Fundamentals and Dynamics of Energy Transport and Conversion The Advanced Photon Source is funded by...
1
Fundamentals and Dynamics of Energy Transport and Conversion The Advanced Photon Source is funded by the U.S. Department of Energy Office of Science Advanced Photon Source • 9700 S. Cass Ave. • Argonne, IL 60439 USA • www.aps.anl.gov • www.anl.gov Opportunities for time-resolved x-ray science at the Advanced Photon Source APS Standard Operating Mode • Provides a large flux in well separated pulses X-rays 6.52 MHz 153 ns 80 ps FWHM X-ray pulse spacing is large enough to isolate signal from individual x-ray pulses ~10 6 photons/pulse at 7ID-D ~10 10 photons/pulse at 14ID-B Diverse pump sources: Optical, electrical, mechanical and THz excitations Electronic origin of photoinduced strain in multiferroics Wen, et al., Phys. Rev. Lett. 110, 037601 (2013) Schick, et al., Phys. Rev. Lett. 112, 097602 (2014) 400 nm 35 nm BiFeO 3 on SrTiO 3 (001) Using ultrafast optical and x-ray probes, we found optically excited carriers screen the depolarization field, which gives rise to significant localized strain as a result of inverse piezoelectric effect. Motivation: Controlling the interplay of electronic, magnetic, optical, mechanical, and thermal properties of materials for efficient energy transport and conversion. + - + + - + - - ++ - + - t<0 t=0 t>0 Complex chemical reactions can be initiated by light and recorded on physically relevant time scales, paving the way for the exploration of of life’s most sophisticated processes. Y. O. Jung et al., Nature Chem. 5, 212(2013) J. Chen, et al., Appl. Phys. Lett. 102, 181903 (2013). Visualizing trans-cis isomerization pathways Time- and momentum- resolved heat transport Ultrafast Materials Science: Understanding and controlling energy transport and conversion among multiple degrees of freedom Q 5um The spatiotemporal-resolved structural probe reveals the deviation of the relaxation process from a sinusoidal profile that quantitatively measure the in-plane transport processes. Introductio n The time-resolved research program at the Advanced Photon Source is targeted at understanding the fundamentals of energy transport and conversion at multi- energy, length and time scales utilizing a suite of advanced ultrafast hard x- ray probes localized at Sector 7, 11 and 14. Spin Charge Lattice Orbital + - + + - + - - ++ - + - - + - + + - + - - ++ - + - + - + + - + - - ++ - + - c a Optical intensity I(x,t) Lattice structure (x,t) Position (µm) Intensity (a.u) Intensity (a.u) 0 2 4 6 8 10 12 17 17.1 17.2 17.3 17.4 17.5 17.6 θ o Delay (ns) Energy transport in nanostructured materials BiFeO 3 FeRh Ultrafast Chemical Science: Elucidating the mechanisms of light induced chemical processes Dye Sensitized Solar Cells Natural photosynthesis Molecular machines Artificial photosynthesis solar fuels: Light → chemical energy Artificial photosynthesis solar cells: Light → electricity Combined Techniques for Complimentary Information XAS (absorption) XES (emission) XRS (scattering) Kα, Kβ sensitive to electronic structure, not geometric structure (spin and oxidation state, electronic correlations) Determine structures of transient intermediates Insight into solvent shell rearrangements XANES: sensitive to electronic and geometric structure (oxidation state, valence orbital occupancy, charge transfer) EXAFS: local bond distances and coordination numbers Element specific, sensitive to local structure Sensitive to all species in the solvent Valence-to-Core sensitive to chemically relevant orbitals Motivation: harnessing the power of light All those techniques can now be applied to study