“Transparent Conductive Oxides Nanocrystals for ......OUTLINE Introduction: Plasmonic Transparent...
Transcript of “Transparent Conductive Oxides Nanocrystals for ......OUTLINE Introduction: Plasmonic Transparent...
Doctoral Thesis Defence in Physics and Nanoscience18-07-2017
Praveen PattathilCycle : XXIX
Academic year : 2014 – 2017
Coordinator: Prof. Rosaria Rinaldi Supervisors: Dr. Michele Manca
Dr. Carlo Giansante
“Transparent Conductive Oxides Nanocrystals for Energetically
Self-Consistent Dynamic Windows”
OUTLINE
Introduction: Plasmonic Transparent Conductive Oxides (TCO) and
Application
Chapter 2ITO Nanocrystal Plasmonic Electrochromic Window for Near infrared light
modulation
Chapter 3 High aspect-ratio 1D Tungsten Oxide Nanorod Plasmonic
Electrochromic Windows for Visible and Near infrared modulation.
Conclusion
Chapter 1
• Doped Semiconductors: ITO, IZO, FTO
• Transition Metal Oxides: ZnO, SnO, WO3
Chapter 1. Introduction
High Visible Transparency (e.g > 3.1 eV)
High Electrical Conductivity (10-3 Ωcm)
Burstein Moss shift
Transparent Conductive Oxide (TCO) Materials
TCO - Applications
• Touch panel
• Solar Cells
• F. P. Display
• Flexible electronics
Optical band gap widening effect
Plasmon Resonance in Colloidal TCO Nanocrystals
𝜔𝑝 =𝑛𝑒2
𝜀0𝑚0
𝜔𝐿𝑆𝑃𝑅
=𝜔𝑝2
1 + 2𝜀𝑚− 𝛾2
Plasmon frequency tunability in TCO NCs
S. Lounis et al, J. Phys. Chem. Lett 5, (2014): 1564-1574.S. C. Warren et al Langmuir, 2012, 28 (24), pp 9093–9102
Dynamic Windows : Critical Need
Plasmonic Electrochromic Smart Windows: Controlling Visible Light and Heat
WARM COOL DARK
Working Principle
𝜔𝑝 =𝑛𝑒2
𝜀0𝑚0𝜔
𝐿𝑆𝑃𝑅𝛼
Optical properties of ITO NC films during electrochemical modulation.
ITO-NCs electrode - 500nm thick
1M LiClO4 in Propylenecarbonate
DTmax 53% at 2000 nm
Experimental Design
NC’s Synthesis Thin Film & Device Fabrication
Morphological, Optical and Electrochemical CharaterizationPhase : 1
Optimized EC Device
Phase : 2Optimized EC
DeviceDSSC
Solar Powered EC Dynamic Windows
Phase : 3
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 Fabrication
Glass
Electrolyte
Glass
Conductive layer
Pt
ITO mesoporous film
Conductive layer
Lab scale Prototype
• Colloidal ITO NCs of variable size and composition
• Film deposition by screen printing (t =500-1000nm)
• Stripping of the hydrophobic capping layer
• High surface area & easy penetration of the
electrolyte
Colloidal Synthesis of ITO NC ITO NCs Viscous Paste As Deposited NCs Film Thermally Annealed NCs Film
@ 3500 C
Visibly Transparent Thin Film
As deposited film
Annealed Filed
As deposited film
Annealed film
Material and Optical Characterisation
TE
MX
RD
SE
M
Transmission and absorption spectra of an ITO-NCs electrode interfaced with DMPII (a,d), LiI (b, e) and LiClO4 (c,f)
Dynamic modulation of LSPR in ITO-NCs
LiI
Electrochemical Measurements
Cyclic voltammograms
Nyquist plots of ITO/EL/Pt EC cells
Time-responsivity at λLSPRmax; potential: ± 1.4 V
C.E of ITO-NC electrodes in different ELs
Table I. Summary of the most meaningful electrochemical and optical figures experimentally detected on six different ELs
EL [email protected] [mF/cm2] JFar @ 1.4V [mA/cm2] ΔTmax
CE
[cm2/C]
tc/tb
[s]
pure solvent / / 8.6% @ 2150 nm -- --
LiI 1M 8.0 96 61.3% @ 1740 nm 222 3/6
DMPII 0.2 M 3.1 66 40.8% @ 1610 nm 145 4/7
DMPII 1M 5.1 111 52.6% @ 1770 nm 187 3/7
DMPII 1M + I2 0.005M 4.8 418 60.8% @ 1800 nm 157 2/5
LiClO4 1M 5.3 / 81.4% @ 2040 nm 1270 82/34
Transmittance Spectra and J-V Curves of SOLAR POWERED NIR EC DEVICE
High maximum transmittance modulation as 73% at 2000 nm @ 1 Sun Transmission spectra J-V curves of three series-
connected DSCs P. Pattathil, R.Giannuzzi, M. Manca. Nano Energy. 30 (2016) 242-251.
