NanoItaly 2015 Roma - Italy Department for Sustainability of the productive and territorial systems (SSPT) Division for Technologies and processes of the materials for the sustainability (SSPT-PROMAS) Laboratory for Nanomaterials and Devices (SSPT-PROMAS-NANO) OLEDs for lighting State of the art and ENEA competence Maria Grazia Maglione, Paolo Tassini, Carla Minarini ENEA Portici Research Centre paolo.tassini@enea.it
OLEDs
OLEDs DISPLAYS! From early samples to marketed products Kodak LS633 photocamera, 2.2" AMOLED display (2003) Samsung S6 Edge, 5.1" (2015) Sony XEL-1, 11" TV set (2007) LG 55EC9300, 55" curved Full HD TV set, US$ 1999 (2014) LG G Flex LS995, 6.0" (2013) Epson 40" TV set, ink-jet printed, polymer-based (2004) OLEDs are an important success of the Organic Electronics LG 77EG9900, 77" flexible 4K TV set, US$ 50,000 (!?) (2015) PANASONIC TX-65CZ950, 65" curved 4K TV set (2015) (LG panel) Images: www.oled-info.com; www.samsung.com; www.lg.com
OLEDs for lighting OLEDs It is a Solid State Lighting technology, with LEDs and EL sources It is an answer for high efficiency very small or zero environmental impact It is THE answer for natural, large area, glare-free light tuneable colour flexible, thin and lightweight sources transparent sources dimmable sources
OLEDs for lighting OLED lighting development is moving fast too! Several prototypes LG Chem (2009) General Electric chandelier World s first OLED lamp by OSRAM and Ingo Maurer design (2008) (price: 25 000) Novaled transparent OLEDs (2010) Novaled Philips
OLEDs for lighting OLED lighting development is moving fast too! first commercial devices in 2009 OSRAM Orbeos diameter = 80 mm efficacy = 25 lm/w CRI (Colour Rendering Index) = 80 price (at launch) = 375 US$ PHILIPS Lumiblade various dimensions and forms efficacy = 20 lm/w (white & RGB) luminance = 1.000 cd/m 2 life = 10.000 hours price (at launch) = 72 @ 44 x 47 mm 2
OLEDs for lighting OLED lighting development is moving fast too! to present (and coming) products OSRAM Novaled OSRAM Blackbody (FIAMM) LG Chem Konica Minolta Fraunhofer COMEDD AUDI etc. AUDI Novaled Konica Minolta Blackbody (FIAMM) LG Chem Fraunhofer COMEDD
OSRAM efficacy = 40 lm/w luminance = 2000 cd/m^2 CRI = 80 lifetime L70 = 10 000 h working voltage = 6 V active area = up to > 11 cm^2 cost = N.A. OLEDs for lighting Characteristics of some OLED lighting products Announced best performances of OLED devices NEC Lighting & Yamagata Univ. (2013) efficacy = 156 lm/w luminance = 1000 cd/m^2 active area = 4 mm^2 LG Chem efficacy = 50+ lm/w luminance = 3000+ cd/m^2 CRI = 90+ lifetime L70 = 30 000+ h working voltage = 6 or 8.5 V active area = up to 1000 cm^2 cost = $566/klm (680 US$/panel) Konica Minolta efficacy = 64 lm/w luminance = 1000 cd/m^2 lifetime L50 = 10 000 h active area = 68 cm^2 cost = N.A. OLED lighting average cost 200 US$/klm 20X LEDs source: www.oled-info.com Konica Minolta (2014) efficacy = 139 lm/w luminance = 1000 cd/m^2 CRI = 81 lifetime L50 = 55 000 h active area = 15 cm^2
OLEDs for lighting OLED lighting market Performances and market continue to grow UBI Research (2014) OLED materials market NanoMarkets (2014) IDTechEx (2014): market < $200million @ 2019 $1.9 billion @ 2025 DOE and IDTechEx (2013) Cintelliq (2014): OLEDs become a strong competitor to LEDs by 2016 By 2020: OLED panels priced at 200/m^2 @ 5 000 cd/m^2, and less than 14/klm By 2023: OLED panel production > 500 million of 100mm x 100mm panel equivalents But, the market is still moving Philips and Panasonic in 2015 decided to drop OLED lighting! but Philips sold its knowhow to OLEDWorks
OLEDs for lighting OLED lighting market (according to OE-A) Years 2014-2015 2016-2018 2019-2022 2023-2027 Efficacy 100 lm/w 130 lm/w 160 lm/w 190 lm/w First products / Prototypes Decorative lighting, High price applications B2B Automotive lighting, High prices flexible Integration for special building, Transparent Free form Mass production / / Flexible lighting Building-integrated, Flexible, Transparent But, to note, OLED lighting market is driven by NEW INSTALLATIONS source: OE-A - White Paper - Roadmap for Organic and Printed Electronics, 6th Ed. (June 2015)
