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Jen Dionne
Jon Scholl, Andrea Baldi, Ashwin Atre, Di Wu, Justin Briggs, Michael Wisser, Aitzol Garcia, Ai Leen Koh, Tim Burke, Alberto Salleo, Mike McGehee
Materials Science & Engineering | Stanford University
Jen Dionne
Jon Scholl, Andrea Baldi, Ashwin Atre, Di Wu, Justin Briggs, Michael Wisser, Aitzol Garcia, Ai Leen Koh, Tim Burke, Alberto Salleo, Mike McGehee
Materials Science & Engineering | Stanford University
Electric field
r<<l
imag
real
10 nm
8x10 nm
Ag
10 nm H2O Ag Ag
5 nm H2O Ag
5 nm
+ 50 e H2O Ag
5 nm
+ 100 e H2O Ag
5 nm
+ 200 e H2O Ag
Hot electrons
e fS EC EF EV Au Si
Au 50 nm 100 nm
A
Knight, Halas, Science (2011); see also Mubeen, Moskovits, Nat. Nano. (2013)
Reaction Sensors
Scattered intensity
Pd
PdH
Pd
D- D+e-Au
Au
Au
Peak wavelength
830,000 e-
50 nm
100 nm
100 nm
Wavelength
Tang, Liu, Dionne, Alivisatos, JACS (2011)
0.3
oxidation 5 m
30
Ag
2.2 nm (x420)
20 nm
Peng, Schatz PNAS (2010)
Ag D=
2.2 nm (x420)
D=
20 nm
Peng, Schatz PNAS (2010) Lindfors, Sandoghdar, PRL (2004)
CCD
Scanning Transmission Electron Microscopy (STEM) EELS has an imaging spatial resolution of ~0.25nm
Organic-ligand-free synthesis minimizes organic contamination and the influence of ligand surface damping
Counts (a.u.) 2
Counts (a.u.) 2
Counts (a.u.) 2
Counts (a.u.) 2
Counts (a.u.) 2
4.5
5 nm
15
Counts (a.u.)
10
2.5
0 5 nm
3.2
Bulk
15
Counts (a.u.)
10
2.5
4.5
0 5 nm
3.2
AvF Classical treatment uses damping term: Bulk R Accounts for peak broadening, predicts a red shift in noble metals Instead, use a quantum approach:
Analytic
Particle Diameter (nm)
Particle Diameter (nm) 20 15 10 5 3 3.2 3.4 3.6 3.8 Energy (eV) 4 20 15 10 5 3 3.2
Ab-initio
DFT permittivity functions based on He & Zeng, JPCC. 2010 Scholl, Koh, Dionne, Nature 483 (2012)
0.3
oxidation 5 m
30
1. Can we detect plasmons from particles in the sub-10nm regime? Yes! Localized plasmons become quantum confined around 5 nm Single electron transitions can significantly impact the collective response of a sea of electrons
0.3
oxidation 5 m
30
Porous TiO2
IrO2nH2O
Porous TiO2
O2
H2O
IrO2nH2O
Ag
TiO2 C.B.
EF V.B.
EtOH EtOH
Andrea Baldi
1. Synthesis of well-dispersed Ag@TiO2 nanoparticles 2. Characterization of their photocatalytic activity in: Ensemble measurements Single particle measurements
200 nm
20 nm
Ag
200 nm
20 nm
Ag Ag TiO2
200 nm
20 nm
Ag Ag TiO2
200 nm
20 nm
Ensemble Measurements
UV irradiation of de-aerated Ag@TiO2
Hg(Ne) lamp
254
19 nm
Ensemble Measurements
UV irradiation of de-aerated Ag@TiO2
Ag
TiO2
EtOH EtOH
19 nm
Ensemble Measurements
Discharge in O2
Ag
TiO2
O2 O2
Bars denote peak full-width at half maximum On-going: correlate single particle structure with catalytic activity
0.3
oxidation 5 m
30
0.3
oxidation 5 m
30
Solar upconversion
Incident Power (W m-2)
1000
5%
800
25%
Power Transmitted
600
50%
400 200 0
75%
Solar cell
Photons with an energy less than the bandgap (Eg) of a solar cell are unused Photons with energy just above Eg are poorly absorbed
5 % Ultraviolet
43 % Visible
52 % Infrared
Solar cell
Insulator
Upconverter
A process where light is emitted with photon energies higher than those of the light generating the excitation Implementation: Solar cell and upconverter are electrically isolated 1) No additional recombination in cell 2) Separate optimization of cell & upconverter
Trupke, et al. J. Appl. Phys. 92 (2002)
44 30
With upconverter
% increase in efficiency
300
200
No upconverter
100
1.0
2.5
1.0
3.0
Peak cell efficiency increases from 30% to 44% Ideal cell bandgap blue-shifts from 1.1 eV to 1.8 eV Solar concentration is not necessary
Trupke, et al. J. Appl. Phys. 92 (2002) A. Atre and J. Dionne. J. Appl. Phys. 115 2 (2011)
cell Eg=1.7 eV
UC Bandwidth (eV)
5
UC FWHM=0.1eV
4 3 2 1
Bandgap (slope=1)
Emitter
Absorber 2
Absorber 1
0 0
0 1
Solar-spectrum matching: dont want UC energy levels to overlap with AM1.5 absorption lines
T. Burke, M. McGehee
UC absorption peak positions: usually in the near-infrared (811nm and 1200nm for a 1.7eV cell)
J. Briggs, A. Atre and J. Dionne. Submitted (2013)
PdOEP
DPA
Upconverted PL
Intensity (au)
PDOEP absorption
PdOEP
PdOEP+DPA
Wavelength (nm)
Photos by Ashwin Atre; and Diane Wu See also: Singh-Rachford, et al. JACS. 131 (2009)
200 nm Upconverted PL
Intensity (au)
400
Photos by Diane Wu Crystal structure from Wang, Nature 2010; Spectra from Hummelen, Nature Photonics 6(2012)
Wavelength (nm)
650
900
Lanthanide systems
Cell efficiency (%) Wavelength (nm)
J. Briggs, A. Atre and J. Dionne. Submitted (2013)
Intensity (a.u.)
