VTT TECHNICAL RESEARCH CENTRE OF FINLAND LTD · 2017-02-07 · Functional Materials Integration into Devices and Systems Meeting 5.-6.9.2016 VTT, ... • InkJet printing Optionally:

VTT TECHNICAL RESEARCH CENTRE OF FINLAND LTD

BET-EUFunctional Materials Integration into

Devices and Systems

Meeting 5.-6.9.2016VTT, presented by Maria Smolander

202/02/2017 2

AgendaMotivation and application opportunities for printed and hybridfunctional solutionsFacilitiesExamples

Printed transistorsHybrid solution on paper (Case ROPAS)Paper based diagnostic platform (e.g. Case Cyanodec)Printed biobattery (Case Cosmetic patch)

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Motivation for R2R Printed & HybridFunctionalities

Form factor & new functionalityFlexibilityWide area

New functions to productsBasis for novel products

Cost effective productionLow material use (per unit)High volume, rapid production

Starting largely from nicheapplications, a basis for disruptiveinnovations

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Application areas for wearable, stretchable anddisposable electronics and diagnostics

Skincare

Sports &Well-being

Elderly care

Smart packaging

Environmentaldiagnostics

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Application areas for printed and hybridfunctionalities on large-area surfaces

Media surfacesPainted walls

WindowsFurnitures

Floors

Textiles

6

World class research facility

Chemical and biochemicallaboratory facilities

Laboratory scaleprinting (flexo,screen,reverseoffset, gravure)

Measurement &charaterisation

Ink jet printing environment

Proof-of-concept Proof-of-manufacturability

Concept development in Lab-scale

PICO – in-air roll-to-rollpilot line

NICO – inert roll-to-roll pilotline

TESLA – functional testing

MAXI – In-air roll-to-roll pilot line

ROKO – in-air roll-to-rollpilot line

EVO - R2R assembly andbonding

ENGEL - Injectionmoulding

Best Technical DevelopmentManufacturing Award2012 Berlin, 2012 SantaClara, 2013 Berlin, 2013Tokyo

Upscaling in pilot factory

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Examples of printed electronic systems

Organic photovoltaics: electricalbalance, people amount counter,

presence sensor, energy harvestingtree, dollhouse, overmoulded OPV, …

Replication: R2R imprinteddiffractive optics,

microfluidics, back-/frontlight, light redirection, …

Printed organic transistors

Printed OLEDs: signage anddisplays, over-moulded OLED, …

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Examples of printed and hybrid solutions

Printed biobattery improving effect of cosmetics,cardboard integrated device for iontophoretic skintreatment

Printed fluidic channels on paper, Paper-based test forconsumers to detect e.g. toxic cyanobacteria

Intelligent swimming paddle(Trainesense), Flexiblewireless platform forwearable applications,Communicating envelope forinsured letters withembedded electronics onpaper, Printed sensor arrays

Intelligent packaging: Visible labels forpackage integrity and anti-tampering,Direct digital marking of consumerproducts, Package integrated smartphone readable sensor for foodproduct quality


Printed transistorsOrganic materials, metaloxidesAri Alastalo, Henrik Sandberg etal.

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Printed transistors

VTT is developing printed TFTs based on organic materials,oxides and CNTs.Organic materials have reached highest maturity and have beendemonstrated on R2ROxide materials have the highest performance but need specialcuring techniques for low-temperature annealingApplications targeted include sensor arrays, sensor tags andlogic of functional cards.

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Organic materials – sheet process

• T. Hassinen et al., “Printed polymer and carbon nanotube thin film transistors with high-k barium titanate insulator”, Japanese Journal of Applied Physics 53(2014)

• T. Hassinen et al., “Gravure printed low voltage polymer transistors and inverters”, Thin Solid Films 548 (2013) 585–589• * Vuokko Lantz, Henrik Sandberg, “Flexible sensor technologies for new device platforms”, LOPEC 2015 conference.

