"Os Avanços na P&D em Células Solares Orgânicas no Brasil" IC Packaging Division Fernando Ely, PhD InovaFV, Campinas, 2013
1. Outline 3 rd Gen. PV (OPV, DSSC) Advantages Techical Issues OPV and DSSC Market Market Outlook Applications Players Brazilian PD&I in OPV/DSSC Universities CTI Startups
3rd Generation of Photovoltaics Organic Photovoltaic - OPV Light Substrate Anode holes LUMO HOMO DONATOR (p) Electron transfer absorption LUMO HOMO ACCEPTOR (n) Cathode electrons OPV Module Source: Konarka
3rd Generation of Photovoltaics Dye Sensitized Solar Cell (DSSC) Light DSSC Module Source: wikepedia (2009). Source: G24 Innovations (2008). DSSC cells involve a dye that absorbs visible light and injects an electron into the conduction band of an inorganic semionductor such as TiO 2. The oxidised dye is re-reduced by an electrolyte giving the required separation of the electron and the hole.
3rd Generation of Photovoltaics Advantages Technical Issues Approaches DSSC Organic PV R2R processing Low price Plastic (flexible, new form factors, lightweight, robust) Semitransparent Colored (tinted) Incidence angleindependent Lifetime Efficiency Reproducibility from module to module DSSC Glass frit sealing (Fraunhofer Inst., Germany) Quasi-solid electrolyte (SolarPrint, Ireland) Nanomaterials (Ohio State Univ., USA, Queensland Univ., Australia) Organic PV O 2 /H 2 O Barriers (Vitex Syst. and 3M, USA) Optical Spacers (UC-Sta. Barbara, USA) Metallic grid (GE, USA) Table 1. Technology transition for module efficiencies Technology 2005 2010 2015 Organic tandem SC 6% 9% 14% DSSC 4% 7% 12% Source: K.Derbyshire. The Future of Photovoltaics to 2015 (2008).
OPV and DSSC Market Portable Power Building Integrated PV - BIPV Electronics charger Fenestration windows, sky-light, spandrels Façade Curtain wall, other building claddings Outdoor events Source: Peng Wang and Michael Gräztel Source: Konarka and Arch Aluminum & Glass
OPV and DSSC Players OPV Players Konarka Global Photonics Heliatek Country: USA and Germany Technology: R2R Plastic OPV Market: BIPV (joint with Arch Aluminum & Glass) and CE (consuming electronics) Goal: went to bankruptcy 2012 sould out to Belectric Country: United States Technology: Flexible Small molecule OPV by evaporation Market: BIPV and CE Goal: no data Country: Germany Technology: tandem cell by R2R thermal evaporation Market: BIPV and CE Goal: setup production team 2013 R2R mass production Flexible OPV prototype panel World efficiency record 12%
OPV and DSSC Players DSSC Players Dye Sol G24 Innovations Limited Fraunhofer Institute Country: Autralia Technology: Screen printing to produce DSSC on glass and Steel Market: BIPV (Façade) Goal: in production Country: Wales, UK Technology: R2R Plastic DSSC Market: at first CE (consuming electronics) but has potential for BIPV Goal: sold out in Dec 12 Country: Germany Technology: Screen printing to produce DSSC on glass Market: BIPV (Façade) Goal: joint development with German industry DSSC BIPV panel DSSC based charging multi adapter DSSC Façade BIPV panel prototype
Brazilian PD&I in OPV/DSSC Universities INCT INEO Subprojeto 2: Desenvolvimento de células solares híbridas orgânicas/inorgânicas contendo nanopartículas e nanotubos (7 grupos - IFSC- USP; IQ-Unicamp; INMETRO; Puc-Rio; UFPR; UFMG; UFPI) PD&I OPV/DSSC CTI Renato Archer INCT NAMITEC A4.4: Fotovoltaicos Alternativos e Eletrônica Orgânica Startups DSSC: Tezca (Unicamp) OPV: Flexsolar (IAP Fraunhofer)
CTI s Activities OPV and DSSC Aceptor (n) Doador (p) Materiais e Nanomateriais Técnicas de gravação/ deposição Equipamentos (R2R) PCBM ~ 6.5 % (1 cm 2 ) P3HT regioregular OPV DSSC Células Solares Flexíveis Células Solares Flexíveis OPV DSSC Eficiência alvo ~ 9 % (120 mm 2 ) Fabricação de Protótipos e Transferência de Tecnologia Investimentos (2007-2012) Fapesp: R$ 480K CNPq: R$ 130K Finep: R$ 1.000K MCTI: R$ 400K
CTI s Activities Deposition Methods Inkjetting Spray R2R T-NIL
CTI s Activities DOD Piezo Inkjet Critical Parameters Substrate 1. Ink Formulation a. Solvent(s) b. Solid content (2-5%) Deposition conditions Ink Formulation Postprocessing c. Additives ( and ) 2. Deposition Conditions a. Waveform b. Cartridge temp. c. Plate/substrate temp. d. Linear velocity (mm/s) 3. Substrate characteristics a. Roughness b. Surface energy (hydrophobic/hydrophilic) 4. Post-processing a. Annealing conditions (heating medium, time, temp, etc.)
CTI s Activities Table. POM images of PEDOT:PSS deposited by IJP using different PEDOT inks in SU8 wells on ITO after surface treatment Ely, F. et. al.synthetic Metals, 161(19), p. 2129-2134, 2011.