transient states ! X-ray absorption spectroscopy X-ray emission spectroscopy X-ray diffuse scattering -direct probe of spin state -insight into solvent shell rearrangements Kα Kβ -electronic and geometric structure Excited state fraction Input for XAS analysis Input for scattering analysis EXAFS yields change in bond length Yields excited state geometric structure KB Mirrors X- rays Ion chamber Pilat us Lase r APD 1 m Rowland circle Analyzer crystal Scintill ator 3 ft. x 3 ft. table Liquid jet Capturing excited state structures at high precision by using full APS flux First demonstration of combined techniques in a pump-probe experiment Low spin t ~650 ps hn Aqueous [Fe(bpy) 3 ] 2+ High spin K. Haldrup et al., J.Phys Chem. A 116, 9878 (2012) G. Vanko et al, JESRP 188, 166 (2013) Sector 7ID-D Combined techniques setup Using flux demanding techniques for time resolved studies: efficient detection at high rep-rate Ex: Von Hamos crystal analyzer for TR-XES J. Szlachetko et al., RSI 83, 103105 (2012). X-ray emission energy Incident x-ray energy ZnO nanoparticles: Observe evolution of charge distribution Laser excitation and x-ray detection @ 1.3 MHz ZnO (35 nm particles) in water @355 nm Optical pulse promotes electrons in conduction band Only ~1% excited state fraction Time-resolved RIXS difference map Data consistent with increased electron density on Zn centers Also demonstrated simultaneous measurement of K a , K b and Valence to Core XES Kb 100 ps delay Ka 100 ps delay Ka ground state Kb ground state Photosystem 1 e - Relay Cataly st Photosensitizer (PS) Relay (R) Cataly st (C) R Bio- inspirati on Photosensitizer Phys. Chem. Lett. 4, 1972 (2013). Natural photosynthesis Interfacial electron transfer in Dye-sensitized solar cell hn VB CB Dye (TiO 2 ) n e - VB CB Dye (TiO 2 ) n + - X-ray probe J. Phys. Chem. Lett. 2, 628 (2011). Angew. Chem. Int. Ed. 51, 12711 (2012). Electron transfer inside a biomimetic supramolecular complex for solar fuel catalysts Science 337, 1200 (2012). Electron transport inside iron oxide nanoparticles Sector 11ID-D A versatile Time resolved X-Ray Absorption setup Showcase experiments using X-ray absorption Energy Conversion Resolution: ~260 nm, ~80 ps Spatiotemporally resolved hard x-ray probe High repetition rate lasers to fully exploit high flux of the APS Tunable (0.2-16 mm) Up to 1 MHz 250 fs Light Conversion PHAROS New! 266 nm 2.5 W (4 μJ/pulse) @ 600 kHz Time Bandwidth DUETTO 50 kHz - 6.52 MHz 10 ps and 130 ps Electric field pulse THz radiation@Sec7 Laser shock excitation Optical excitation Energy Transport 0.4% strain Electric-field-driven domain dynamics P. Chen, et al., Phys. Rev. Lett. 110, 047601 (2013) The time-resolved changes of the diffuse scattering show primarily a quasi- thermal phonon distribution that is established in 100 ps and that follows the time-scale of thermal transport. Superionic phase transition T. A. Miller et al., Nature Comm. 4, 1369 (2013) H. Wen, G. Doumy, B. Adams, A. D. DiChiara, E. M. Dufresne, T. Graber, Y. Li, A. M. March, Q. Kong, A. R. Sandy, S. H. Southworth, D. A. Walko, J. Wang, X. Zhang, Y. Zhu Time-Resolved Research, Atomic Molecular and Optical Physics, and Structural Science Groups, X-ray Science Division, Advanced Photon Source, Argonne National Laboratory Position (µm) PbO SrO PbO TiO 2 TiO 2 TiO 2 TiO 2 TiO 2 TiO 2 TiO 2 SrO … … 0.3 0.5 0.16 -10 0 10 20 0.10 0.15 0.4n s 0.1n s 1ns 1.4n s 9.5 10.0 12 18 9 12 -20 -10 0 10 20 10 12 -2n s (18m s) 0.1n s 4ns 20ns
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Transcript of Fundamentals and Dynamics of Energy Transport and Conversion The Advanced Photon Source is funded by...