Logic circuits

Ring oscillator Ring oscillator output

Printed sensor and switching transistor arrayson flexible substrate*

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Organic materials – R2R process 1 - self-alignment for bottom gateMetal gate electrode and wiring:Resist printing (MAXI, flexo) + Ag Evaporation(EVA) + Lift-off (ROKO): Gate width 20 m

Organic dielectric printing:1st and 2nd layer (ROKO, reverse gravure)

Metal source & drain electrode formation:Resist printing (ROKO, flexo) + Backsideexposure (ROKO) + Development (ROKO) +Resist printing (MAXI, flexo) + Evaporation (EVA)+ Lift-off (ROKO)

Organic semiconductor printing:1st and 2nd layer (ROKO, reverse gravure) +lamination (ROKO)

• Vilkman, M., Ruotsalainen, T., Solehmainen, K., Jansson, E., Hiitola-Keinänen, J., “Self-Aligned MetalElectrodes in Fully Roll-to-Roll Processed Organic Transistors”, Electronics (Printed Electronics specialissue), 5(1) (2016) 2, DOI: 10.3390/electronics5010002.

• S. Jussila et al., ” Self-aligned patterning method of poly(aniline) for organic field-effect transistor gateelectrode, Organic Electronics 13 (2012) 1308 – 1314

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Organic materials – R2R process 2 - Lownumber of processing steps for top gate

Metal source & drain electrode:Ag Evaporation (EVA) or readily metallized substrateGel etch printing (MAXI/ROKO, screen / gravure)

TFT channel width 100 m (30 µm lab process)

Organic semiconductor and dielectric direct printing:1) Semiconductor solution (MAXI, gravure)2) Dielectric solution (MAXI, gravure)

Metal Gate electrode formation:Direct printing of metal particulate ink• Ag (MAXI, screen/flexo)• InkJet printingOptionally: Printed organic gate or metal shadow maskevaporation

• M. Vilkman et al., ”Fully roll-to-roll processed organic top gate transistors using a printable etchantfor bottom electrode patterning” Organic electronics, Volume 20, May 2015, Pages 8–14

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Oxide materials – sheet process with UV

• J. Leppäniemi et al., “Rapid low-temperature processing of metal-oxide thin film transistors with combined far ultraviolet and thermal annealing”, AppliedPhysics Letters 105 (2014) 113514

• H. Majumdar et al., “Low temperature processing of printable metal oxide thin film transistors”, Proc. ESTC2014, Sept. 16-18, 2014, Helsinki, Finland.• A. Alastalo et al., “Modelling of Printable Metal-Oxide TFTs for Circuit Simulation”, Proc. ESTC2014, Sept. 16-18, 2014, Helsinki, Finland.• http://youtu.be/yNpF_brcOj4

• Indium nitrate (In(NO3)3 xH2O, 99.9%) and Znnitrate precursor in 2-methoxyethanol (2-ME,99.8%) solvent

• Si, glass or PI substrate• Bottom-gate-top-contact TFT structure• Evaporation of Al gate electrodes using a shadow

metal mask (glass / PI).• ALD growth at 300 °C of 90 nm of Al2O3 insulator

to serve as the gate dielectric.• Spin coating or flexo / inkjet printing of the nitrate

precursor.• Annealing of the semiconductor at 300 °C for 30

min or at 200 °C for 15 min with FUV on ahotplate.

• Evaporation of the Al source and drain electrodesusing a metal shadow mask for 50 m channellength.

• Post annealing of the devices at 150 °C for 30min on a hotplate.

• Star map shownat LOPE-C 2014

• on-off circuit andLED driver onglass

• 3 discrete LEDs• Enfucell flexible

battery• See video

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Flexography-printed In2O3 TFTs on PI plastic

Electronic properties of In2O3 TFTs annealed at 300 °C:Optimized process gives µsat = 8 cm2/(Vs) on average and Von ~ 0 V

NC-In2O3

High-performance oxide devices with flexographic printing on plastic

• “Flexography-Printed In2O3 Semiconductor Layers for High-Mobility Thin-Film Transistors on Flexible Plastic Substrate”, J. Leppäniemi et alAdvanced Materials, 2015, 27, 7168–7175 http://dx.doi.org/10.1002/adma.201502569


