Inelastic and Elastic Scattering and RIXS at Synchrotron Sources

School on Synchrotron and Free-Electron-Laser
Based Methods: Multidisciplinary Applications and

Perspectives | (smr 3202) | 7-18 May 2018
Giacomo Ghiringhelli
Dipartimento di Fisica - Politecnico di Milano
giacomo.ghiringhelli@polimi.it
9 May, 2018
Summary
Introducing resonant x-ray inelastic scattering

dd excitations
Cu L3 RIXS and spin excitations in cuprates
Giacomo Ghiringhelli 2016

Transition metal oxides
matwww.technion.ac.il
Giacomo Ghiringhelli 2016 3
Introduction to Resonant X-ray Scattering
X-ray
Absorption Energy Loss
Spectroscopy Spectroscopy
XAS ELS
RXS
XRD
X-Ray
Diffraction

From XRD to X-ray Scattering
X-Ray X-Ray
Diffraction Scattering
q
|k'|=|k| |k'|=|k| q=G
2q
crystal l = l' l = l'
Real space
Bragg law Reciprocal lattice
Laue condition: q=G
(0,2)
l l'
k k' (0,1) (1,1)
q = k' - k
(0,0) (1,0)
ELS: from Raman to Inelastic X-ray Scattering
Energy Loss w w'

Spectroscopy Inelastic
k k' X-ray
Scattering
Raman
light scattering
k0, q0,
W=w-w' w w'
X-ray photons W=w-w'
q = k' - k
w w'
W W
Resonant X-ray Absorption
2.5
Photoelectric 1
OK
530 eV Cu L2,3
CuO
2.0
effect dominates 930-950 eV
Absorption coefficient (arb. u.)

x-ray absorption 0.1
1.5
below 100,000 eV
0.01 Cu K
9000 eV 1.0
1E-3
0.5
1E-4
0.0
10 100 1000 10000
Photon Energy (eV)
Edges are univocally element specific
And often are dressed with a

strong resonance
Core level binding energies and edges
C O Si Sc Fe Zn Y Mo Cd Ce Gd Lu Au Th
3dTM 4dTM RE Actinides
100000
Hard X-Rays
10000
Binding energy (eV)
Soft X-Rays
1000
100
UV
2p3/2 3p
10 1s 3/2 3d5/2 4p3/2 4d5/2
0 10 20 30 40 50 60 70 80 90 100
Atomic number Z
GG - Politecnico di Milano; Source: X-ray data booklet, Lawrence Berkeley National Laboratory 25/03/02 18:29:59

XAS of 3d transition metals
E 3dTM Spin-Orbit
splitting
Ev
4sp
Mn L2,3 XAS
EF 3d
hnin w La0.7Sr0.3MnO3
3p
2p
MnO
640 645 650 655 660

1s photon energy (eV)

Resonant Inelastic X-ray Scattering
Resonant Inelastic w, l w', l'

X-ray X-ray k k'
Absorption Scattering
RIXS
W=w-w'
X-Ray q = k' - k
Scattering

The choice of the resonance: 2p 3d, L3 edge
3d Transition Metal oxides: a lucky coincidence for soft x-rays
3d TM E Oxygen
4sp
3d 2p
2s
M2,3 edges (28-77 eV) 3p
K edge 530 eV
1s Soft x rays
L2,3 edges (400-950 eV) 2p
K edge (4.5-9.0 keV) 1s Hard x rays
Strong resonances

L3 RIXS
Phonons
E dd
Spin
EF
3d e-h
hnout - hn in
Eloss 0
hn in hn out E
(930 eV) hnin hnout
2p3/2 core-hole:
high energy
low energy
Ground Intermediate Final
state states states
L edge RIXS : energy and momentum transfer
Resonant Inelastic
X-ray Scattering:
• an energy loss experiment
e E’, k’, ’
pl • made with photons of high energy
a m
S • at a core absorption resonance
E, k, 
Energy
Scattering plane
hw = E - E’ k’
Conservation laws:
• Energy
q = k-k’
• Momentum
Momentum
• “Angular momentum” k

Photon momentum and kinematics
Photons vs Neutrons: energy and momentum
Wavevector of particles used in inelastic scattering
Thermal
neutrons
10
s
on
utr
1 Ne 1st Brillouin zone boundary
k (Ang )
-1
K edges
0.1
L edges
0.01
M edges
ns
to
1E-3
o
Ph
1m 10m 100m 1 10 100 1k 10k 100k

energy (eV)
L2,3 edge RIXS: intermediate and final states
3d
hnin hnout De- excitation s