Chpater 3: Near-Infrared Selective Dynamic Windows Controlled by Charge
Transfer Impedance at the Counter Electrode
@ 3
60
0 C
-ai
r
Met
hodolo
gy
Electroly
te
Composition
#1 1M LiClO4 in PC/AcN (70/30)
#2 1M LiClO4 + 0.005M LiI in PC/AcN
(70/30)
#3 0.7M LiClO4 + 0.3M LiI in PC/AcN
(70/30)
Mat
eria
l an
d O
pti
cal
Char
acte
risa
tion
Lab scale Prototype
WARM COOL_Single Band DARK_Dual Band
WO3-NR-based EC
∆TMAX
CE @ 1000
nm
[cm2/C]
MAX
∆TLUM
MAX
∆TSOL
MAX
TLUM /TSOL
MAX
∆TNIR
74.1%
at 1500 nm
160
at 1500 nm
17.7 % 38.6 % 1.68 85.1 %
Warm Cool
Optical Properties
SUN
LIGH
T INTE
NSITY
“cool” “dark”CoolDark
∆TMAX
CE @ 1000
nm
[cm2/C]
MAX
∆TLUM
MAX
∆TSOL
MAX
TLUM /TSOL
MAX
∆TNIR
80.1%
at 1500 nm
127
at 1500 nm
66.4 % 61.0 % 1.96 99.8 %
Electrochemical Measurements
i(V)=k1v+k2v1/2
Cyclic voltammograms Nyquist plots of WO3/EL/Pt EC cells
Surface capacitance vs Diffusion currents Variation of the solar irradiance transmitted
across the three EC devices
P. Praveen, et al. Nanoscale 8.48 (2016): 20056-20065
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 WO3 NCs
mesoporous electrodes.
• ITO mesoporous electrode dynamically filter out the NIR radiation: 38% at 780 - 2400
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 780-1500 nm and VIS 66.4 % at 350 -750 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.
1. P. Pattathil, R. Scarfiello, R. Giannuzzi, G. Veramonti, T. Sibillano, A. Qualtieri, C. Giannini, P.D. Cozzoli and M. Manca, Near-
infrared selective dynamic windows controlled by charge transfer impedance at the counter electrode, Nanoscale. 48 (2016)
20056-20065.
2. 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) 242-251.
3. 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) 1614-1622.
4. 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 ionic liquid, Chem. Commun. 28 (2015) 6092-6095.
List of Publications
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 16 -18 October 2014, Lecce, Italy.
2. Praveen Pattathil, Riccardo Scarfiello, Roberto Giannuzzi, Giulia Veramonti, Davide P. Cozzoli and Michele Manca “From Capacitance-
controlled 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 16-18 September, 2015 at Electrochemistry Department , University of
Bologna, Italy
Attended Conference, Poster Presentation and Workshops
DYE SOLAR GROUP @ IIT-CBN