Recent developments in PEDOT/PSS - Formulations and Ink for Printable Electrodes

Transcription

1 Recent developments in PEDOT/PSS - Formulations and Ink for Printable Electrodes Bavo Muys Application Manager ORGACON Electronic Materials T: F: M: Bavo.muyst@agfa.com Dr. Frank Louwet Business Manager ORGACON Electronic Materials T: F: M: frank.louwet@agfa.com

2 Agfa in the world Sales organizations in 40 countries Representations in 100 countries Manufacturing sites in 10 countries 2 Membrane Switch + Advanced Functional Printing

3 Agfa in the World Agfa Gevaert Group 2009: FTE Headquarters in Mortsel (Antwerp), Belgium Group Sales 2009 : Billion Graphics B Healthcare B Specialty Products B Healthcare: No 1-2 Prepress: No 1-2 Sales organizations in 40 countries Manufacturing sites in 10 countries Representations in 100 countries Listing Brussels Stock Exchange By Business Group 2009 Graphics 48% Agfa-Gevaert Group Parent Company HealthCare 43% 9% Specialty Products By Region 2009 Asia & ROW 22% Latin America 8% NAFTA 19% Agfa Gevaert Group Europe 51% Agfa Graphics Agfa HealthCare Agfa Materials Specialty Products Integrated prepress solutions to the printing and industrial ink jet printing industry: consumables, hardware, software and services for production workflow, project and color management. Integrated solutions for capturing, processing and managing diagnostic images and IT solutions that integrate the imaging workflow into the overall hospital operations across departmental disciplines (PACS, HIS, RIS, CIS). Supplies film-based products and high-tech solutions to large B2B customers outside the graphic and healthcare markets, e.g. synthetic paper, functional foils, conductive materials, specialty inks. 3 Membrane Switch + Advanced Functional Printing

4 BACKGROUND :ANTISTATICS O S O + SO 3 H y Na 2 S 2 O 8 (Fe 2 (SO 4 ) 3 ) H 2 O H O S O O O O O O O O O + + S S S H S SO 3 H SO 3 - SO 3 H SO 3 - SO 3 H "EDOT" "PEDOT/PSSA" ORGACON TM First use as antistatic in photographic films, since 1990 More than 20 years experience R&D - development, Production - Application Strong IP position Over 200 million m² /Y coated films 4 Membrane Switch + Advanced Functional Printing

5 Effect of HBS High Boiling Solvent Standard PEDOT:PSS: antistatic behaviour Can be spin-coated or cast onto any substrate Highly transparent & flexible film But rather low conductivity Adding high boiling solvent (NMP, DMSO, ) Conductivity increase of 3 to 6 orders of magnitude Binders & temperature flexibility: C Antistatic PEDOT:PS 0.1 S/cm S + HB S >500 S/cm without HBS formation of network with HBS Morphological studies: Angle dependent XPS (IFM Linkoping Sweden) and TOFSIMS showed a change in the PEDOT/PSSA ratio at the surface AFM (KULeuven Belgium), TEM and HR SEM (IMOMEC Belgium) showed a phase separation: more spongy structure formation of a network Confirmation by third party studies 5 Membrane Switch + Advanced Functional Printing

6 Key properties of ORGACON TM 1. Low surface resistance ( SER ) combined with high Visual Light Transmission ( VLT ) 2. Good stability to high T/RH and light 3. High flexibility and formability => high speed R2R compatibility 4. Direct patterning Availability of inks with low curing T 6 Membrane Switch + Advanced Functional Printing

7 Orgacon TM as ITO alternative Apparel Remote controls Transparent ESD protection Signage Car interior lighting Applications E-paper displays OLED light Solar cells Printable electronics Mobile phones Tablet PC Displays (flexible) Car license plates Wearable EL Sensors Flex -EL lamps In-mould EL lamps Capacitors Printed Memories Touch pads Touch screens Modules PEDOT Electrodes HTL coatings AS hard coats Grid technology Sub-component Coating solutions Coating solutions Orgacon Dry Orgacon Dry inks inks films films PEDOT: PSS PEDOT: PSS Dispersion Dispersion 7 Membrane Switch + Advanced Functional Printing

