C. Laulhé, S. Ravy, P. Fertey, E. Elkaïm, F. Legrand

E. Collet, M. Lorenc, M. Buron-Le Cointe, H. Cailleau

Studies of ultrafast structural changes at SOLEIL synchrotron:

sub-ns and sub-ps pump-probe diffraction on CRISTAL beamline

(CRISTAL beamline - SOLEIL synchrotron)

(Institute of Physics - Rennes)

Ph. Hollander, S. Hustache, J.-P. Ricaud, P. Féret, T. Moreno(SOLEIL synchrotron)

M.-L. Boillot(Institut de Chimie Moléculaire et Matériaux d’Orsay)

ANR ULTiMATE – « ULTrafast co-operative and coherent photo-switching of molecular MATErials »

Outline

Studies of ultrafast structural changes at SOLEIL synchrotron:

sub-ns and sub-ps pump-probe diffraction on CRISTAL beamline

I. Pump-probe diffraction: how ?

II. Pump-probe diffraction: motivations

III. Test experiment: photoinduced effects in [TPA Fe(III) TCC] PF6

IV. Summary

Outline

Studies of ultrafast structural changes at SOLEIL synchrotron:

sub-ns and sub-ps pump-probe diffraction on CRISTAL beamline

I. Pump-probe diffraction: how ?

II. Pump-probe diffraction: motivations

III. Test experiment: photoinduced effects in [TPA Fe(III) TCC] PF6

IV. Summary

Pump-probe diffraction

→ Natural temporal width of a synchrotron X-ray pulse: 70 ps FWHM

→ « low- » mode: 10 ps FWHM (preliminary tests in Dec 2011)

→ « Slicing » mode: 80 fs FWHM (2014)

Making a movie of structural evolutions on the timescales of atomic vibration

E ~ 10 meV ↔ Tosc ~ 400 fs

• Following photoinduced structural changes as a function of time

Undulator

80 fs // 70 ps

Laserh = 1.55 eV

Δt

25 fs

RX

• Toward ultrashort X-ray pulses at SOLEIL synchrotron…

Onduleur147.6 ns(6.8 MHz)

70 ps

Onduleur147.6 ns(6.8 MHz)

70 ps

0 m31.25 m36.00 m

CRISTAL: future installation for pump-probe experiments

6-circle 4-circle

Undulator

Onduleur147.6 ns(6.8 MHz)

70 ps

Onduleur147.6 ns(6.8 MHz)

70 ps

0 m31.25 m36.00 m

CRISTAL: future installation for pump-probe experiments

6-circle 4-circle

42.13 m

Ti:Sa oscillator + regenerative Ti:Sa amplifier • = 800 nm, 25 fs FWHM• 500 µJ/pulse @ 10 kHz, 6 mJ/pulse @ 1 kHz

~ 1 ms(~ 1 kHz)

Undulator

Onduleur147.6 ns(6.8 MHz)

70 ps

Onduleur147.6 ns(6.8 MHz)

70 ps

0 m31.25 m36.00 m

CRISTAL: future installation for pump-probe experiments

6-circle 4-circle

42.13 m

Ti:Sa oscillator + regenerative Ti:Sa amplifier • = 800 nm, 25 fs FWHM• 500 µJ/pulse @ 10 kHz, 6 mJ/pulse @ 1 kHz

~ 1 ms(~ 1 kHz)

Undulator

XPAD detector• Photon counting enabled on level high of a logic gate• Up to 847 kHz frequency

90 ns

Delay

0 50 100 150 200 2500.0

0.5

1.0

1.51.5

2.0

2.5

Delay [ns]Tota

l in

tensi

ty

[a.u

.]

x 106

Outline

Studies of ultrafast structural changes at SOLEIL synchrotron:

sub-ns and sub-ps pump-probe diffraction on CRISTAL beamline

I. Pump-probe diffraction: how ?

II. Pump-probe diffraction: motivations

III. Test experiment: photoinduced effects in [TPA Fe(III) TCC] PF6

IV. Summary

Laser-induced phenomena in condensed matter

t : few fs

→ Out-of-equilibrium states→ Decoupled degrees of freedom

cond.