Case ROPAS: Hybrid solutionon paper

Henrik Sandberg, Liisa Hakola, ElinaJansson, Arttu Huttunen, Maria Smolander

174th March 2015 A3PLE conference LOPE-C (ROPAS | VTT, Sandberg) 17

ROPAS demonstrators

Security tag Smart label Smart Envelop

Shipping of valuablegoods

Shipping of preciousgoods

Registered post

Open/close detection Humidity andtemperature sensor

Track and tracePassword control

Target on logistics

18

Demonstrators

• Security Tag• Conductive tracks

• Components placing

• Smart label• Chip integration

• NFC integration

• Printed sensors

• Smart envelope• Smaller print features

• Antenna integration

• ICT (Security / password)


Com

plexityofdem

onstrators

Com

plexityofelectronics

Com

plexityofprinting

19

Process up-scaling

Three main technologiesConductive tracks and dielectrics

PrintingScreen, FLEXO, Inkjet

Hot foil transferPostprocessing

Thermal, UV, IR, Flash sinteringIntegration

Heterogeneous & monolithicEncapsulation / packaging

Lamination, overcoat, inlay



VTT: MAXI & ROKO PRINTING

PlateAnilox

Paper

Cameraforregistration

Circuit (MAXI)

Dielectric (MAXI)

Antenna & bridges (ROKO)

21

Integration of components

Direct printing of resistors (~4 k )

Reel-to-reel pick'n'place process in“stop-and-go“ mode



Security Tag


Smart envelope – track and trace

Electronic layout

Antennaperformance

Wirelesscommunication

Web access andsecurity

23

Envelope Design


MATERIALS & METHODS

• R2R printing of circuit,dielectric, and antennalayers– Registration to circuit

layer– All the layer have

different register marks• Visual marks and marks

for automatic system

CIRCUIT – RED2xINSULATOR – DARK GREEN & CYANANTENNA - GREEN


BRIDGE PRINTING

• Bridges wereconductive– 0.26 ± 0.01 (8 mm

distance)

• No shorts (yield 100 %)were detected


ANTENNA PRINTING

• Antenna structure was nicelyreproduced

• Low square resistance valuewas obtained, < 9 Ohm

• Layer is rather rough anduneven

Ink Thickness(µm) Ra (nm) Rq (nm) Spreading

(µm)

Squareresistance

(m )

Volume resistivity·cm)

Antenna 18.1 ± 2.8 3020 ± 520 3710 ± 660 50 14.8 2.7E-05


Component placing

• Pick’n’place process at VTT (Oulu site)– 23 basic two terminal packages– 1 oscillator– 1 chip– Flex integration:

• Battery (enfucell)• Antenna (if separately printed)

• Main challenges– Number of components e.g. ST adhesive is

slow– Types of components need for different types

of adhesives


Smart Envelope

Printed paper antennacommunication >300m

Keyboard

LED

Battery powered

Patent application: EP13176531.5

Logic


Printed paper baseddiagnostics

Maria Smolander, Liisa Hakola, TuijaTeerinen, Kaisa Kiri

3002/02/2017 30

Printed visual indicators anddiagnostic tests

Sensors that give indication on the stateof an item or analyte concentration byvisual colour change or appearancePrinting methods for cost-efficiency, highthroughout and integration into productsVTT expertise in development of inks andmaterials (e.g. enzymes), optimisation ofmanufacturing process and up-scaling fromlaboratory to pilot scaleDemonstration of food quality, health &well-being and environmental indicators

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Paper-based diagnostics

Simple design and low-costPortable, flexible, disposableand bio-compatibleHigh throughput inmanufacturing can beachievedReproducible with highsensitivity and accuracyNo need for professionalmedical personnel orcomplicated instruments

Potential for integration ofhigh-density detectionsystems into a small device

Reference: Andres W. Martinez, Scott T. Phillips, and George M.Whitesides. Diagnostics for the Developing World: Microfluidic Paper-

Based Analytical Devices. Anal. Chem. vol. 82 (2010) p. 3–10.

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Flexographically printed paper microfluidics

Fluidic structures formed into chromatography paper (a) and clean room paper (c) byflexographic printing 5 w% polystyrene in xylene.

Flexographically printed fluidic structures in paper.Olkkonen J, Lehtinen K, Erho T.Anal Chem. 2010 Dec 15;82(24):10246-50.

