Transparent Conductive Oxides Nanocrystals for Energetically Self-Consistent Dynamic Windows

Transcription

1 Transparent Conductive Oxides Nanocrystals for Energetically Self-Consistent Dynamic Windows Doctoral Thesis Defence in Physics and Nanoscience Praveen Pattathil Cycle : XXIX Academic year : Coordinator: Prof. Rosaria Rinaldi Supervisors: Dr. Michele Manca Dr. Carlo Giansante

2 OUTLINE Chapter 1 Chapter 2 Chapter 3 Introduction: Plasmonic Transparent Conductive Oxides (TCO) and Application ITO Nanocrystal Plasmonic Electrochromic Window for Near infrared light modulation High aspect-ratio 1D Tungsten Oxide Nanorod Plasmonic Electrochromic Windows for Visible and Near infrared modulation. Conclusion

3 Chapter 1. Introduction Transparent Conductive Oxide (TCO) Materials Doped Semiconductors: ITO, IZO, FTO Transition Metal Oxides: ZnO, SnO, WO 3 Burstein Moss shift TCO - Applications Touch panel Solar Cells F. P. Display Flexible electronics High Visible Transparency (e.g > 3.1 ev) High Electrical Conductivity (10-3 Ωcm) Optical band gap widening effect

4 Plasmon Resonance in Colloidal TCO Nanocrystals ω LSPR = ω p ε m γ 2 Plasmon frequency tunability in TCO NCs ω p = ne2 ε 0 m 0 S. Lounis et al, J. Phys. Chem. Lett 5, (2014): S. C. Warren et al Langmuir, 2012, 28 (24), pp

5 Dynamic Windows : Critical Need Plasmonic Electrochromic Smart Windows: Controlling Visible Light and Heat WARM COOL DARK

6 Working Principle ITO-NCs electrode - 500nm thick 1M LiClO 4 in Propylenecarbonate DT max 53% at 2000 nm Optical properties of ITO NC films during electrochemical modulation. ω LSPR α ω p = ne2 ε 0 m 0

7 Experimental Design Phase : 1 NC s Synthesis Thin Film & Device Fabrication Morphological, Optical and Electrochemical Charaterization Optimized EC Device Phase : 2 Optimized EC Device DSSC Phase : 3 Solar Powered EC Dynamic Windows

8 Chapter 2: Self-powered NIR-selective dynamic windows based on broad tuning of the LSPRs in mesoporous ITO electrodes Mesoporous ITO-NCs Electrode preparation and Device C Colloidal Synthesis of ITO NC ITO NCs Viscous Paste As Deposited NCs Film Thermally Annealed NCs Film Visibly Transparent Thin Film Glass Conductive layer Pt Electrolyte ITO mesoporous film Conductive layer Glass Lab scale Prototype Colloidal ITO NCs of variable size and composition Film deposition by screen printing (t = nm) Stripping of the hydrophobic capping layer High surface area & easy penetration of the electrolyte

9 XRD TEM SEM Material and Optical Characterisation As deposited film Annealed As deposited film film Annealed Filed

10 Dynamic modulation of LSPR in ITO-NCs LiI Transmission and absorption spectra of an ITO-NCs electrode interfaced with DMPII (a,d), LiI (b, e) and LiClO 4 (c,f)

11 Electrochemical Measurements Cyclic voltammograms Time-responsivity at λ LSPR max; potential: ± 1.4 V Nyquist plots of ITO/EL/Pt EC cells C.E of ITO-NC electrodes in different ELs

12 Table I. Summary of the most meaningful electrochemical and optical figures experimentally detected on six different ELs EL C [mf/cm 2 ] J 1.4V [ma/cm 2 ] ΔT max CE [cm 2 /C] pure solvent / / 2150 nm LiI 1M nm 222 3/6 DMPII 0.2 M nm 145 4/7 DMPII 1M nm 187 3/7 DMPII 1M + I M nm 157 2/5 LiClO 4 1M 5.3 / 2040 nm /34 t c /t b [s] Transmittance Spectra and J-V Curves of SOLAR POWERED NIR EC DEVICE High maximum transmittance modulation as 73% at Sun Transmission spectra J-V curves of three seriesconnected P. Pattathil, R.Giannuzzi, M. Manca. Nano Energy. 30 (2016) DSCs