valence

E

cond.

valence

E

• t = 0 : laser driven electronic transition = 800 nm ↔ E = 1.55 eV

t < few ps : coherent phonons

µsnspsfs10 100 10 100 1010010

Laser-induced phenomena in condensed matter

t : few fs

→ Out-of-equilibrium states→ Decoupled degrees of freedom

cond.

valence

E

cond.

valence

E

• t = 0 : laser driven electronic transition = 800 nm ↔ E = 1.55 eV

Diff

ract

ed

in

ten

sity

(a.u

.)

-0.5 0.0 0.5 1.0 1.5Time (ps)

La0.42Ca0.58MnO3

P. Beaud et al.,PRL (2009)

Sudden shift of the equilibrium coordinates of

the ions:

Displacive excitation

(5 3/2 2)

Coherent phonons

t < few ps : coherent phonons

µsnspsfs10 100 10 100 1010010

Laser-induced phenomena in condensed matter

t : few fs

→ Out-of-equilibrium states→ Decoupled degrees of freedom

cond.

valence

E

cond.

valence

E

• t = 0 : laser driven electronic transition = 800 nm ↔ E = 1.55 eV

Diff

ract

ed

in

ten

sity

(a.u

.)

-0.5 0.0 0.5 1.0 1.5Time (ps)

La0.42Ca0.58MnO3

P. Beaud et al.,PRL (2009)

Sudden shift of the equilibrium coordinates of

the ions:

Displacive excitation

(5 3/2 2)

Coherent phonons

t < few 100 ps : ultrafast phase transitions

P. Baum et al., Science (2007)

VO2

Photoinduced ph. tr.

Diff

ract

ed in

tens

ity (

a.u.

)D

iffra

cted

inte

nsity

(a.

u.)

Diff

ract

ed in

tens

ity (

a.u.

)

T ˂ Tc T ˃ Tc

t0 t1 t2

TemperatureLaser excitation

t0

t1

t2

t < few ps : coherent phonons

µsnspsfs10 100 10 100 1010010

Laser-induced phenomena in condensed matter

t : few fs

→ Out-of-equilibrium states→ Decoupled degrees of freedom

cond.

valence

E

cond.

valence

E

• t = 0 : laser driven electronic transition = 800 nm ↔ E = 1.55 eV

Diff

ract

ed

in

ten

sity

(a.u

.)

-0.5 0.0 0.5 1.0 1.5Time (ps)

La0.42Ca0.58MnO3

P. Beaud et al.,PRL (2009)

Sudden shift of the equilibrium coordinates of

the ions:

Displacive excitation

(5 3/2 2)

Coherent phonons

t < few 100 ps : ultrafast phase transitions

P. Baum et al., Science (2007)

VO2

Photoinduced ph. tr.

Diff

ract

ed in

tens

ity (

a.u.

)D

iffra

cted

inte

nsity

(a.

u.)

Diff

ract

ed in

tens

ity (

a.u.

)

T ˂ Tc T ˃ Tc

t0 t1 t2

TemperatureLaser excitation

t0

t1

t2

t in range [10 fs - 100 ps]:

lattice dynamics driven by interactions with electronic degrees of freedom

µsnspsfs10 100 10 100 1010010

Laser-induced phenomena in condensed matter

t : few fs

→ Out-of-equilibrium states→ Decoupled degrees of freedom

cond.

valence

E

cond.

valence

E

• t = 0 : laser driven electronic transition = 800 nm ↔ E = 1.55 eV

Coherent phonons Photoinduced ph. tr.

t ~ 1 - 100 ns : propagation of deformation waves

Phonon creation: local increase of temperature

Stressed regions: propagation of a strain wave

cond.

valence

E Phonon creation

cond.

valence

E Phonon creation

compressive strain

Strain waves Heat diff.

t ~ 1 - 10 µs : laser-induced heat diffusion

Heat diffusion: homogeneisation of temperature

µsnspsfs10 100 10 100 1010010

Laser-induced phenomena in condensed matter

t : few fs

→ Out-of-equilibrium states→ Decoupled degrees of freedom

cond.