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Printed and coated biomolecules on fibre based products

Bioactive functionalities (such as enzymesor antibodies) deposited into fiber basedstructuresCost effective manufacturing by printingand coating

incorporated in different paper coatingsmicroencapsulated and screen printedflexo printedink jet printed as distinct pattern

Heini Virtanen, Hannes Orelma, Tomi Erho, Maria Smolander, Process Biochemistry, Vol 47 (2012) 1496 – 1502.Savolainen, Anne; Zhang, Yufen; Rochefort, Dominic; Holopainen, Ulla; Erho, Tomi; Virtanen, Jouko; Smolander, Maria;Biomacromolecules, 12 (2011) 2008-2015.

Matilainen, K, Hämäläinen, T, Savolainen, A, Sipiläinen-Malm, T, Peltonen, J,Erho, T, Smolander, M. 2012. Colloids and Surfaces B: Biointerfaces, 90:1, 119-128

Cellulose as a novel substrate for lateral flow assay Lappalainen, T., Teerinen, T., Vento, P., Hakalahti, L., Erho, T. 2010 NordicPulp and Paper Research Journal 25 (4) , pp. 536-550

3402/02/2017 34

Glucose test demonstratorTesorb paper substrate (80 g/m2, Tervakoski)Four layers printed:

1. Flexography printed polystyrene (5 wt-%) layer for liquid guiding, both sides of paper2. Flexography printed PEI (polyethylene imine, 5 wt-%) layer for pH modification3. Inkjet printed pH ink (2 wt-%) layer for visual colour change4. Inkjet printed enzyme ink (glucose oxidase 5 mg/ml) for reaction with glucose

Four demonstrators: different combinations of lab and pilot scale inkjet and flexography

Pilot scaleMAXI line forlayer 1(15 cm3/m2 &25 cm3/m2)

Laboratory scaleprinter for layers1 & 2 (18 cm3/m2)

Laboratory scale printer(DMP, 10 pl, 1270 dpi)for layers 3 & 4

Industrial printheads(SE-128, 30 pl, 600 dpi)for layers 3 & 4

Print layoutfor inkjet

Print layoutfor flexography

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Principle of glucose test

1. Analyte (glucose) pipetted

2. Liquid flowin channels

to reaction spotscontaining pH dye

and enzyme

3. Colour change from red to yellowdue to analyte triggegred enzyme reactioncausing pH change

Pink area= channel boundaries

White areas= liquid channels

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Onsite Detection of Cyanobacteria Toxins

Value proposition:

Inexpensive and simple-to-use test kit for detection of cyanobacterial toxins in water

Based on mass-manufacturing methods for cost-effectiveness and disposability

Competitive edge: Paper or polymer based immunoassay test specific for toxinproducing cyanobacteria (microcystin, nodularin)

Offering: Test kit for cyanobacteria toxins with market potential defined

Outcome: Accurate results in short time , onsite testing, user friendly, cost effective

R&D infrastructure: Printing technology, laboratory and pilot scale equipment,upscale manufacturing process

Process: Manufacturing process

Channelprinting

Addition of celllysis reagents

Inkjetprinting/dosingof Au-conjugate

& antibodies

Sealing=Teststrip Sealing=Test

strip

Covering Graphics printing

Integration =test

Sample treatment, including external cell lysis (if needed)

Instruction of usePackaging =

Test kit

Production of antibodies

373702/02/2017

Prototype for Cyanobacter testhttps://www.youtube.com/watch?v=WhgwaOS_-ek


Printed biofuel cell

Saara Tuurala & Maria Smolander

3902/02/2017 39

Operating Principle of Biofuel Cell

Chemical energy of organic substrate(e.g. sugar or alcohol) is transformedinto electricity via biocatalysis (byenzymes or living cells)

The use of enzymes as catalysts forthe power source enables:

operation in mild conditionsuse of renewable chemicals asfueldisposability

VTT’s printed biofuel cell – biobattery –uses glucose and air as fuel

The biobattery produces µ-power;typically 1 µA/cm2 at 0.5 V

Oxidizedsubstrate

Anode CathodeSubstrate(e.g. sugar or alcohol)

O2 (air)