13 Material and Optical Characterisation C - air Chpater 3: Near-Infrared Selective Dynamic Windows Controlled by Charge Transfer Impedance at the Counter Electrode Lab scale Prototype Electroly te Composition #1 1M LiClO 4 in PC/AcN (70/30) #2 1M LiClO M LiI in PC/AcN (70/30) #3 0.7M LiClO M LiI in PC/AcN (70/30)

14 WO 3 -NR-based EC WARM COOL_Single Band DARK_Dual Band

15 Optical Properties Warm Cool 1000 T MAX nm [cm 2 /C] MAX T LUM MAX T SOL MAX T LUM /T SOL MAX T NIR 74.1% 160 at 1500 nm at 1500 nm 17.7 % 38.6 % %

16 Cool cool dark Dark SUNLIGHT INTENSITY 1000 T MAX nm [cm 2 /C] MAX T LUM MAX T SOL MAX T LUM /T SOL MAX T NIR 80.1% 127 at 1500 nm at 1500 nm 66.4 % 61.0 % %

17 Electrochemical Measurements Cyclic voltammograms Nyquist plots of WO 3 /EL/Pt EC cells i(v)=k 1 v+k 2 v 1/2 Surface capacitance vs Diffusion currents P. Praveen, et al. Nanoscale 8.48 (2016): Variation of the solar irradiance transmitted across the three EC devices

18 CONCLUSION This study demonstrates two modes of electrochromism (EC) such as plasmonic (at near infrared region) and polaronic (at visible region) in colloidal ITO and 1D WO 3 NCs mesoporous electrodes. ITO mesoporous electrode dynamically filter out the NIR radiation: 38% at nm and 35.0% by solar powered plasmonic window under 1 sun illumination. The tungsten oxide NRs showed an outstandingly wide modulation of the NIR solar transmittance 99.0 % at nm and VIS 66.4 % at nm. The experimental achievements presented here have the potential for next generation of dynamic glazed building facades, which are prospected to maximize both thermal and visual comfort at any climatic condition while reducing the overall energy use and environmental impact.

19 List of Publications 1. P. Pattathil, R. Scarfiello, R. Giannuzzi, G. Veramonti, T. Sibillano, A. Qualtieri, C. Giannini, P.D. Cozzoli and M. Manca, Nearinfrared selective dynamic windows controlled by charge transfer impedance at the counter electrode, Nanoscale. 48 (2016) P. Pattathil, R. Giannuzzi and M. Manca, Self-powered NIR-selective dynamic windows based on broad tuning of the localized surface plasmon resonance in mesoporous ITO electrodes, Nano Energy 30 (2016) R. Giannuzzi, M. Balandeh, A. Mezzetti, L. Meda, P. Pattathil, G. Gigli, F. Di Fonzo and Michele Manca, On the Li Intercalation Kinetics in Tree like WO3 Electrodes and Their Implementation in Fast Switchable Electrochromic Devices, Adv. Opt. Mater. 11 (2015) A. Paravannoor, S.V. Nair, P. Pattathil, M. Manca and A. Balakrishnan, High voltage supercapacitors based on carbon-grafted NiO nanowires interfaced with an aprotic ionicliquid, Chem. Commun. 28 (2015) Attended Conference, Poster Presentation and Workshops 1. Mara Serrapede, Praveen Pattathil, Roberto Giannuzzi, Mehrdad Balandeh, Luisa De Marco, Simone Valente, Giuseppe Gigli, Fabio Di Fonzo, Michele Manca, Smart modulation of the optical transmittance in dye-sensitized photovoltachromic devices International Conference on Photovoltaics: new frontiers and applications October 2014, Lecce, Italy. 2. Praveen Pattathil, Riccardo Scarfiello, Roberto Giannuzzi, Giulia Veramonti, Davide P. Cozzoli and Michele Manca From Capacitancecontrolled to Diffusion-controlled Electrochromism in Shape-Tailored 1D Tungsten Oxide Nanocrystals 12th International Meeting on Electrochromism (IME-12), August 28th to September 01, 2016, Delft University of Technology, Delft, Netherlands. 3. Attended the 2nd International Workshop on Technologies for Optogenetics during 16th 17th, December,2015 at Lecce, Italy. 4. Attended International Workshop on Electrochemistry held on September, 2015 at Electrochemistry Department, University of Bologna, Italy

20 DYE SOLAR IIT-CBN

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