Download BET-EU Functional Materials Integration into Devices and Systems

VTT TECHNICAL RESEARCH CENTRE OF FINLAND LTD
BET-EU
Functional Materials Integration into
Devices and Systems
Meeting 5.-6.9.2016
VTT, presented by Maria Smolander
Agenda
Motivation and application opportunities for printed and hybrid
functional solutions
Facilities
Examples
Printed transistors
Hybrid 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 & Hybrid
Functionalities
Form factor & new functionality
Flexibility
Wide area
New functions to products
Basis for novel products
Cost effective production
Low material use (per unit)
High volume, rapid production
Starting largely from niche
applications, a basis for disruptive
innovations
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Application areas for wearable, stretchable and
disposable electronics and diagnostics
Skincare
Sports &
Well-being
Elderly care
Smart packaging
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Environmental
diagnostics
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Application areas for printed and hybrid
functionalities on large-area surfaces
Painted walls
Media surfaces
Textiles
Furnitures
Floors
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Windows
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World class research facility
Concept development in Lab-scale
Ink jet printing environment
Chemical and biochemical
laboratory facilities
Upscaling in pilot factory
Laboratory scale
printing (flexo,
screen,reverse
offset, gravure)
Measurement &
charaterisation
Best Technical Development
Manufacturing Award
2012 Berlin, 2012 Santa
Clara, 2013 Berlin, 2013
Tokyo
MAXI – In-air roll-to-roll pilot line
Proof-of-concept
NICO – inert roll-to-roll pilot
line
PICO – in-air roll-to-roll
pilot line
TESLA – functional testing
ROKO – in-air roll-to-roll
pilot line
ENGEL - Injection
moulding
EVO - R2R assembly and
bonding
Proof-of-manufacturability
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Examples of printed electronic systems
Printed OLEDs: signage and
displays, over-moulded OLED, …
Organic photovoltaics: electrical
balance, people amount counter,
presence sensor, energy harvesting
tree, dollhouse, overmoulded OPV, …
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Replication: R2R imprinted
diffractive optics,
microfluidics, back-/front
light, light redirection, …
Printed organic transistors
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Examples of printed and hybrid solutions
Printed fluidic channels on paper, Paper-based test for
consumers to detect e.g. toxic cyanobacteria
Intelligent packaging: Visible labels for
package integrity and anti-tampering,
Direct digital marking of consumer
products, Package integrated smart
phone readable sensor for food
product quality
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Intelligent swimming paddle
(Trainesense), Flexible
wireless platform for
wearable applications,
Communicating envelope for
insured letters with
embedded electronics on
paper, Printed sensor arrays
Printed biobattery improving effect of cosmetics,
cardboard integrated device for iontophoretic skin
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treatment
VTT TECHNICAL RESEARCH CENTRE OF FINLAND LTD
Printed transistors
Organic materials, metal
oxides
Ari Alastalo, Henrik Sandberg et
al.
Printed transistors
VTT is developing printed TFTs based on organic materials,
oxides and CNTs.
Organic materials have reached highest maturity and have been
demonstrated on R2R
Oxide materials have the highest performance but need special
curing techniques for low-temperature annealing
Applications targeted include sensor arrays, sensor tags and
logic of functional cards.
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Organic materials – sheet process
Ring oscillator
Ring oscillator output
Printed sensor and switching transistor arrays
on flexible substrate*
Logic circuits
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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.
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Organic materials – R2R process 1 - selfalignment for bottom gate
Metal 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) + Backside
exposure (ROKO) + Development (ROKO) +
Resist printing (MAXI, flexo) + Evaporation (EVA)
+ Lift-off (ROKO)
Organic semiconductor printing:
1st and 2nd layer (ROKO, reverse gravure) +
lamination (ROKO)
•
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Vilkman, M., Ruotsalainen, T., Solehmainen, K., Jansson, E., Hiitola-Keinänen, J., “Self-Aligned Metal
Electrodes in Fully Roll-to-Roll Processed Organic Transistors”, Electronics (Printed Electronics special
issue), 5(1) (2016) 2, DOI: 10.3390/electronics5010002.