Fundamentals and Dynamics of Energy Transport and Conversion
The Advanced Photon Source is funded by the U.S. Department of Energy Office of Science
Advanced Photon Source • 9700 S. Cass Ave. • Argonne, IL 60439 USA • www.aps.anl.gov • www.anl.gov
Opportunities for time-resolved x-ray science at the Advanced Photon Source
APS Standard Operating Mode
• Provides a large flux in well separated pulses
X-rays 6.52 MHz
153 ns80 ps
FWHM
X-ray pulse spacing is large enough to isolate signal from individual x-
ray pulses
~106 photons/pulse at 7ID-D
~1010 photons/pulse at 14ID-B
Diverse pump sources: Optical, electrical, mechanical and THz excitations
Electronic origin of photoinduced strain in multiferroics
Wen, et al., Phys. Rev. Lett. 110, 037601 (2013)Schick, et al., Phys. Rev. Lett. 112, 097602 (2014)
400 nm
35 nm BiFeO3 on SrTiO3 (001)
Using ultrafast optical and x-ray probes, we found optically excited carriers screen the depolarization field, which gives rise to significant localized strain as a result of inverse piezoelectric effect.
Motivation: Controlling the interplay of electronic, magnetic, optical, mechanical, and thermal properties of materials for efficient energy transport and conversion.
+-
+
+ -+
- -
+ +
-
+
-
t<0 t=0 t>0Complex chemical reactions can be initiated by light and recorded on physically relevant time scales, paving the way for the exploration of of life’s most sophisticated processes.
Y. O. Jung et al., Nature Chem. 5, 212(2013)
J. Chen, et al., Appl. Phys. Lett. 102, 181903 (2013).
Visualizing trans-cis isomerization pathways
Time- and momentum-resolved heat transport
Ultrafast Materials Science: Understanding and controlling energy transport and conversion among multiple degrees of freedom
Q
5um
0.3
0.5
0.16
-10 0 10 200.10
0.15
0.4ns
0.1ns
1ns
1.4ns
The spatiotemporal-resolved structural probe reveals the deviation of the relaxation process from a sinusoidal profile that quantitatively measure the in-plane transport processes.
IntroductionThe time-resolved research program at the Advanced Photon Source is targeted at understanding the fundamentals of energy transport and conversion at multi- energy, length and time scales utilizing a suite of advanced ultrafast hard x-ray probes localized at Sector 7, 11 and 14.
Spin
Charge
Lattice
Orbital
+-
+
+ -+
--
++
-
+
-
-+
-
+
+ -+
--
++
-
+
-+
-
+
+ -+
--
++
-
+
-c
a
Optical intensity I(x,t)
Lattice structure (x,t)
9.5
10.0
12
18
9
12
-20 -10 0 10 20
10
12
-2ns (18s)
0.1ns
4ns
20ns
Position (µm)
Inte
nsity
(a.
u)In
tens
ity (
a.u)
0 2 4 6 8 10 12
17
17.1
17.2
17.3
17.4
17.5
17.6
θ o
Delay (ns)
Energy transport in nanostructured materials
BiFeO3
FeRh
Ultrafast Chemical Science: Elucidating the mechanisms of light induced chemical processes
Dye Sensitized Solar Cells
Natural photosynthesis
Molecular machines
Artificial photosynthesis solar fuels: Light → chemical energy
Artificial photosynthesissolar cells: Light → electricity
Combined Techniques for Complimentary Information
XAS(absorption)
XES(emission)
XRS(scattering)
Kα, Kβ sensitive to electronic structure,
not geometric structure
(spin and oxidation state, electronic correlations)
Determine structures of transient
intermediates
Insight into solvent shell rearrangements
XANES: sensitive to electronic and
geometric structure (oxidation state, valence orbital occupancy, charge
transfer)
EXAFS: local bond distances and
coordination numbers
Element specific, sensitive to local structure
Sensitive to all species in the
solvent
Valence-to-Core sensitive to chemically
relevant orbitals
Motivation: harnessing the power of light
All those techniques can now be applied to study transient states !
