EU Project No. 611019

PiezoMAT Introduction

Alain GRAILLOT

SPECIFIC POLYMERS

Research and Development Functional Monomers, Polymers and Materials

2

PRESENTATION OUTLINE

• Company Profile - Partners

• R&D Activities

COMPANY PRESENTATION

• NWs Encapsulation

• Polymer/Silver hybrid materialsSP &

PIEZOMAT

• Functional dielectric materials

• Optical layers

• e- and h+ transporting layers

OPTO-ELECTRONICDEVICES

3

SPECIFIC POLYMERS – COMPANY PROFILE

SME created in 2003

Headquarters: CASTRIES (MONTPELLIER - FRANCE)

Annual turnover : 2015 – 620 K€ / 2016 – 800 K€

400 customers in more than 30 countries

50 % : R&D services

30 % : Catalog product sells

20 % : Custom synthesis

11 employees : 3 PhDs, 5 Engineers, 2 Technicians, 1 Adm

4

SPECIFIC POLYMERS – ACTIVITIES

F R&D

PCustom synthesis

Si Analyses

MATERIALS CHEMISTRY

OR

GA

NIC

CH

EM

IS

TR

YP

OLY

MER

S C

HEM

IS

TR

Y

Thermosets Thermoplastics

Synthesis of functional monomers, polymers and materials

5

SPECIFIC POLYMERS – ACTIVITIES

CH3 C4H9 CnH2n+1

NH2OH N3SH Cl Br

CH2 CH2 O CH3n

C CH

CO

OH

C6F13

P

OH

OH

O Si

OCH3

OCH3

OCH3

CH2

CH

CH2

O

OO

CCH CH2

O

O

OO

OC

C CH2

O

CH3

CH CH2CH2OCH CH2O

N

O

O

CH CH2

OH

OH

CH2 OH

CH2 CH O CH3

CH3n

Functions

Polymerizable group

Polymers and Materials Epoxy

Phenolics

Polyuréthane Acrylics

Styrenics

Monomers

Synthesis of functional monomers, polymers and materials

6

SPECIFIC POLYMERS – COMPANY PROFILE

INTERNALR&D

• New Chemistries• New Functionalities• New Building Blocks

New Monomers & Polymers

INNOVATION ENGINE

INNOVATIONS

More than 1000 references

CATALOGS

COLLABORATIVE

PROJECTS

• 1 ANR Project

2 ADEME Projects

2 European projects

• Expert in polymers and materials

• Breakthrough innovation

• More than 200 Academics

partners

• R&D Proofs of Concepts project

• Custom synthesis

• Production Batch test

Up-scaling ( 1g 1 Kg)

• More than 200 Industrial partners

INDUSTRIAL

PARTNERS

7

SPECIFIC POLYMERS – PARTNERS

INDUSTRIAL

PARTNERS

R&D Research Programs & Collaboratives Projects

15-20 Research Program / year

8

SPECIFIC POLYMERS – PARTNERS

ACADEMIC

PARTNERS

Catalog Products and Custom-synthesis – Academic Partners

200-250 Catalog Products / year

30-50 Custom Synthesis / year

9

SPECIFIC POLYMERS & PIEZOMAT

PiezoelectricZnONWs

Mechanicaldeformation

Piezo-potentials

1

2

One NW One pixel

3

Encapsulatingpolymer

Compatibility with NWs and seed layers : liquid and solvent free

Adjustable mechanical properties: soft to tough materials

Accurately and easily processable: liquid formulation

Encapsulation polymeric materials in multi-NWs pressure based fingerprint sensors

Required properties

CH C

O

O C6H12 O C

O

CH CH2CH2

CH C

O

OCH2 CH2 CH

CH3

O C

O

CH CH2

n=12

Acrylate basedUV crosslinked materials

Chemical and Thermal resistant : Crosslinked thermoset materials

10

SPECIFIC POLYMERS & PIEZOMAT

Encapsulation polymeric materials in multi-NWs pressure based fingerprint sensors

0 20 40 60 80 1000

20

40

60

80

100

120

Viscosity

Vis

co

sity

(cP

)

PPGdA content (wt%)

10 20 30 40 50 60 70 80 900,0

0,2

0,4

0,6

0,8

1,0

E* (DMA)

Tg (DSC)

T(DMA)

PPGdA content (wt%)

Yo

un

g m

od

ulu

s E

* (

GP

a)

-40

-20

0

20

40

60

Tra

nsitio

n te

mp

era

ture

s (°C)

(a) (b)Mastering mechanical properties

Low PPGA content

High crosslinking degree

High Young Modulus (E*)

High PPGA content

Low crosslinking degree

Low Young Modulus (E*)

Comsol Model

E* > 0.1 GpaOpt : 0.2 – 0.5 GPa

CH C

O

O C6H12 O C

O

CH CH2CH2

CH C

O

OCH2 CH2 CH

CH3

O C

O

CH CH2

n=12

Acrylate basedUV crosslinked materials

11

SPECIFIC POLYMERS & PIEZOMAT

Encapsulation polymeric materials in multi-NWs pressure based fingerprint sensors

0 20 40 60 80 1000

20

40

60

80

100

120

Viscosity

Vis

co

sity

(cP

)

PPGdA content (wt%)

10 20 30 40 50 60 70 80 900,0

0,2

0,4

0,6

0,8

1,0

E* (DMA)

Tg (DSC)

T(DMA)

PPGdA content (wt%)

Yo

un

g m

od

ulu

s E

* (

GP

a)

-40

-20

0

20

40

60

Tra

nsitio

n te

mp

era

ture

s (°C)

(a) (b)