S. Jussila et al., ” Self-aligned patterning method of poly(aniline) for organic field-effect transistor gate
electrode, Organic Electronics 13 (2012) 1308 – 1314
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Organic materials – R2R process 2 - Low
number of processing steps for top gate
Metal source & drain electrode:
Ag Evaporation (EVA) or readily metallized substrate
Gel 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 printing
Optionally: Printed organic gate or metal shadow mask
evaporation
•
02/02/2017
M. Vilkman et al., ”Fully roll-to-roll processed organic top gate transistors using a printable etchant
for bottom electrode patterning” Organic electronics, Volume 20, May 2015, Pages 8–14
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Oxide materials – sheet process with UV
•
Indium nitrate (In(NO3)3 xH2O, 99.9%) and Zn
nitrate 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 a
hotplate.
Evaporation of the Al source and drain electrodes
using a metal shadow mask for 50 m channel
length.
Post annealing of the devices at 150 °C for 30
min on a hotplate.
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Star map shown
at LOPE-C 2014
on-off circuit and
LED driver on
glass
3 discrete LEDs
Enfucell flexible
battery
See video
J. Leppäniemi et al., “Rapid low-temperature processing of metal-oxide thin film transistors with combined far ultraviolet and thermal annealing”, Applied
Physics 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
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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
High-performance oxide devices with flexographic printing on plastic
NC-In2O3
•
“Flexography-Printed In2O3 Semiconductor Layers for High-Mobility Thin-Film Transistors on Flexible Plastic Substrate”, J. Leppäniemi et al
Advanced Materials, 2015, 27, 7168–7175 http://dx.doi.org/10.1002/adma.201502569
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VTT TECHNICAL RESEARCH CENTRE OF FINLAND LTD
Case ROPAS: Hybrid solution
on paper
Henrik Sandberg, Liisa Hakola, Elina
Jansson, Arttu Huttunen, Maria Smolander
ROPAS demonstrators
Target on logistics
Security tag
Smart label
Smart Envelop
Shipping of valuable
goods
Shipping of precious
goods
Registered post
Open/close detection Humidity and
temperature sensor
4th March 2015
Track and trace
Password control
A3PLE conference LOPE-C (ROPAS | VTT, Sandberg)
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Demonstrators
• Security Tag
• Chip integration
• NFC integration
• Printed sensors
Complexity of printing
• Smart label
Complexity of electronics
• Components placing
Complexity of demonstrators
• Conductive tracks
• Smart envelope
• Smaller print features
• Antenna integration
• ICT (Security / password)
4th March 2015
A3PLE conference LOPE-C (ROPAS | VTT, Sandberg)
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Process up-scaling
Three main technologies
Conductive tracks and dielectrics
Printing
Screen, FLEXO, Inkjet
Hot foil transfer
Postprocessing
Thermal, UV, IR, Flash sintering
Integration
Heterogeneous & monolithic
Encapsulation / packaging
Lamination, overcoat, inlay
4th March 2015
A3PLE conference LOPE-C (ROPAS | VTT, Sandberg)
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VTT: MAXI & ROKO PRINTING
Camera
for
registrati
on
Anilox
Plate
Dielectric (MAXI)
Paper
Circuit (MAXI)
Antenna & bridges (ROKO)
4th March 2015
A3PLE conference LOPE-C (ROPAS | VTT, Sandberg)
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Integration of components
Direct printing of resistors (~4 k )
Reel-to-reel pick'n'place process in
“stop-and-go“ mode
4th March 2015
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Security Tag
4th March 2015
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Smart envelope – track and trace
Wireless
communication
Electronic layout
Envelope Design
Antenna
performance
4th March 2015
A3PLE conference LOPE-C (ROPAS | VTT, Sandberg)
Web access and
security
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MATERIALS & METHODS
•
R2R printing of circuit,
dielectric, and antenna
layers
– Registration to circuit
layer
– All the layer have
different register marks
• Visual marks and marks
for automatic system
CIRCUIT – RED
2xINSULATOR – DARK GREEN & CYAN
ANTENNA - GREEN
4th March 2015
A3PLE conference LOPE-C (ROPAS | VTT, Sandberg)
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BRIDGE PRINTING
• Bridges were
conductive
– 0.26 ± 0.01
distance)
(8 mm
• No shorts (yield 100 %)
were detected
4th March 2015
A3PLE conference LOPE-C (ROPAS | VTT, Sandberg)
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ANTENNA PRINTING
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Antenna structure was nicely
reproduced
•
Low square resistance value
was obtained, < 9 Ohm
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Layer is rather rough and
uneven
Ink
Thickness
(µm)
Ra (nm)
Antenna
18.1 ± 2.8
3020 ± 520
4th March 2015
Rq (nm)
Spreading
