Printed Electronicson/in Paper with Commercial Potential

“Paper Accelerometer Could Mean Disposable Devices,” X. Liu, et al.

“Cheap Microfluidic Device Made From Paper and Tape,” G.M. Whitesides

Electrochemical Paper Display, Acreo, SE

Pharma DDSi, StoraEnso

“Zero-Cost Diagnostics,” G.M. Whitesides

Gas sensor on paper, Peltonen et al., FunMat/FlexSens


Fabrication of Solution ProcessableDevices on Paper•Success of fabrication (printability) is determined bycompatibility of ink – printing method – substrate:

› Inks (solution processable functional materials): • Conductive particulate inks, e.g. nanoparticle/micron-size silver,

carbon, gold, copper…• Conductive polymer inks, e.g. PEDOT:PSS, PANI…• Semiconducting inks, e.g. P3HT, PQT…• Insulators, e.g. PVP, PMMA…

› Printing / coating method: • Inkjet, flexography, rotogravure, screen printing…• Reverse gravure, spray, slot, curtain…

› Substrate: Paper or board, i.e. natural fiber-based substrate


Inkjetted Particulate Silver Ink

R. Bollström et al., 2013.

Functional Printing on Uncoated Paper

• Poor performance due to:› high surface roughness› uncontrolled spreading› uncontrolled absorption

Inkjetted PEDOT:PSS-SWCNT Ink

P. Angelo et al. NPPRJ 27(2):486, 2012

200 µm200 µm


FunMat Substrate Concept For Paper Electronics

Bollström, R., A. Määttänen, D. Tobjörk, P. Ihalainen, N. Kaihovirta, R. Österbacka, J. Peltonen, and M. Toivakka. "A multilayer coated fiber-based substrate suitable for printed functionality." Organic Electronics 10, no. 5 (2009): 1020–1023.

Barrier layer (Latex) 1 - 25 µm

Topcoating (Kaolin) 0.5 - 5 µm

Precoating (GCC)

Smoothing layer (Kaolin)

Basepaper


Multilayer Substrate Manufacturing I

+

Bollström R., Tuominen M., Määttänen A., Peltonen J. and Toivakka M. (2012), Top layer coatability on barrier coatings. Progress in Organic Coatings, 73(1), 26–32.

Blade coating Reverse gravure coating


Slide die curtain coating

Multilayer Substrate Manufacturing II


Slide die curtain coating

Multilayer Substrate Manufacturing II


Pilot Scale Manufacturing

R. Bollström et al., FlexSens-project


•Transistor•Ring oscillator•Electrochromic pixels•Hydrogen sulfide sensor•Oxygen sensor•Ion-selective electrodes•Reaction array•Printable circuit for gas sensors

Proof-of-concept Devices on Paper


Important Paper Properties that Control Functional Ink Behavior•Barrier properties (permeability)

•Surface roughness

•Surface energy

•(Surface) porosityand pore volume


P3HT in DCB

Barrier Properties against Functional Inks Formulated in Solvents


0

10

20

30

40

50

60

70

80

90

100

0 100 200 300 400 500 600 700 800 900 1000

MΩ

Time (s)

A 1 A 2 A 3

B 1 B 2 B 3

C 1 C 2 C 3Deviation for paper CDeviation for paper B

Measuring Solvent Barrier Properties

Bollström R., Saarinen J.J., Räty J. and Toivakka M. (2012) Measuring solvent barrier properties of paper. Measurement Science and Technology, 23, 015601.


Barrier Layer Performance is Determined by Barrier Polymer Chemistry and Barrier Layer Tortuosity

Bollström R., Nyqvist R., Preston J., Salminen P. and Toivakka M. (2013) Barrier properties created by dispersion coating. TAPPI Journal, 12(4), 45–51.


Barrier layer(Latex)

RMS 260 nm

Calandered topcoating(Kaolin)

RMS 55 nm

Precoating(GCC)

RMS 580 nm

Smoothing layer(Kaolin)

RMS 300 nmMylar® A

RMS 30 nm

Surface Smoothness Control

J. Järnström, P. Ihalainen, K. Backfolk, J. Peltonen: Applied Surface Science 2542 (2008) 5741R. Bollstrom, D. Tobjörk, A. Määttänen, P. Ihalainen, R. Österbacka, J. Peltonen, M. Toivakka,: Org. Electronics, 10, 1020 (2009)R. Bollström, A. Määttänen, P. Ihalainen, M. Toivakka, J. Peltonen: Patent application PCT/FI2010/050056


Surface Energy Control of the Substrate

SiO2

TiO2

Stepien M., Saarinen J.J., Teisala H., Tuominen M., Aromaa M., Haapanen J., Kuusipalo J., Makela J.M. and Toivakka M. (2013) ToF-SIMS Analysis of UV-Switchable TiO2-Nanoparticle-Coated Paper Surface. Langmuir, 29(11), 3780–3790.


A thinner and less porous topcoat preferableBollström R., Tobjörk D., Dolietis P., Salminen P., Preston J., Österbacka R. and Toivakka M. (2013) Printability of functional inks on multilayer curtain coated paper. Chemical Engineering and Processing: Process Intensification, 68, 13–20.