OLEDs for lighting Anyway, there are still "red brick walls" to face Lifetime Encapsulation New Barriers for large area and flexible devices integrated in-line production Devices Efficiency Light Outcoupling/Extraction intelligent glass substrates and lenses (micro lenses, pyramid array, prism foil) index-matched materials and adhesives encapsulation, for matched index plastic substrates Standardization Manufacturing Costs Improved Processes LowerPrices and High Production Volumes high throughput and material utilization efficiency for vacuum deposition solution processing and printing tooling promises must turn intoreality for lower cost manufacturing, but must deliver high performance devices this red brick wall is becoming the most dominant one Investments, to move from R&D and pilot lines to real production source: OE-A - White Paper - Roadmap for Organic and Printed Electronics, 6th Ed. (June 2015)
Lab. ENEA NANO competence OLEDs OPV OTFTs Innovative process technologies Raw materials recovery from waste Laboratory NANO is organized as a lab-scale full processing line for simulation, design, fabrication and test of materials, devices and systems of ORGANIC and PRINTED ELECTRONICS, its applications in horticulture, and study the recovery and recycling of raw materials from waste Activities address the EIT priorities for RAW MATERIALS Images: ENEA SSPT-PROMAS-NANO; COATEMA
Lab. ENEA NANO competence OLEDs on glass
Lab. ENEA NANO competence OLEDs on plastic
Lab. ENEA NANO competence ENEA NANO - OLEDs activity Objectives Improvement of Performances of the devices, through materials devices architecture fabrication technologies (high through-put methods, printing techniques, etc.) simulations (physical and electrical) Stability and lifetime, and methods to improve them Life cycle of devices and systems to study low eco-impact materials and processes, to reduce the waste and improve the recovery of valuable materials Usefulness of the devices to develop and transfer useful knowledge to the companies and the public
Lab. ENEA NANO competence ENEA NANO OLEDs Materials and architecture Encapsulation Cathode EIL ETL HBL EML HTL HIL Anode Substrate Substrate Glass; PET; PEN; etc. Anode ITO; doped PEDOT:PSS; ZnO; AZO; etc. HIL - Hole Injection Layer PEDOT:PSS, Metal Oxides (MoO 3 ), CuPc HTL - Hole Transport Layer α-npd, TPD EML - Emitting Layer Small Molecules, Polymers, Blends and Nanocomposites deposited by evaporation in vacuum and from solution host materials: CBP, SimCP guest materials: Ir(Fppy)3, Ir(ppy)3, etc. HBL - Hole Blocking Layer BCP ETL - Electron Transport Layer Alq3 Cathode LiF+ Al; Ca + Al; Li + Al; etc. Encapsulation rigid: glass lid + epoxy resinsealant + getter flexible: thin film encapsulation: inorganic barriers, organic-inorganic multilayer
Lab. ENEA NANO competence Improvement of the devices performances Anode surface treatments Charge injection layers (HIL, EIL) PEDOT:PSS, CuPc, LiF, etc. Low work-function cathodes Phosphorescent emitting materials Light outcoupling Materials: CBP + Ir(ppy)3; LiF/Al Turn-on voltage 2.0 V Luminance 40 000 cd/m^2 @ 9 V Current efficiency 20 cd/a Efficacy 15 lm/w No light outcoupling
Lab. ENEA NANO competence White OLEDs Blue OLEDs Violet OLEDs
Lab. ENEA NANO competence getter Encapsulation and lifetime studies Rigid encapsulation getter Water vapour transmission rate (WVTR) of10-5 g/m 2 /day at room temperature (T = 25 C, RH = 50%; measured by ENEAelectrical Ca test) has been obtained. US Patent 2009/0066244 A1: "Encapsulated organic electronic device with improved resistance to degradation", 12/03/2009 Italian patent TO2007U000116: "Dispositivo elettronico organico incapsulato, con migliorata resistenza al degrado", 11/09/2007 In progress Study of the intrinsic degradation phenomena through shelf life experiments, performed at different storage conditions (by using a climate chamber). Flexible encapsulation Multilayer barrier of sputtered Al 2 O 3, on the device (Thin Film Encapsulation (TFE)). WVTRof 10-3 g/m 2 /day at room conditions (T = 25 C, RH = 50%; below the detection limit of our permeabilimeter (< 10-2 g/m 2 /day)) can be reached. Lamination of transparent barrier film (Foil Encapsulation (FE)). WVTRof 10-1 to 10-3 g/m 2 /day at room conditions (T = 25 C, RH = 50%; measured by permeabilimeter) has been achieved.