Excit ation eout
E
2p3/2
hnou t
hnin
Ti me
Ground Intermediate Fin al
state stat es stat es
Resonant scattering without relaxation of intermediate s

3dn 2p53dn+1 3dn
The potential of soft RIXS (for 3dTM systems)
Site selective,
q resolved probe of
elementary excitations
• charge excitations across the gap
• dd excitations
• magnetic excitations
• phonons
3dn: elastic, magnetic and phonons

3dn 2p53dn+1 3dn*: dd excitations
3dnL: Charge Transfer excitations

Cuprates: the “easy” case
In cuprates Cu is divalent: Cu2+ 3d9 CuO
This makes XAS almost trivial: 1 peak only
3d9 (2p3/2)33d10
928 930 932 934
Photon Energy (eV)
RIXS can be calculated even by hand:

3d9 (2p3/2)33d10 (3d9)*
Even for magnetic excitations (spin waves),

because fast collision approximation is a very
good approximation
dd excitations in Cu2+ systems z
x2-y2
x2-y2, z2 eg b1 z x
y
z2
a1
d states 10Dq 10Dq x
z
y
xy
b2 z z x
y
yz,zx
xy, yz,zx t2g eg
x
x
Spherical Cubic Tetragonal Interatomic y y
O3 Oh D4h exchange
x2-y2
b1
z2
a1
10Dq
xy
b2
yz,zx
eg
3d9 2p53d10 3d9
Cu L3 RIXS of cuprates: mainly dd excitations
3d9: elastic, magnetic and phonons
3d9 2p53d10 3d9*: dd excitations
3d10L: Charge Transfer excitations
600 All final states

Sr2CuO2Cl2 are reached via
500 2 electric dipole
allowed transitions!
400
Photons get coupled
300
to electrons spin
thanks to 2p
200
spin-orbit interaction
At L3 edge elastic
100
peak is very small
(not the case at K)
0
-8 -6 -4 -2 0
Energy loss (eV)
Cu L3 edge: CuO, La2CuO4, Malachite SAXES
& Swiss Light Sourc e
Politec nic o di Milano
Cu2+ in square
21 approximately
planar coordination
Intensity (ph. s-1 eV-1)
CuO Cu-O distances:

14 CuO 1.7 – 2-2 Ang
LCO 1.9 – 2.4 Ang
Malachite 1.9 – 2.6 Ang
La2CuO4
x2 Different Cu2+
7
coordination,
symmetry,
Cu2(OH)2CO3
hybridization
0
-3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0
Energy loss (eV) Different dd excitations
G. Ghiringhelli, A. Piazzalunga, X. Wang, A. Bendounan, H. Berger, F. Bottegoni, N. Christensen, C. Dallera, M. Grioni, J.-C. Grivel,
M. Moretti Sala, L. Patthey, J. Schlappa, T. Schmitt, V. Strocov , and L. Braicovich, Eur.Phys. J. Special topics 169, 199 (2009)

This is a very direct way of measuring the dd-excitation energies
M. Moretti Sala, et al New J. Phys. 13, 043026 (2011)

dd-excitation energies from fitting using atomic cross sections
Ground state: 3𝑑 ↓ 𝑥 2 −𝑦 2
Spin along [001] Spin along [110]
Spin flip: 3𝑑 ↑ 𝑥 2 −𝑦 2
F(qin,fin,qout,fout,qspin,fspin,in,out)
NdBCO

Crystal field trends in cuprates

Crystal field trends in cuprates: theory vs experiment
CASSCF: complete-active-space self-consistent-field method
NBCO (exp)
Liviu Hozoi, Liudmila Siurakshina, Peter Fulde & Jeroen van den Brink,
SCIENTIFIC REPORTS 1 : 65 (2011)
[14] M. Moretti Sala, et al New J. Phys. 13, 043026 (2011) 2016

dd excitations: Cu L3 vs M2,3 edges
L3
M2,3
Very weak signal

No spin excitations with respect to
at Gamma point the elastic peak
J. Schlappa et al NATURE 485, 82 (2012) L.A. Wray et al arXiv:1203.2397v1

Ni L3 edge: NiO, NiCl2
Ni2+ (3d8) in octahedral
coordination
c
40
z
y
x
a
NiO
20
x y
NiCl2
0 a b
-4 -3 -2 -1 0
Energy loss (eV)
dd and CT excitations in
simple oxides
G. Ghiringhelli, A. Piazzalunga, X. Wang, A. Bendounan, H. Berger, F.