Surface Pore Volume vs. SemiconductorPerformance (inkjet + soluble ink)

R² = 0.9348

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

0 20 40 60 80 100TΩ

/sq

Pore volume [nl/cm²]

Measurement of Surface Porosity

Hg-p

oro

sim

etr

y


High Surface Pore Volume minimizes the Halo Effect (”Squeeze”) in Flexography

Low surface porosity High surface porosity

A thicker and more porous topcoat preferable


Paper as a Substrate for Printed Electronics and Functionality•No universal “Paper for printed electronics” exists (excluding plastic coated paper)

•Device(s) to be fabricated, i.e. end-use application, determine which paper properties need to be controlled:

› Barrier properties, surface roughness, surface energy, surface porosity, dimensional stability, thermal resistance…

› …while maintaining the low cost and recyclability


Arjowiggin's Powercoat® Paper for Printed Electronics

PowerCoat® outperforms even the best plastics and is recyclable and sustainable. This novel paper has excellent smoothness and higher thermal stability than most PET/PEN plastics. Additionally, since POWERCOAT allows higher printing speeds than most plastics, because of its impressive thermal stability…

•100% recyclable•Heat resistance 5 min @ 200°C•Smoothness Ra < 20nm (AFM)


Paper as a Substrate for Printed Electronics and Functionality•No universal “Paper for printed electronics” exists (excluding plastic coated paper)

•Device(s) to be fabricated, i.e. end-use application, determine which paper properties need to be controlled:

› Barrier properties, surface roughness, surface energy, surface porosity, dimensional stability, thermal resistance…

› …while maintaining the low cost and recyclability


Conclusions and Outlook•FunMat has developed multilayer coated specialty paper and demonstrated printed transistors and numerous devices on it

•Main challenges are niche market position, market ”resistance” and non-existence of suitable hybrid printers

•First products will be simple sensors for biological, biomedical and chemical applications lab-on-a-chip & bioanalytics


Towards Mass Fabrication of Paper-based Electronics – FunPrinter

Roger Bollström: Roll-to-roll fabrication of low-cost paper-based electronic devices and sensors


Publications• Bollström R., Nyqvist R., Preston J., Salminen P. and Toivakka M. (2013) Barrier properties created by dispersion

coating. TAPPI Journal, 12(4), 45–51.• Bollström R., Tobjörk D., Dolietis P., Salminen P., Preston J., Österbacka R. and Toivakka M. (2013) Printability of

functional inks on multilayer curtain coated paper. Chemical Engineering and Processing: Process Intensification, 68, 13–20.

• Stepien M., Saarinen J.J., Teisala H., Tuominen M., Aromaa M., Haapanen J., Kuusipalo J., Makela J.M. and Toivakka M. (2013) ToF-SIMS Analysis of UV-Switchable TiO2-Nanoparticle-Coated Paper Surface. Langmuir, 29(11), 3780–3790.

• Valtakari D., Bollström R., Tuominen M., Teisala H., Aromaa M., Toivakka M., Kuusipalo J., Mäkelä J.M., Uozumi J. and Saarinen J.J. (2013) Flexographic printing of PEDOT:PSS on coated papers for printed functionality. Journal of Print and Media Technology Research, 2(1), 7–13.

• Ylikantola A., Linnanto J., Knuutinen J., Oravilahti A. and Toivakka M. (2013) Molecular modeling studies of interactions between sodium polyacrylate polymer and calcite surface. Applied Surface Science, 276, 43–52. 2012

• Bollström, R., M. Tuominen, A. Määttänen, J. Peltonen, and M. Toivakka. "Top layer coatability on barrier coatings." Progress in Organic Coatings 73, no. 1 (2012): 26–32.

• Bollström, R., J. J. Saarinen, J. Räty, and M. Toivakka. "Measuring solvent barrier properties of paper." Measurement Science and Technology 23 (2012): 015601.

• Tobjörk, D., H. Aarnio, P. Pulkkinen, R. Bollström, A. Määttänen, P. Ihalainen, T. Mäkelä, J. Peltonen, M. Toivakka, H. Tenhu et al. "IR-sintering of ink-jet printed metal-nanoparticles on paper." Thin Solid Films 520, no. 7 (2012): 2949–2955.

• Ihalainen, P., A. Määttänen, U. Mattinen, M. Stepien, R. Bollström, M. Toivakka, J. Bobacka, and J. Peltonen. "Electrodeposition of PEDOT-Cl film on a fully printed Ag/polyaniline electrode." Thin Solid Films 519 (2011): 2172–2175.

• Saarinen, J. J., P. Ihalainen, A. Määttänen, R. Bollström, and J. Peltonen. "Printed sensor and electric field assisted wetting on a natural fibre based substrate." Nordic Pulp and Paper Research Journal 26, no. 1 (2011).

• Määttänen, A., D. Fors, S. Wang, D. Valtakari, P. Ihalainen, and J. Peltonen. "Paper-based planar reaction arrays for printed diagnostics." Sensors and Actuators B: Chemical 160, no. 1 (2011): 1404–1412.Mää ä A P Ih l i R B ll ö M T i kk d J P l "W i d i li d f i kj

http://www.abo.fi/lpcc

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