X-ray absorption spectroscopy
X-ray emission spectroscopy
X-ray diffuse scattering
-direct probe of spin state
-insight into solvent shell rearrangements
Kα
Kβ
-electronic and geometric structure
Excited state fraction
Input for XAS analysis Input for
scattering analysis
EXAFS yields change in bond length
Yields excited state geometric structure
KB Mirrors
X-rays
Ionchamber
Pilatus
Laser
APD
1 m Rowland circle
Analyzer crystal
Scintillator
3 ft. x 3 ft.table
Liquid jet
Capturing excited state structures at high precision by using full APS flux
First demonstration of combined techniques in a pump-probe experiment
Low spin ~t 650 ps
hn
Aqueous [Fe(bpy)3]2+
High spin
K. Haldrup et al., J.Phys Chem. A 116, 9878 (2012) G. Vanko et al, JESRP 188, 166 (2013)
Sector 7ID-D
Combined techniques
setup
Using flux demanding techniques for time resolved studies: efficient detection at high rep-rate
Ex: Von Hamos crystal analyzer for TR-XES
J. Szlachetko et al., RSI 83, 103105 (2012).
X-ra
y em
issi
on e
nerg
y
Incident x-ray energy
ZnO nanoparticles: Observe evolution of charge distribution
Laser excitation and x-ray detection @ 1.3 MHz
ZnO (35 nm particles) in water @355 nm
Optical pulse promotes electrons in conduction band
Only ~1% excited state fraction
Time-resolved RIXS difference map
Data consistent with increased electron density on Zn centers
Also demonstrated simultaneous measurement of Ka, Kb and Valence to Core XES
Kb 100 ps delay
Ka 100 ps delayK a ground state
K b ground state
Photosystem 1
e -
Relay
Catalyst
Photosensitizer(PS)
Relay(R)
Catalyst(C)
R
Bio-inspiration
Pho
tose
nsiti
zer
Phys. Chem. Lett. 4, 1972 (2013).
Natural photosynthesis
Interfacial electron transfer in Dye-sensitized solar cell
h
VB
CBDye
(TiO2)n
e -
VB
CBDye
(TiO2)n
+
-
X-ray probe
J. Phys. Chem. Lett. 2, 628 (2011). Angew. Chem. Int. Ed. 51, 12711 (2012).
Electron transfer inside a biomimetic supramolecular complex for solar fuel catalysts
Science 337, 1200 (2012).
Electron transport inside iron oxide nanoparticles
Sector 11ID-D
A versatile Time resolved
X-Ray Absorption
setup
Showcase experiments using X-ray absorption
Energy Conversion
Resolution: ~260 nm, ~80 ps
Spatiotemporally resolved hard x-ray probeHigh repetition rate lasers to fully exploit high flux of the APS
Tunable (0.2-16 mm)
Up to 1 MHz
250 fs
Light Conversion PHAROSNew!
266 nm 2.5 W (4 μJ/pulse) @ 600 kHz
Time Bandwidth DUETTO
50 kHz - 6.52 MHz
10 ps and 130 ps
Electric field pulse
THz radiation@Sec7
Laser shock excitation
Optical excitation
Energy Transport
0.4% strain
Electric-field-driven domain dynamics
P. Chen, et al., Phys. Rev. Lett. 110, 047601 (2013)
The time-resolved changes of the diffuse scattering show primarily a quasi-thermal phonon distribution that is established in 100 ps and that follows the time-scale of thermal transport.
Superionic phase transition
T. A. Miller et al., Nature Comm. 4, 1369 (2013)
H. Wen, G. Doumy, B. Adams, A. D. DiChiara, E. M. Dufresne, T. Graber, Y. Li, A. M. March, Q. Kong, A. R. Sandy, S. H. Southworth, D. A. Walko, J. Wang, X. Zhang, Y. ZhuTime-Resolved Research, Atomic Molecular and Optical Physics, and Structural Science Groups,X-ray Science Division, Advanced Photon Source, Argonne National Laboratory
Position (µm)
PbO
SrO
PbO
TiO2
TiO2
TiO2
TiO2
TiO2
TiO2
TiO2
SrO
……