Bottegoni, N. Christensen, C. Dallera, M. Grioni, J.-C. Grivel, M. Moretti Sala,
L. Patthey, J. Schlappa, T. Schmitt, V. Strocov , and L. Braicovich, Eur.Phys.
J. Special topics 169, 199 (2009)

RIXS of NiO: incident photon energy SAXES
depencence ...
852 853 854 855 856 857 858
Intensity (arb.u.)
NiO
Ni L3 XAS
S
P
852 853 854 855 856 857 NiO

858 S P P
5 -5 5
RIXS NiO NiCl2
4 -4 x5 4
Energy loss (eV)
Energy loss (eV)

3 -3 3
2 -2 2
1 -1 1
0 0 0
852 853 854 855 856 857 858 0 25 50 75 100

Incident photon energy (eV) RIXS Intensity (ph.-1 s eV -1 )
G. Ghiringhelli A. Piazzalunga, C. Dallera, L. Braicovich, T. Schmitt, V.N. Strocov, J. Schlappa,
L. Patthey, X. Wang, H. Berger, and M. Grioni, PRL 102, 027401 (2009)
... and magnetic excitations in NiO
Interatomic exchange splitting : ~115 meV
Main peak
Satellite
6 V pol S H pol 6
RIXS intensity (ph. s eV )
-1
-1
4 4
-1 -1
q (A ) q (A )
0.36 0.36
2 2
0.61 0.61
0.78 0.78
0 0
-4 -3 -2 -1 0 0.4 0.3 0.2 0.1 0.0 -0.1 0.4 0.3 0.2 0.1 0.0 -0.1
Energy loss (eV) Energy loss (eV) Energy loss (eV)

No evident dispersion of these magnetic excitations
G. Ghiringhelli A. Piazzalunga, C. Dallera, L. Braicovich, T. Schmitt, V.N. Strocov, J. Schlappa,
L. Patthey, X. Wang, H. Berger, and M. Grioni, PRL 102, 027401 (2009)
Many excited states
relative scattered photon energy (eV)
Crystal field model: Sugano-Tanabe diagrams
-4.0 -3.5 -3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0
Ni L3 RIXS
(x2-y2), (z2)
intensity (arb. u.)
F eg
10Dq
H
t2g
(xy), (yz), (zx)
1.5
10Dq (eV)
1.0
0.5 Single ion
1
G
3
P D
1 3
F
0.0 Octahedral C.F.
1
1
T2g 1
A1g3T1g 3
T2g 1E1g 3
A2g 3d spin-orbit
T
3 1g
T1g Exchange
1
1.5
E
1 g
T2g 1.0
10Dq (eV)
0.5
1 3
0.0
G P 1D 3
F Single ion
4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
relative state energy (eV)
Octahedral C.F.
G. Ghiringhelli et al, J. Phys. Cond. Mat. 17, 5397 (2005) S.G.Chiuzbaian, G. Ghiringhelli et al, Phys. Rev. Lett. 95, 197402 (2005)
Mn L3 edge: MnO, LaMnO3
15 Mn2+ and Mn3+

in octahedral
coordination
10
Mn2+: 3d5
MnO
5
LaMnO3 x10
0 Mn3+: 3d4
-10 -5 0
Energy loss (eV)

dd of Mn2+: Sugano-Tanabe, Single ion,
Single Ion Impurity Model
Ground state: 3d5, high spin (6S for 10Dq=0)
G. Ghiringhelli et al, PRB 73,