CTI s Activities Goal: Production of Flexible Transparent Conductive Electrode (TCE) to Replace ITO Conducting Polymer: PEDOT SWCNT Metallic nanowires Handheld airbrush Versus Focused ultrasonic nozzle
CTI s Activities PEDOT:PSS Table 1. EG chemical post-treatment effect on conductivity and roughness. Spray T Before EG After EG system ( C) (S.cm -1 ) R rms (nm) (S.cm -1 ) R rms (nm) Airbrush 75 96.1 41.7 432.9 39.4 Ultrasonic 75 310.0 16.3 398.0 28.2 Airbrush 100 125.3 68.9 280.1 33.8 Ultrasonic 100 268.0 26.2 415.0 31.9 Airbrush 125 102.3 29.6 429.2 48.2 Ultrasonic 125 266.0 21.4 336.0 21.8 Airbrush 150 191.2 37.9 284.1 43.5 Ultrasonic 150 315.0 23.2 453.0 52.2
CTI s Activities Sprayed PEDOT:PSS for Plastics AC Electroluminescent Devices Screen-printed layers CIE coordenates = 7.59 lm/w (100V @400Hz) Luminance x V Power x V
CTI s Activities Single walled Carbon Nanotube networks Table 2. Electrical and Optical characterization of the SWNT films prepared with baking and acid treatment. SWCNT by Ultrasonic spraying AFM images
CTI s Activities CTI s Customized T-NIL System Continuous T-NIL Pressure sensing Control software Printing rollers Control panel
CTI s Activities Ni Rigid Mold Fabrication Example: Ni mold w/ Microstructures
CTI s Activities Inkjet Printed Quantum Dot-OPV Active Layer CdSe QD + P3MET N N N N CdSe N N N N + O O OCH 3 * S * n P3MET PET ITO PEDOT P3MET/ CdSe QD Al/Ag 37% v/v of CdSe QD 50% v/v of CdSe QD AFM for the composites CdSe:Py/P3MET spin-coated films on Si substrate Indicative of phase separation Device on plastic after printing and electrode deposition. PCE = 0.27 % (AM 1.5) Out of glove-box!
CTI s Activities LC additive effect in Fullerene-OPV Goal: Liquid crystalline (LC) material as functional additive to lead higher charge carrier mobility and facilitate the electron-hole pair separation. N N O H 19 C 9 O O 2 N C 9 H 19 NPEOXA O PCE = 0.015 % (AM 1.5G)
I / A Absorbance (a.u.) CTI s Activities New active layer PCDTBT-Fullerene-OPV Aceptor (n) PC 71 BM * Donor (p) N C 8 H 17 C 8 H 17 S S N N PCDTBT S n 180.0µ 120.0µ 60.0µ Cyclic Voltammetry - PCDTBT blank film PCDTBT E oxi (Fc/Fc + )= 0.93-0.2 = 0.73 V HOMO = 5.63 ev LUMO = 3.90 ev E g = 5.63-3.90 = 1.73 ev 0.20 0.16 0.12 0.08 UV-Vis PCDTBT:PC71BM (1:2.6) PCDTBT:PC 70 BM on glass/zno np 0.0-60.0µ E red (Fc/Fc + )= -1.0-0.2 = -1.2 V -2-1 0 1 2 E / V vs Pt 0.04 DCB:CB @ 7000 rpm DCB:CB @ 5000 rpm DCB:CB @ 3000 rpm 0.00 350 400 450 500 550 600 650 700 Wavelength (nm)
Current (A) CTI s Activities New active layer PCDTBT-Fullerene-OPV DCB:CB (3:1) @7000rpm 450µ w/zno Nanoparticles Buffer PCDTBT:PC70BM/ZnO np - (4D) 300µ Dark Ligth 150µ 0-0.2 0.0 0.2 0.4 0.6-150µ Cell 4D J sc = 1.25 ma/cm 2-300µ V oc = 200.6 mv Voltage (V) FF = 0.31 PCE = 0.1%
Brazilian Startups Flexsolar Células Solares From Lab to Fab: Development of an industrial process for the commercialization of organic solution processed Photovoltaic systems on a roll-to-roll pilot line! Pilot Line at Fraunhofer IAP Collaboration with MBraun Sheet-to-Sheet with 15 x 15cm Inkjet, Slot Die, ALD, Encapsulation 3 Million invest Pilot Line Flexsolar Developed in 4 years with company 3D Micromac 4 printing/coating stations Lamination and Test modules Next step: 120 cm web width
Brazilian Startups Flexsolar Células Solares Fraunhofer IAP Police jacket with textile integrated OPV and OLED Bus stop with integrated OPV and OLED modules
Brazilian Startups Tezca Células Solares Startup established since Nov. 2008 1 Office 4 laboratories Currently located at Ciatec Incubator Campinas, SP, Brazil Team of 5 members Main goal: TCO-free dye-sensitized solar cells based solely on flexible foils TCO ~ 45% Dye ~ 9% (after scaling up)
Brazilian Startups Tezca Células Solares SS DSSC cell from Tezca
Summary 3 rd gen. solar cells represent a great opportunity for RD&I with huge number of potential applications. OPV and DSSC are attactive for BIPV because the flexibility, semitransparency, low cost and colour option. International cooperation and networks are essential to increase lifetime and efficiency for widespread adoption.
Obrigado! Fernando Ely, PhD Tecnologista pleno III Full Technologist fernando.ely@cti.gov.br Tel.: +55 19 3746-6229 - Fax: +55 19 3746-6028 www.cti.gov.br