0 20 40 60 80 1000

20

40

60

80

100

120

Viscosity

Vis

cosi

ty (

cP

)

PPGdA content (wt%)

10 20 30 40 50 60 70 80 900,0

0,2

0,4

0,6

0,8

1,0

E* (DMA)

Tg (DSC)

T(DMA)

PPGdA content (wt%)

Yo

un

g m

od

ulu

s E

* (

GP

a)

-40

-20

0

20

40

60

Tra

nsitio

n te

mp

era

ture

s (°C)

(a) (b)

Mastering mechanical properties

Comsol Model

E* > 0.1 GpaOpt : 0.2 – 0.5 GPa

PPGA content20–40 wt%

FormulationViscosity

Processabilty

Best Compromise

40 wt% PPGdA

Mastering thin layer thicknessesFormulation : 60%wt HdA / 40%wt PPGdA

2000 3000 4000 5000 6000 7000 80000

2

4

6

8

10

Encapsu

lati

on l

ayer

thic

kness

(µ

m)

Spin-coating rotation speed (rpm)

(a)

(b)

Influence of spin-coating

rotation speed

9µm 7µm 1.5µm

Polymer layer thickness from 1 to 9 µm

Suitable process for both options

12

SPECIFIC POLYMERS & PIEZOMAT

Encapsulation polymeric materials in multi-NWs pressure based fingerprint sensors

Improving surface properties

Perfluoro octyl acrylate (PFA) hydrophoby / oleophoby

O

OF

FF

FF

FF

FF

F

F

F

F

0 5 10 15 20

20

25

30

35

40

45

50

55

60

65

Water

Co

nta

ct

An

gle

(°)

- W

ate

r d

rop

PFA content (wt%)

0

5

10

15

20

25

30

Hexadecan

Co

nta

ct A

ng

le (°) - H

ex

ad

ecan

e d

rop

(a) (b)

20 wt% PFA – 2000 rpm

20 wt% PFA – 2000 rpm

8000 rpm

Polymer – silver flakes hybrid material

Conductive polymer layer as top electrod

PoC3 chips

PoC2 chips

Polymer layer thickness lower than NWs lenght

Polymer layer thickness higher than NWs lenght

Top conductive layer:Silver based polymeric

hybrid material (SP)

Top conductive layer:Gold metal deposition

(Fraunhofer)

PoC3 chips

PoC2 chips

Polymer layer thickness lower than NWs lenght

Polymer layer thickness higher than NWs lenght

Top conductive layer:Silver based polymeric

hybrid material (SP)

Top conductive layer:Gold metal deposition

(Fraunhofer)

Encapsulation

layer

Top conductive

layer

Compression option

iSheet resistance

1 and 60 Ω/sqFurther improvements of hydrophoby and

oleophoby are on going

13

OPTO-ELECTRONIC DEVICES

OrganicPhotovoltaïcs

Electrods

Dielectrics

Active layer

Transfer layers

Optical layers

One polymer for every layers

Organic LightEmitting Diodes

Organic Field-EffectTransistor

14

OPTO-ELECTRONIC DEVICES

Optical layer : Low refractive index layer

Poly(HFPO) acrylate (SP-0P4-7-002)

CH2OC

O

CHCH2 CH2 O C

O

CF

CF3

O CF2 CF

CF3

Fn

OC

O

CHCH2 CH2 C6F12 CH2 O C

O

CH CH2

Fluorinated diacrylate crosslinker

RI = 1.4

UV-CrosslinkedLow Refractive index material

Hybrid thin layer under study(SrTiO3, BaTiO3,NaF, LiF, CaF2)

OPTO-ELECTRONIC DEVICES

e-/h+ transporting and blocking layers

O CH CH2 O CH CH2 O CH2 CH O S

O

O

CH3S

O

O

C H3

CH3 CH3CH3 DMF

NaN35 5

CH CH2 O CH CH2 O C H2 CH

CH3 CH3CH3

N3 N3

S C2H4 S CH2 CH2CH2CH 2CH2N3 CH2 N3

A gent de réti cula tio n 1 Agent de réti cula tio n 2

CH2 CH2 O CH2OCH2CH2N3 CH 2 N3

n

2. PEG 6 00 (SP -SO L -4 8) ; 3 . P EG 10 00 (SP -SO L -44 ) ; 4. PEG 2 00 0 (SP-SO L - 50)

1 .SP- SO L -72SP-SOL-72

N

x yn

C60 grafed polystyrene

Avoid recombination of excitons

F

F

F

F

F

F

F

F

F

F

P

O

OHHOF

F

F

F

F

F

F

F

F

FF

Fluorophosphonic acids on PEDOT:PSS layer

Hole injection ITO Adhesion

• Electron transporting layers

• Hole transporting layers

Better hole transport

Enhanced luminous efficacy

SP & EUROSENSORS

Innovative polymers and materials in the fields of sensors

Smart Stimuli Responsive Polymers

3D-printing

• Functional materials for 3D printing applications

• Thermal and pH sensitive polymers

Materials for Microfluidic

• Sol-Gel materials – Functional alcoxysilane• Functional PDMS, poly(methacrylate), etc.

• Amphiphilic block copolymers

…

CONCLUSIONS

SPECIFIC POLYMERS R&D services providerPolymers and materials science

R&D Department

Analyses

Custom syntheses

Scale-Up

Processing

Production form gram to kilogram

Chemistry – Polymers & Materials

PiezoMAT European ProjectInnovative UV-crosslinked encapsulationlayers for multi-NWs based sensors

Opto-Electronic devices and sensorsSP is involved in optoelectronicsLooking for collaborations in Sensors

www.specificpolymers.fr

THANKS