G. Ghiringhelli et al, PRB 78,
035111 (2006)
117102 (2008)
An application to thin film: Mn2+ in LaxMnO3
LaxMnO3-d/STO films
x=La/Mn ratio
for x<1 becomes FM (self doping)
MnO
x=0.66
x=0.88
XAS reveals the presence x=0.98
of Mn2+ for x<1 x=1.07
P. Orgiani, A. Galdi, C. Aruta, V. Cataudella, G. De Filippis, C.A. Perroni, V. Marigliano Ramaglia, R. Ciancio, N.B. Brookes, M.
Moretti Sala, G. Ghiringhelli, and L.
Giacomo Ghiringhelli Maritato, Phys. Rev. B 82, 205122 (2010)
2016
An application to thin film: Mn2+ in LaxMnO3
RIXS shows that Mn2+ is at
site A, ie, it replaces La3+ The Mn2+ in site A allows new
Double Exchange paths,
increasing TMI
P. Orgiani, A. Galdi, C. Aruta, V. Cataudella, G. De Filippis, C.A. Perroni, V. Marigliano Ramaglia, R. Ciancio, N.B. Brookes, M.
Moretti Sala, G. Ghiringhelli, and L.
Giacomo Ghiringhelli Maritato, Phys. Rev. B 82, 205122 (2010)
2016
STO/LAO superlattice: RIXS at Ti L3

What about the “quasi-elastic” spectral features?
Phonons: up to 90meV
Magnons (2J at BZB): up to 300 meV (Jeff ≈ 140 meV)
Multi mangons...
600
Sr2CuO2Cl2
500
400
300
200
100
0
-8 -6 -4
-2 0
High Tc superconductors

High Tc superconducting cuprates
La2-xSrxCuO4 (LSCO)
YBa2Cu3O6+d (YBCO)
Spin excitations in HTcS: undoped AF
INS: La2CuO4
2D AF
DIRECT SPACE RECIPROCAL SPACE

nuclear BZ
(p, p)
G (0,0) (p,0) N. S. Headings, S. M.

Hayden, R. Coldea, and T.
G. Perring, Phys Rev Lett.
105 247001 (2011)
magnetic BZ
The mysteries of HTcS
La2-xSrxCuO4 (LSCO) YBa2Cu3O6+d (YBCO)
Eduardo Fradkin and Steven A.

Kivelson, Nature Physics, 8, 864 (2012)

Spin excitations in HTcS: doped SC
http://for538.wmi.badw.de/projects/P4_crystal_growth/index.htm
0.5,0.5
p,p
J.M. Tranquada, in Handbook of High-Temperature

INS Superconductivity: Theory and
Experiment, J.R. Schrieffer and J.S. Brooks, eds.,
0,0 Springer, 2007,
p,0
V. Hinkov et al, Eur. Phys. J. Special Topics 188, 113–129 (2010)

RIXS: Experimental conditions
0.5,0.5
p,p Cu L3 resonance:
• E0 = 930 eV
Cu L3 RXS
• qmax = 0.86 Ang-1
0,0 • confined inside a region around G
0.5,0
p,0
• 2p core hole: spin-orbit interaction
• E resolution: 120-240 meV
Wavevector of particles used in inelastic scattering
• q resolution: 0.005 rlu
Thermal
neutrons • ½ - 1 hour per spectrum
10
s
on
eu
tr L3 RIXS
3dTM K edges, 5dTM L edges
1 N 1st Brillouin zone boundary
E
k (Ang )
-1
0.1
INS
3dTM M edges
3dTM L edges
0.01
s
on
ot
1E-3
Ph
1m 10m 100m 1 10 100 1k 10k 100k

q
energy (eV) Giacomo Ghiringhelli 2016
spin-flip excitations and the 2p S-O coupling
3d9 2p53d10 3d9

x2-y2 x2-y2 x2-y2
930 eV
The 3d spin must not

be pure UP or DOWN
2p3/2 2p3/2 2p3/2
20 eV
2p1/2 2p1/2 2p1/2

Linear polarization of x-rays and orbital orientation
hnin hnin
z hnin z
hnin
x
y x
y
Empty 3d state a1 z2
b1 x2-y2
High absorption Weak absorption
No absorption High absorption

3d hole symmetry in cuprates
3d9 (2p3/2)33d10
q
hn E
Result: the hole in Cu2+ has

100% x2-y2 symmetry

Linear polarization of x-rays and orbital orientation (2)
The same rules hold for emission (radiative de-excitation)
p
p
p’ s p’
s z
hnout hnout
z
s’ s’
x x
y y
b1 x2-y2 a1 z2
High emission Weak emission
No emission High emission

Polarization dep. of Cu L3 RIXS intensity
Sr2CuO2Cl2
p xy q//>0
s
q=+0.37 rlu
Elastic
2M
1M
-3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0

Energy loss (eV)

Polarization dependent cross-sections
LSCO, opt. doping
p incid polarization s incid polarization
Energy (eV)
phonons phonons phonons
h (rlu) h (rlu)
q//<0 q//>0 q//<0 q//>0
M. Hashimoto, L.Braicovich, M. Minola, GG et al. unpublished