8 Cholesteric color display Kent Display 8 Membrane Switch + Advanced Functional Printing

9 AC EL Application Examples EL-IML prototype 9 Membrane Switch + Advanced Functional Printing

10 Piëzo with clean backlight Conductive Silver Piezo Switch Invisible Orgacon Ink 10 Membrane Switch + Advanced Functional Printing

11 CH Orgacon S300 Reflective PDLC displays Boogie Board 40% 5% Kent Displays bistable, cholesteric liquid crystal display technology PEDOT/PSS electrodes (Orgacon TM ) Bright (planar) Dark (focal-conic) Substrate Liquid Crystal Substrate Absorb Electrodes 11 Membrane Switch + Advanced Functional Printing

12 Combining conductivity and transparency: SER * OD Optical density mainly proportional to layer thickness: Surface resistance 1 SER = σ h Optical density: OD = α h α SER OD ± constant σ σ α h specific conductivity absorption coefficient dry layer thickness Transparent conductivity of PEDOT:PSS defined by both parameters Surface resistance [Ohm/sq] ,00 0,05 0,10 0,15 0,20 0,25 Optical density [1] S103 coating formulation on PET Air drying 3 min at 140 C SER*OD Wet layer thickness [µm] S103 coating formulation on PET Air drying 3 min at 140 C 12 Membrane Switch + Advanced Functional Printing

13 Key property : low surface resistance high VLT Test: Orgacon S30X coating formulation (Coated 40µm wet, dry C) SER * O.D Orgacon SER Ohm/sq VLT % excl PET Generation of Orgacon OD SER*OD Excl PET Gen 1 Gen 2 Gen 3 Gen ,7 87,3 86,9 90, Gen , ,4 Typical values, no specification 4,33x improvement 13 Membrane Switch + Advanced Functional Printing

14 Key property : low surface resistance high VLT Continuous improvement of intrinsic conductivity 600 GEN1 GEN2 500 GEN3 Surface Resistance [ohm/sq] GEN4 GEN5 Improvement High end Low end ITO on flexible substrate 0 70% 75% 80% 85% 90% 95% 100% Visual Transparency [%] Agfa coating formulation S30x on PET Ambient test environment Drying conditions: 3 min at 130 C 14 Membrane Switch + Advanced Functional Printing

15 Key property: Improved Stability Orgacon S305 and S305plus coated 40µm wet thickness on PET and dried 130 C Stability test at 60 C/95%RH 900 hr S305 S305 plus SER (Ohm/sq) S305 S305 plus C/95%R.H. 15 Membrane Switch + Advanced Functional Printing

16 Key property: Improved Stability Orgacon S305 and S305plus coated 40µm wet thickness on PET and dried 130 C Suntest : x hrs at Xenon_Arc_outdoor 87.1W/m² irradiance (W/cm) 8,E-04 7,E-04 6,E-04 5,E-04 4,E-04 3,E-04 2,E-04 NO-filter (quarz glass) UV-filter (Outdoor) WG-filter (Indoor) 1,E-04 SER (Ohm/sq) ,E Wavelength (nm) 2500 S305 S305plus Suntest Outdoor S305 S305plus 0 hr hr 8 1, hr Suntest 196 hr 64 3,4 16 Membrane Switch + Advanced Functional Printing

17 Key property : low surface resistance high VLT PET SER Ohm/sq VLT% (hazeguard) a* b* Haze % Optical grade PET Ref S305plus AGFA PET Ref S305plus Membrane Switch + Advanced Functional Printing

18 Key property : low surface resistance high VLT Different formulation types Coating formulations & coated film New! Orgacon GEN5 available: S305 and S305Plus Property ITO Orgacon S305 Orgacon S305plus SER (Ohm/sq) VLT (%) on 188µm PET > 86-90% 91,4% 90% Stability (ratio R/R0) 240hr@60 C/90%RH <1,1 1,3 0,9 240hr@80 C <1,1 1,4 0,8 Typical values, no specification Temperature & UVstabilized 18 Membrane Switch + Advanced Functional Printing