valence

E

cond.

valence

E

• t = 0 : laser driven electronic transition = 800 nm ↔ E = 1.55 eV

Coherent phonons Photoinduced ph. tr.

t ~ 1 - 100 ns : propagation of deformation waves

Phonon creation: local increase of temperature

Stressed regions: propagation of a strain wave

cond.

valence

E Phonon creation

cond.

valence

E Phonon creation

compressive strain

Strain waves Heat diff.

t ~ 1 - 10 µs : laser-induced heat diffusion

Heat diffusion: homogeneisation of temperature

t in range [100 ps - 10 µs]:

Laser induced strain waves and heat diffusion - control of the electronic properties ??

Outline

Studies of ultrafast structural changes at SOLEIL synchrotron:

sub-ns and sub-ps pump-probe diffraction on CRISTAL beamline

I. Pump-probe diffraction: how ?

II. Pump-probe diffraction: motivations

III. Test experiment: photoinduced effects in [TPA Fe(III) TCC] PF6

IV. Summary

Test experiment: photoinduced effects in [TPA Fe(III) TCC] PF6

[TPA (FeIII) TCC]Tris(2-pyridylméthyle)3,4,5,6-tetrachlorocatecholate

Lattice ↔ cooperative effects?

↑↓ ↑↓ ↑

↑ ↑ ↑↑↑

ETransfert de charge

ligand-métal

h

ΔtΔt = 0 ~ 1 ps1.

55 e

V

10 m

eV

↑↓ ↑↓ ↑

↑ ↑ ↑↑↑

ETransfert de charge

ligand-métal

h

ΔtΔt = 0 ~ 1 ps1.

55 e

V

10 m

eV

[TPA (FeIII) TCC] PF6

Test experiment: photoinduced effects in [TPA Fe(III) TCC] PF6

[TPA (FeIII) TCC]Tris(2-pyridylméthyle)3,4,5,6-tetrachlorocatecholate

Lattice ↔ cooperative effects?

↑↓ ↑↓ ↑

↑ ↑ ↑↑↑

ETransfert de charge

ligand-métal

h

ΔtΔt = 0 ~ 1 ps1.

55 e

V

10 m

eV

↑↓ ↑↓ ↑

↑ ↑ ↑↑↑

ETransfert de charge

ligand-métal

h

ΔtΔt = 0 ~ 1 ps1.

55 e

V

10 m

eV

[TPA (FeIII) TCC] PF6

M. Lorenc et al., PRL 103 028301 (2009)

• Time-resolved structure determination at 180 K:

<Fe-N> :fraction of molecules

in the HS state

Unit cell parameter a :elastic deformations

Debye-Waller factor B:crystal temperature

Test experiment: photoinduced effects in [TPA Fe(III) TCC] PF6

[TPA (FeIII) TCC]Tris(2-pyridylméthyle)3,4,5,6-tetrachlorocatecholate

Lattice ↔ cooperative effects?

↑↓ ↑↓ ↑

↑ ↑ ↑↑↑

ETransfert de charge

ligand-métal

h

ΔtΔt = 0 ~ 1 ps1.

55 e

V

10 m

eV

↑↓ ↑↓ ↑

↑ ↑ ↑↑↑

ETransfert de charge

ligand-métal

h

ΔtΔt = 0 ~ 1 ps1.

55 e

V

10 m

eV

[TPA (FeIII) TCC] PF6

M. Lorenc et al., PRL 103 028301 (2009)

• Time-resolved structure determination at 180 K:

<Fe-N> :fraction of molecules

in the HS state

Unit cell parameter a :elastic deformations

Debye-Waller factor B:crystal temperature

1

Photoinduced effects in [TPA Fe(III) TPP] PF6:

1) Laser induced switching of molecules

Test experiment: photoinduced effects in [TPA Fe(III) TCC] PF6

[TPA (FeIII) TCC]Tris(2-pyridylméthyle)3,4,5,6-tetrachlorocatecholate

Lattice ↔ cooperative effects?