H2O

Cathode enzyme

Membrane

Anode enzyme

e-

h+

e-

Cathode shell

Anode shell

Cathode

Current collectors

Separator membrane

Anode

4002/02/2017 40

Development Path of biobattery / microcurrent patchHalf enzymatic,

printed power sourceCosmetic patch in industrial

sheet-to-sheet process

Production of bioactive electrodelayers in R2R pilot scale

Scale-up of manufacturing of printed enzymeelectrodes for enzymatic power sourceapplications, S. Tuurala et al., Journal of AppliedElectrochemistry 44(7) (2014) 881-892Increasing performance and stability of mass-manufacturable biobatteries by inkmodification, S. Tuurala et al., Sensing and Bio-Sensing Research 4 (2015) 61-69Increasing the Operational Lifetime of aPrinted Enzymatic Power Source usingSuperabsorbent Polymers as the AnodeSupport, S. Tuurala et al., Energy Technology,online on September 2015

Fully enzymatic, printedpower source

2005 2009 20122014

A mediated glucose/oxygenenzymatic fuel cell based onprinted carbon inks containingaldose dehydrogenase andlaccase as anode and cathode,P. Jenkins et al., Enzyme andMicrobial Technology50(3) (2012) 181-187

A comparison of glucoseoxidase and aldosedehydrogenase as mediatedanodes in printed,glucose/oxygen enzymatic fuelcells using ABTS/laccasecathodes, P. Jenkins et al.,Bioelectrochemistry 87 (2012)172-177

Development of a printablelaccase-based biocathode forfuel cell applications, M.Smolander et al., Enzyme andMicrobial Technology43(2) (2008) 93-102

Characterization and StabilityStudy of Immobilized PQQ-Dependent AldoseDehydrogenase Bioanodes, S.Tuurala et al., Electroanalysis24(2) (2012) 229-238

US2009280408AUS2013017457AWO2011073519WO15092153A1FI20155619

IPR

4102/02/2017 41

Application of the biofuel cell in microcurrentskin patch

Biofuel cell based microcurrent patchfacilitates the delivery of cosmeticsubstances efficiently into the skinVTTs microcurrent patch has followingfeatures:

efficacy shown by in vitro skinmicroscopy - increases the metabolicactivity and density of collagen fibers ofthe skinstability - can be stored in dry state evenfor years and is activated by moistureactivationenvironmentally friendly - is based onrenewable, enzymatic cathodic catalystdisposable - not interpretated as abattery according to the definition

4202/02/2017 42

Roll-to-roll printed biocatalysts for electrochemicalapplication

Scale-up of manufacturing of printedenzyme electrodes for enzymaticpower source applications

Saara Tuurala, Otto-Ville Kaukoniemi, Leo vonHertzen, Johanna Uotila, Anu Vaari, Mikael Bergelin,Pia Sjöberg, Jan-Erik Eriksson, Maria Smolander,accepted to J Appl Electrochem,DOI 10.1007/s10800-014-0702-2

*ROKO pilot scale printing line4 replaceable printing unitsDirect and reverse gravure, rotary screen, andflexography unitsCorona and lamination unitsDrying units (air, UV, IR)Web width 300 mmMax. web velocity 10 m/min

Anodic & cathodic layers ofprinted, enzyme-basedbiobattery printed and

dried in ROKO pilot scaleprinting line

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Unique environmentally friendlychemistry• cathodic catalysts is laccase

enzyme• renewable, produced in

biotechnical process• enables operation in mild

conditions• enables disposability

Environmentally friedly chemistry

4402/02/2017 44

Overall conclusions

Several printing and hybrid integration methodshave been successfully used for embeddingelectronic, chemical and biological functionalities intoR2R processed, flexible substrates including paperValue addition of R2R processes due to flexibility,possibility for large area, cost effective productionenabling high volume and disposable productsMain focus to be selected according to concept andapplication, materials and process need to meet thespecsPilot scale trials to demonstrate the proof-of-manufacturability

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TECHNOLOGY FOR BUSINESS

VTT TECHNICAL RESEARCH CENTRE OF FINLAND LTD · 2017-02-07 · Functional Materials Integration into Devices and Systems Meeting 5.-6.9.2016 VTT, ... • InkJet printing Optionally:

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