Trasmittance (%) Luminance (Cd/m 2 ) 100 Lab. ENEA NANO competence 90 80 70 60 50 40 30 20 PEDOT:PSS doped with DMSO 10 200 300 400 500 600 700 800 10000 1000 100 10 1 0.1 0.01 Transparent conductive materials for ITO substitution Wavelenght (nm) PEDOT:PSS DMSO-PEDOT:PSS Transmittance > 85% UV -Vis 1E-3 0 2 4 6 8 10 12 14 16 Current (A) 0,01 1E-3 1E-4 1E-5 1E-6 1E-7 OLEDs performances DMSO-PEDOT:PSS anodo PEDOT:PSS anodo ITO anodo Voltage (V) Lower optical turn-on voltage Higher luminance with DMSO PEDOT:PSS anode DMSO-PEDOT:PSS anode initial 0,1 1 Voltage (V) I vs. V Conductivity 700 S/cm In progress Ag weight (%) Transmittance (%) 100 90 PEDOT:PSS doped with DMSO + CNT UV-Vis DMSO-PEDOT:PSS with 1wt% CNT DMSO-PEDOT:PSS with 0.5wt% CNT DMSO-PEDOT:PSS with 0.1wt% CNT DMSO-PEDOT:PSS Transmittance > 85% 80 400 500 600 700 Wavelenght (nm) Conductivity (S/cm) 1000 950 900 850 800 750 700 0,0 0,2 0,4 0,6 0,8 1,0 DWCNT-COOH % loading Conductivity 950 S/cm In-situ polymerization of Ag nanoparticles in doped PEDOT:PSS Thickness (nm) Roughnes (Rq) (nm) Sheet Resistance (Ω/ ) 10 300 35 25 1250 2.5 285 17 43 830-150 1.9 2.85*10 2 650 Aluminium doped zinc oxide (AZO) Conductivity (S/cm) MWCNT Thickness Roughness Sheet Resistance Conductivity (%) (nm) (Rq) (nm) (Ώ/sq) (S/cm) - 155 0.3 129 500 0.01 162 6.8 117 524 0.05 158 7.6 102 620 0.1 170 10.2 82 740
Lab. ENEA NANO competence OLEDs fabrication facilities KURT J. LESKER integrated process system: Evaporator, Sputter, Spin-coaters, integrated in a glove box with inert atmosphere OXFORD OpAL Atomic Layer Deposition system (ALD), for barrier layers deposition: Al2O3, SiN, SiO2 Modular and upgradable COATEMA Smartcoater roll-to-roll printing system: gravure and screen-printing, slot-die coating, lamination, inert atmosphere
Lab. ENEA NANO competence OLEDs fabrication facilities Clean room (class 100), for photolithography and chemical processes Excimer laser processing: Laser assisted deposition Crystallization PECVD cluster system Mask Aligner with Nano Imprint Lithography (NIL) (EVG620 NT) Direct Writing Laser system, for high resolution photolithography Ink-jet printing system Hot embossing system
Lab. ENEA NANO competence OLEDs fabrication facilities SEM Electro-optical bench Probe station Organic Material Analyzer Profilometer Spectrofluorometer Climatic chamber Contact angle
Lab. ENEA NANO competence Encapsulation and degradation studies KURT J. LESKER integrated process system Glove box system (O2 and H2O < 1 ppm) for sealing of organic devices, using automatic dispensing of UV-curable resins and lamps Climate chamber for ageing and testing of the encapsulated devices (10 C < T < 50 C; 10% < RH < 98%) Electro-optical characterization tools Water vapour permeabilimeter (10 C < T < 50 C) Laminator (in glove box)
Lab. ENEA NANO competence People Salvatore Aprano (PhD student) Elena Santoro (PhD student) Maria Fiorillo (PhD student) Valeria Criscuolo (PhD student) Tania Prontera(PhD student) Michele Tesoro (SESMAT) Giovanni Cotella(former SESMAT) Emanuele Bezzeccheri(former UniSA) Giuseppe Pandolfi (ENEA) Enzo Calò (ENEA) Tommaso Fasolino (ENEA) Giuseppe Nenna (ENEA) Giuliano Sico (ENEA) Anna De Girolamo (ENEA) Claudia Diletto (ENEA) Paolo Tassini (ENEA) Maria Grazia Maglione (ENEA) Carla Minarini (ENEA)
Department for Sustainability of the productive and territorial systems (SSPT) Division for Technologies and processes of the materials for the sustainability (SSPT-PROMAS) Laboratory for Nanomaterials and Devices (SSPT-PROMAS-NANO) Paolo Tassini C. R. ENEA Portici p.le E. Fermi, 1 Località Granatello I-80055 Portici Italy paolo.tassini@enea.it +39 081 7723 289