19 Key property: High Flexibility PEDOT/PSS is very flexible compared to for example ITO Bending test 8 mm Direct benefits in flexible applications But also direct benefits in high speed / low cost manufacturing processes Can also be stretched after coating and drying 19 Membrane Switch + Advanced Functional Printing

20 Ultra high conductivity Orgacon coatings Need of conductivity well above existing transparent solutions Combine with Orgacon with metallic grid: Highly & conductive transparent Good contact with i.e. printed Ag-inks High resolution (until ± 10 µm) Patented technology Agfa Ag-grid 150 µm line width 97% transparent SER < 2 Ohm/sq Cu grid PEDOT PET substrate Transparent electrodes for OLED and OPV applications 20 Membrane Switch + Advanced Functional Printing

21 OLED/OPV Cross section Barrier Grid & contacts Counter electrode Active Material HIL TCO Barrier Substrate Goal : Replace ITO as a transparent electrode with Orgacon Focuspoints: Improved PEDOT for TCO and HIL Combination of metal grids and PEDOT R2R production Industrial Member in HOLST program and participant in FAST2LIGHT 21 Membrane Switch + Advanced Functional Printing

22 Orgacon for OLED lighting Special formulations to combine high conductivity + high work function Formulations ready for Spin coating: HILHC5 SC Inkjet: HILHC5 IJ (IJ-1005) Slot die: HILHC5 High work function level: -5,2..-5,4 ev OLED performance PEDOT/grid equal to ITO/PEDOT Routinely used at TNO Holst Centre for flexible OLED s PEDOT:PSS anode combined with metal support structure 12x12cm device 22 Membrane Switch + Advanced Functional Printing

23 Orgacon TM for OPV Contribution of PEDOT/PSS in OPV Typical use of PEDOT/PSS: efficiency increase Normal geometry Backside illumination Tandem geometry High conduct. Low WF electrode (Al) Donor:Accept or PEDO T TCO (ITO) Substrate High conduct. electrode PEDO (Ag) T Donor:Accept or ETL (ZnO) TCO Substrate High conduct. Low WF electrode (Al) Donor:Accept or PEDO T ETL (ZnO) Donor:Accept or PEDO T TCO (ITO) Substrate Key parameters of using PEDOT/PSS Hole transport properties Smoothening ITO layer, avoiding shortcuts Recombination layer in tandem 23 Membrane Switch + Advanced Functional Printing

24 Orgacon TM for OPV Cost decrease: normal geometry Optimal use of PEDOT/PSS in OPV: ITO-less design Normal geometry High conduct. Low WF electrode (Al) Donor:Accept or PEDO T TCO (ITO) Substrate 2004 High conduct. Low WF electrode (Al) Donor:Accept or PEDO T Current collector (Ag) Substrate Holst/ECN Needed properties of PEDOT/PSS Hole transport properties High conductive: Impact on cost + efficiency With grid: high cell scalability Printable / coatable to allow R2R Orgacon EL-P5010 /ELP5015 Orgacon IJ Membrane Switch + Advanced Functional Printing

25 Key property: Direct patterning - inks 1 2 Water-based Formulation High boiling solvent exchange Solvent-based Formulation Water-based dispersion of PEDOT/PSS PEDOT powder Re-dispersion in Solvents 3 Solvent-based Formulation 25 Membrane Switch + Advanced Functional Printing

26 26 Membrane Switch + Advanced Functional Printing

27 Key property: Direct patterning - inks Orgacon IJ-1000 and IJ-1005 new! Printers Piëzo Inkjet platform: Dimatix DMP2831, spectra Galaxy,.. Use as transparent conductive layer and/or as HIL Orgacon Dry pellets Dispersible in different kind of solvents or water 27 Membrane Switch + Advanced Functional Printing