Intensity (a.u.)
Ag NW
4.1x
4.7x 4.3x
5 m
500 550 600 650 Wavelength (nm) 700
Nanowires are promising, but have a strong polarization and angle-dependent response. Further, need UC in near-field of wire.
Absorptance (a.u.)
Solar cell
Insulator Upconverter Ag shell, upconverterdoped core Intensity (E2) enhancement of ~100x throughout the entire upconverting volume
Atre, Alaeian, Garcia, Dionne. Journal of Optics (Invited Review), January 2012
Solar cell
Insulator Upconverter Ag shell, upconverterdoped core
Solar cell
Insulator Upconverter Ag shell, upconverterdoped core
With nanocrescent
Upconverted power
Solar cell
Solar cell
Crescent Orientation
50 nm 50 nm
The refractive index of the upconverting metamaterial can be matched to the solar cell above it.
A. Atre, A. Garcia, H. Alaeian, J. Dionne, Advanced Optical Materials, in press (2013)
min
Nanocrescent fabrication
100 nm
1 m
Nanocrescent fabrication
1 m
100 nm
Nanocrescent characterization
Intensity (a.u.)
Intensity (a.u.)
2.5 2
1.5 1
400 400
600
e-
800 1200 1600 800 1000 1200 1400 1600 1800 Wavelength (nm) Wavelength (nm) =700 nm
=600 nm
800 nm
900 nm
100 nm
Li, Z. Nanotechnology 2008
Upconversion at 445 nm
Synthesis based on Wohnhass, Macromol. Biosci 11, 772 (2011)
50 nm
Summary
Absorption Particle Diameter (nm) 20 15 10 5
1. Can we detect plasmons from particles in the sub-10nm regime? 2. Can we use these plasmons to monitor photocatalytic reactions in-situ? 3. Can we improve below-bandgap absorption of solar photons for photocatalysis & photovoltaics? Some see things as they are and ask why?. Others dream things that never were and ask, why not?. George Bernard Shaw.
1 m
Thanks to our funders: Stanford, AFOSR, NSF, SLAC/SIMES, DOE, GCEP, Intel!
Summary
Absorption Particle Diameter (nm) 20 15 10 5
1. Can we detect plasmons from particles in the sub-10nm regime? 2. Can we use these plasmons to monitor photocatalytic reactions in-situ? 3. Can we improve below-bandgap absorption of solar photons for photocatalysis & photovoltaics? Some see things as they are and ask why?. Others dream things that never were and ask, why not?. George Bernard Shaw.
1 m
Thanks to our funders: Stanford, AFOSR, NSF, SLAC/SIMES, DOE, GCEP, Intel!
1S 1S S*
ISC
3S*
TET
1E
1E* 3E*
TTA
1E*
1E 1E
h2
1S
1S
5
Ideal Peak Position (eV)
All FWHM=0.1eV
4 3 2 1
Bandgap (slope=1)
Emitter
Absorber 2
Absorber 1
0 0
0 1
Solar-spectrum matching: dont want UC energy levels to overlap with AM1.5 absorption lines
Burke, McGehee. In preparation (2012)
UC absorption peak positions: usually in the near-infrared (811nm and 1200nm for a 1.7eV cell)
Briggs, Dionne. In preparation (2012)
Maverick Chea
2H 11/2 4S 3/2 4F 9/2
Michael Wisser
4I 11/2
980 nm
2F
4I 13/2
7/2
Yb3+
Er3+
4I 15/2
Ruby sample
500 500 550 550 600 600 650 650
Wavelength (nm)
Wavelength (nm)
Photoluminescence
540 540
540
542.5
Wavelength (nm)
540 540
Wavelength (nm) Wavelength(nm)
Intensity (a.u.)
545 545
547.5
550 550
550 550
550
555 552.5
555 555 1.15 1.15 12.9 28.3 12.9 28.3 Pressure (GPa) (GPa) Pressure
2000 Pressure (GPa) 0.58 13.5 18.4 25.8 20.2 9.34 2.87 0.58 13.5 18.4 25.8 20.2 9.34 2.87 14.1 1.15Pressure (GPa) Pressure (GPa)
Intensities are affected by pressure: changes to interionic separations and Yb3+/Er3+ energy level resonance
Upconversion
6
Photoluminescence
3 2 1 0 -1 0
3 2 1 0 -1 0
10
10
15
20
25
Pressure (GPa)
Pressure (GPa)
Peak shifts are also pressure-dependent: peaks spread apart as pressure is increased, suggesting a distortion in the crystal field