↑↓ ↑↓ ↑

↑ ↑ ↑↑↑

ETransfert de charge

ligand-métal

h

ΔtΔt = 0 ~ 1 ps1.

55 e

V

10 m

eV

↑↓ ↑↓ ↑

↑ ↑ ↑↑↑

ETransfert de charge

ligand-métal

h

ΔtΔt = 0 ~ 1 ps1.

55 e

V

10 m

eV

[TPA (FeIII) TCC] PF6

M. Lorenc et al., PRL 103 028301 (2009)

• Time-resolved structure determination at 180 K:

<Fe-N> :fraction of molecules

in the HS state

Unit cell parameter a :elastic deformations

Debye-Waller factor B:crystal temperature

1 2

Photoinduced effects in [TPA Fe(III) TPP] PF6:

1) Laser induced switching of molecules

2) Deformation wave propagation

Test experiment: photoinduced effects in [TPA Fe(III) TCC] PF6

[TPA (FeIII) TCC]Tris(2-pyridylméthyle)3,4,5,6-tetrachlorocatecholate

Lattice ↔ cooperative effects?

↑↓ ↑↓ ↑

↑ ↑ ↑↑↑

ETransfert de charge

ligand-métal

h

ΔtΔt = 0 ~ 1 ps1.

55 e

V

10 m

eV

↑↓ ↑↓ ↑

↑ ↑ ↑↑↑

ETransfert de charge

ligand-métal

h

ΔtΔt = 0 ~ 1 ps1.

55 e

V

10 m

eV

[TPA (FeIII) TCC] PF6

M. Lorenc et al., PRL 103 028301 (2009)

• Time-resolved structure determination at 180 K:

<Fe-N> :fraction of molecules

in the HS state

Unit cell parameter a :elastic deformations

Debye-Waller factor B:crystal temperature

1 2 3

Photoinduced effects in [TPA Fe(III) TPP] PF6:

1) Laser induced switching of molecules

2) Deformation wave propagation3) Heat diffusion in the crystal

Test experiment: photoinduced effects in [TPA Fe(III) TCC] PF6

[TPA (FeIII) TCC]Tris(2-pyridylméthyle)3,4,5,6-tetrachlorocatecholate

Lattice ↔ cooperative effects?

↑↓ ↑↓ ↑

↑ ↑ ↑↑↑

ETransfert de charge

ligand-métal

h

ΔtΔt = 0 ~ 1 ps1.

55 e

V

10 m

eV

↑↓ ↑↓ ↑

↑ ↑ ↑↑↑

ETransfert de charge

ligand-métal

h

ΔtΔt = 0 ~ 1 ps1.

55 e

V

10 m

eV

[TPA (FeIII) TCC] PF6

M. Lorenc et al., PRL 103 028301 (2009)

• Time-resolved structure determination at 180 K:

<Fe-N> :fraction of molecules

in the HS state

Unit cell parameter a :elastic deformations

Debye-Waller factor B:crystal temperature

1 2 3 4

Photoinduced effects in [TPA Fe(III) TPP] PF6:

1) Laser induced switching of molecules

2) Deformation wave propagation3) Heat diffusion in the crystal4) Relaxation

Test experiment: photoinduced effects in [TPA Fe(III) TCC] PF6

Nd:YAG laser

Open flow N2 cryostat

XPAD 3.2 X-rays

6-circle diffractometer

Continuum – Minilite I

kphikphi

100 µm

kphi

Sample: [TPA Fe(III) TCC] PF6

Pump and probe beam characteristics

Laser X-rays

Wavelength / energy 1064 nm 18.623 keV

Pulse duration 6 ns 70 ps

Power 100 µJ/pulse/mm²

1.3 105

photon/pulse

Spot characteristics Φ 2 mm Rectangular,135 x 450 µm²

Repetition rate: 10 Hz

• Test experiment on CRISTAL• Experimental setup

Test experiment: photoinduced effects in [TPA Fe(III) TCC] PF6

Nd:YAG laser

Open flow N2 cryostat

XPAD 3.2 X-rays

6-circle diffractometer

Continuum – Minilite I

kphikphi

100 µm

kphi

Sample: [TPA Fe(III) TCC] PF6

Pump and probe beam characteristics

Laser X-rays

Wavelength / energy 1064 nm 18.623 keV

Pulse duration 6 ns 70 ps

Power 100 µJ/pulse/mm²

1.3 105

photon/pulse

Spot characteristics Φ 2 mm Rectangular,135 x 450 µm²

Repetition rate: 10 Hz

• Test experiment on CRISTAL• Experimental setup kphi

X-rays

002

ckphi

• Rocking curve measurements

Ewald sphere

kphi-scan ↔ Imaging the 002 Bragg spot in 3D

Bragg spot extensions along a and b:

Spread of (002) lattice plane tiltingsin the a and b directions

a

cb

Test experiment: photoinduced effects in [TPA Fe(III) TCC] PF6

0 ns

- 10 µs

50 ns

100 ns

300 ns

700 ns

1 µs

5 µs

10 µs

50 µs

100 µs

500 µs

log

0 ns0 ns

- 10 µs- 10 µs

50 ns50 ns

100 ns100 ns

300 ns300 ns

700 ns700 ns

1 µs1 µs

5 µs5 µs

10 µs10 µs

50 µs50 µs

100 µs100 µs

500 µs500 µs

loglog

a

cb

a

cb ∑

Test experiment: photoinduced effects in [TPA Fe(III) TCC] PF6

0 ns

- 10 µs

50 ns

100 ns

300 ns

700 ns

1 µs

5 µs

10 µs

50 µs

100 µs

500 µs

log

0 ns0 ns

- 10 µs- 10 µs

50 ns50 ns

100 ns100 ns

300 ns300 ns

700 ns700 ns

1 µs1 µs

5 µs5 µs

10 µs10 µs

50 µs50 µs

100 µs100 µs

500 µs500 µs

loglog

a

cb

a

cb ∑

a

cb

a

cb∑

Test experiment: photoinduced effects in [TPA Fe(III) TCC] PF6

0 ns

- 10 µs

50 ns

100 ns

300 ns

700 ns

1 µs

5 µs

10 µs

50 µs

100 µs

500 µs

log

0 ns0 ns

- 10 µs- 10 µs

50 ns50 ns

100 ns100 ns

300 ns300 ns

700 ns700 ns

1 µs1 µs

5 µs5 µs

10 µs10 µs

50 µs50 µs

100 µs100 µs

500 µs500 µs

loglog

a

cb

a

cb ∑

a

cb

a

cb∑

Two characteristic timescales:- Few 100 ns after excitation: peak broadening without profile change - Few µs after excitation: peak broadening with apparition of a tail

Two lattice plane deformation cycles:- During step 2) propagation of deformation waves- During step 3) heat diffusion

Summary

First time-resolved experiment at the CRISTAL beamline [ns resolution]

[TPA Fe(III) TCC] PF6: lattice plane deformations in laser-induced transient states

Improvement of the temporal resolution:- November 2011: reception of a fs laser → 70 ps resolution

- Year 2012: optimization of the low-alpha mode of operation → 10 ps resolution

- Year 2014: « slicing » mode of operation → 100 fs resolution

Study of the interplays between lattice and electronic degrees of freedom

Control of electronic properties in molecular crystals

undulator

laser

wiggler

bending

magnet

e-be

am

70ps

75fs

75fs

Sub-ps resolution: slicing

• Time resolution ~ 100 fs

wiggler

electron bunch(70 ps)

Laser pulse: 25 fs, few mJ2.5 kHz, 800 nm

Exchange of energybetween electrons and IR photons

bending

magnet

In the “sliced” zone, the electrons have energies spanning the range [E-ΔE ; E+ ΔE]. They will be

spatially dispersed during their pass in the bending magnet.

electron bunch(75 fs)

Seminal paper :Zholents and Zolotorev, PRL 76 912 (1996)Available at Bessy, SLS, ALS

Laser