28 Orgacon Screen printing inks Orgacon SER Ohm/sq OD excl PET SER*OD viscosity remark EL P > 8 Pas a), c) EL P 3145 new! > 8 Pas b), c) EL P Pas b), c) EL P 5015 new! Pas b), c) a) Printed with P79 b) printed with P77 c) drying C Printed WWD on PET = Autostat CT7 Typical values, no specification The Stork Democenter in the Netherlands Orgacon screen inks in AC EL lighting 28 Membrane Switch + Advanced Functional Printing

29 Rotary screen printing Stork Prints BV The Stork Democenter in the Netherlands 29 Membrane Switch + Advanced Functional Printing

30 Rotary screen printing EL- P 3145 Lines printed at 15m/min (speed limited by drying capacity) Line width >2mm -> printing orientation no significant impact on SER Mesh RM 305 The Stork Democenter in the Netherlands SER lines - 2 / M 4 / 5 2 / 5 length width diagonal 30 Membrane Switch + Advanced Functional Printing

31 Improved AC EL: LUMIFLUX High Bright AC EL Inverse build up Classical build up Rear ELectrode Front Electrode ZnS Dielectric TCO Substrate AC Dielectric ZnS TCO Substrate AC + Lumiflux Technology V, 400hz V, 400hz 31 Membrane Switch + Advanced Functional Printing

32 Key Features of Lumiflux Technology Fully printed devices No special barrier films required Standard ZnS quality (eg GG45) High brightness State of the art stability (typically t1/2 = hrs) Lower driving V or frequency gives good brightness and extended lifetime Long Life ZnS (eg GG41L) 75% increase in Cd/m² over classical EL (58% higher efficiency) Stability t1/2 = hrs 100V/600Hz Long life low V or low freq => > hrs life More information: On technology : (Kabay & Co) On Materials : Agfa Materials % initial brightness 100% 75% 50% 25% 0% GG V, 400hz 70V/400Hz 32 Membrane Switch + Advanced Functional Printing

33 EL-P 3145 for high resolution printing Printing conditions: RVS-screen M325 (thr/inch) Printing speed 500 mm/sec WetDry Minimal squeegee pressure Substrate PET 175µm without primer layer Cap film on mesh: CDF/Matrix-UV: for mesh counts of 420/inch (165/cm.) or finer. SER= +/- 300Ohm/sq VLT=+/-94.5% (excl support) After 70 prints, non conductive gaps between conductive lines are achieved: Parallel with printing direction: 100 µm Perpendicular to printing direction: 200 µm After 70 prints, continous conductive lines are printed: Parallel with printing direction: 100 µm Perpendicular to printing direction: 100 µm 33 Membrane Switch + Advanced Functional Printing

34 High resolution printing EL-P 3145 versus P3042 Processimmulatie (mpa.s, 25 C) Start Run 1 Run s -1 Dyn. viscositeit (mpa.s) s s s s s s s s EL-P /1 P / Tijd (s) Viscosity recovery after shear-> higher resolution printing possible 34 Membrane Switch + Advanced Functional Printing

35 EL-P 3145 for high resolution printing Capacitive Touch Sensors Can be backlighted Or used on top of display if transparant 35 Membrane Switch + Advanced Functional Printing

36 Conclusions ORGACON products are good alternatives for any transparent conducting material on the market today The SER/ %VLT ratio is closing the gap with ITO New! Orgacon GEN5 based products ORGACON products are well suited in AC EL / CT-Sensors/OLED s/ OPV Very flexible and stretchable Combine with metallic grids: High conductivity + high efficiency R2R compatible / printable 36 Membrane Switch + Advanced Functional Printing

37 Thank You For Your Attention! 37 Membrane Switch + Advanced Functional Printing

38 Profile Bavo Muys Current ( ) Application manager Orgacon Electronic Materials at Agfa Materials. Past Master Chemistry-Biotechnology (1984) Research leader Antistatic coatings (1995) Research leader Electrostatics & Surface Modification (2006) 38 Membrane Switch + Advanced Functional Printing