(µm)
Square
resistance
(m
)
Volume resistivity
·cm)
3710 ± 660
50
14.8
2.7E-05
A3PLE conference LOPE-C (ROPAS | VTT, Sandberg)
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Component placing
• Pick’n’place process at VTT (Oulu site)
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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
4th March 2015
A3PLE conference LOPE-C (ROPAS | VTT, Sandberg)
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Smart Envelope
Printed paper antenna
communication >300m
Logic
LED
Battery powered
Patent application: EP
13176531.5
4th March 2015
Keyboard
A3PLE conference LOPE-C (ROPAS | VTT, Sandberg)
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VTT TECHNICAL RESEARCH CENTRE OF FINLAND LTD
Printed paper based
diagnostics
Maria Smolander, Liisa Hakola, Tuija
Teerinen, Kaisa Kiri
Printed visual indicators and
diagnostic tests
Sensors that give indication on the state
of an item or analyte concentration by
visual colour change or appearance
Printing methods for cost-efficiency, high
throughout and integration into products
VTT expertise in development of inks and
materials (e.g. enzymes), optimisation of
manufacturing process and up-scaling from
laboratory to pilot scale
Demonstration of food quality, health &
well-being and environmental indicators
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Paper-based diagnostics
Simple design and low-cost
Portable, flexible, disposable
and bio-compatible
High throughput in
manufacturing can be
achieved
Reproducible with high
sensitivity and accuracy
No need for professional
medical personnel or
complicated instruments
02/02/2017
Potential for integration of
high-density detection
systems into a small device
Reference: Andres W. Martinez, Scott T. Phillips, and George M.
Whitesides. Diagnostics for the Developing World: Microfluidic PaperBased 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) by
flexographic printing 5 w% polystyrene in xylene.
02/02/2017
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 enzymes
or antibodies) deposited into fiber based
structures
Cost effective manufacturing by printing
and coating
incorporated in different paper coatings
microencapsulated and screen printed
flexo printed
ink 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 Nordic
Pulp and Paper Research Journal 25 (4) , pp. 536-550
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Glucose test demonstrator
Tesorb paper substrate (80 g/m2, Tervakoski)
Four layers printed:
1. Flexography printed polystyrene (5 wt-%) layer for liquid guiding, both sides of paper
2. Flexography printed PEI (polyethylene imine, 5 wt-%) layer for pH modification
3. Inkjet printed pH ink (2 wt-%) layer for visual colour change
4. 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
Print layout
for inkjet
Print layout
for flexography
02/02/2017
Pilot scale
MAXI line for
layer 1
(15 cm3/m2 &
25 cm3/m2)
Laboratory scale
printer for layers
1 & 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
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Principle of glucose test
1. Analyte (glucose) pipetted
2. Liquid flow
in channels
to reaction spots
containing pH dye
and enzyme
Pink area
= channel boundaries
White areas
= liquid channels
3. Colour change from red to yellow
due to analyte triggegred enzyme reaction
causing pH change
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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 toxin
producing 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
Channel
printing
Addition of cell
lysis reagents
Inkjet
printing/dosing
of Au-conjugate
& antibodies
Sealing=Test
strip
Covering
Sealing=Test
strip
Graphics printing
Integration =
test
Production of antibodies
Sample treatment, including external cell lysis (if needed)
Instruction of use
02/02/2017
Packaging =
Test kit
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Prototype for Cyanobacter test
https://www.youtube.com/watch?v=WhgwaOS_-ek
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VTT TECHNICAL RESEARCH CENTRE OF FINLAND LTD
Printed biofuel cell
Saara Tuurala & Maria Smolander
Operating Principle of Biofuel Cell
Chemical energy of organic substrate
(e.g. sugar or alcohol) is transformed
into electricity via biocatalysis (by
enzymes or living cells)
The use of enzymes as catalysts for
the power source enables:
operation in mild conditions
use of renewable chemicals as
fuel
disposability
e-
Oxidized
substrate
eAnode enzyme
Cathode enzyme
h+
H2O
Substrate
Anode
(e.g. sugar or alcohol)
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
O2 (air)
Membrane
Cathode
Current collectors
Cathode shell
Cathode
Separator membrane
Anode
Anode shell
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Development Path of biobattery / microcurrent patch
Half enzymatic,
printed power source
Fully enzymatic, printed
power source
2009
2005
Development of a printable
laccase-based biocathode for
fuel cell applications, M.
Smolander et al., Enzyme and
Microbial Technology
43(2) (2008) 93-102
Characterization and Stability
Study of Immobilized PQQDependent Aldose
Dehydrogenase Bioanodes, S.
Tuurala et al., Electroanalysis
24(2) (2012) 229-238
02/02/2017
Cosmetic patch in industrial
sheet-to-sheet process
A mediated glucose/oxygen
enzymatic fuel cell based on
printed carbon inks containing
aldose dehydrogenase and
laccase as anode and cathode,
P. Jenkins et al., Enzyme and
Microbial Technology
50(3) (2012) 181-187
A comparison of glucose
oxidase and aldose
dehydrogenase as mediated
anodes in printed,
glucose/oxygen enzymatic fuel
cells using ABTS/laccase
cathodes, P. Jenkins et al.,
Bioelectrochemistry 87 (2012)
172-177
2012
2014
Production of bioactive electrode
layers in R2R pilot scale
Scale-up of manufacturing of printed enzyme
electrodes for enzymatic power source
applications, S. Tuurala et al., Journal of Applied
Electrochemistry 44(7) (2014) 881-892
Increasing performance and stability of massmanufacturable biobatteries by ink
modification, S. Tuurala et al., Sensing and BioSensing Research 4 (2015) 61-69
Increasing the Operational Lifetime of a
Printed Enzymatic Power Source using
Superabsorbent Polymers as the Anode
Support, S. Tuurala et al., Energy Technology,
online on September 2015
IPR
US2009280408A
US2013017457A
WO2011073519
WO15092153A1
FI20155619
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Application of the biofuel cell in microcurrent
skin patch
Biofuel cell based microcurrent patch
facilitates the delivery of cosmetic
substances efficiently into the skin
VTTs microcurrent patch has following
features:
efficacy shown by in vitro skin
microscopy - increases the metabolic
activity and density of collagen fibers of
the skin
stability - can be stored in dry state even
for years and is activated by moisture
activation
environmentally friendly - is based on
renewable, enzymatic cathodic catalyst
disposable - not interpretated as a
battery according to the definition
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Roll-to-roll printed biocatalysts for electrochemical
application
Anodic & cathodic layers of
printed, enzyme-based
biobattery printed and
dried in ROKO pilot scale
printing line
Scale-up of manufacturing of printed
enzyme electrodes for enzymatic
power source applications
Saara Tuurala, Otto-Ville Kaukoniemi, Leo von
Hertzen, 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
02/02/2017
*ROKO pilot scale printing line
4 replaceable printing units
Direct and reverse gravure, rotary screen, and
flexography units
Corona and lamination units
Drying units (air, UV, IR)
Web width 300 mm
Max. web velocity 10 m/min
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Environmentally friedly chemistry
Unique environmentally friendly
chemistry
• cathodic catalysts is laccase
enzyme
• renewable, produced in
biotechnical process
• enables operation in mild
conditions
• enables disposability
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Overall conclusions
Several printing and hybrid integration methods
have been successfully used for embedding
electronic, chemical and biological functionalities into
R2R processed, flexible substrates including paper
Value addition of R2R processes due to flexibility,
possibility for large area, cost effective production
enabling high volume and disposable products
Main focus to be selected according to concept and
application, materials and process need to meet the
specs
Pilot scale trials to demonstrate the proof-ofmanufacturability
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TECHNOLOGY FOR BUSINESS
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