First demonstration: La2CuO4
La2CuO4
p
s
q//>0
q//<0
-3.5 -3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5

Energy loss (eV)
L. Braicovich, J. van den Brink, V. Bisogni, M. Moretti Sala, L. Ament, N.B. Brookes, G.M. de Luca, M.
Salluzzo, T. Schmitt, and G. Ghiringhelli Giacomo
PRL 104 077002
Ghiringhelli 2016 (2010)
La2CuO4, RIXS vs INS
La2CuO4
R. Coldea et al, Phys. Rev. Lett. 86, 5377 (2001).
L. Braicovich, J. van den Brink, V. Bisogni, M. Moretti Sala, L. Ament, N.B. Brookes, G.M. de Luca, M. Salluzzo, T.
Schmitt, and G. Ghiringhelli PRL 104 077002 (2010)
Magnetic excitations in AF cuprates SAXES
2008
Sr2CuO2Cl2 DE 0.12 eV
M. Guarise, B. Dalla Piazza, M. Moretti Sala, G. Ghiringhelli, L. Braicovich, H. Berger, J.N. Hancock, D. van der Marel, T.
Schmitt, V.N. Strocov, L.J.P. Ament, J. van den Brink, P.-H. Lin, P. Xu, H. M. Rønnow, and M. Grioni. Phys. Rev. Lett. 105,
157006 (2010)
AF NdBa2Cu3O6+d: magnon optical branch
NBCO (H-polarization) ERXS@ID32
8000
July 2015 BW = 50 meV
0
-60
6000
p pol. – spin-flip
J// = 136 meV; J = 6 meV

Intensity
4000
0
0
2000
0
0 Y.Y. Peng, G. Dellea, M. Minola, G.M. De Luca, M.
+60
Salluzzo, M. Le Tacon, B. Keimer, L. Braicovich, N.B.
-0.5 0.0
Brookes, and G. Ghiringhelli, unpublished
Energy (eV)
Comparing RIXS with INS
YBCO AF
NBCO AF
INS
RIXS
“YBa2Cu3O6.15 with mass 96 g.

[…]the resolution in energy was
2 meV and in Q was 0.05 Å-1.”
100 nm thick film NdBa2CuO6.2.
BW 55meV, DQ=0.02 Ang-1.
S. Hayden et al PRB 54 R6905 (1996)
YY Peng, GG et al, unpublished
Magnons at Fe L3 edge in BaFe2As2
Ke-Jin Zhou, Yao-Bo Huang, Claude Monney, Xi Dai, Vladimir N. Strocov, Nan-Lin Wang, Zhi-Guo Chen, Chenglin Zhang, Pengcheng Dai, Luc
Patthey, Jeroen van den Brink, Hong Ding & Thorsten Schmitt, Nature Comm. 4, 1470 (2013)
Magnetic and orbital excitations in Sr2IrO4
Ir4+
5d5
Strong spin-orbit in the 5d
L3 at 11.2 keV
Jungho Kim, D. Casa, M. H. Upton, T. Gog, Young-June Kim, J. F. Mitchell, M. van Veenendaal, M. Daghofer, J. van den Brink, G.
Khaliullin, and B. J. Kim, Phys. Rev. Lett. 108, 177003 (2012)
Magnetic excitations in bilayer iridates
Sr3Ir2O7
Jc<J Jc>J
M. Moretti Sala, et al, PRB 92, 024405 (2015)

Superconductors: LSCO, YBCO and NdBCO
LSCO & NdBCO: 100 nm films on STO. YBCO: detwinned single crystals
Dispersing magnetic excitations are almost as strong in SC as in the
AF parent compounds: they can be involved in Cooper pairing
L. Braicovich, J. van den Brink, V. Bisogni, M. Moretti Sala, L. Ament, N.B. Brookes, G.M. de Luca, M. Salluzzo, T. Schmitt,
and G. Ghiringhelli PRL 104 077002 (2010)
M. Le Tacon, G. Ghiringhelli, J. Chaloupka, M. Moretti Sala, V. Hinkov, M.W. Haverkort, M. Minola, M. Bakr, K. J. Zhou,
S. Blanco-Canosa, C. Monney, Y. T. Song, G. L. Sun, C. T. Lin, G. M. De Luca, M. Salluzzo, G. Khaliullin, T. Schmitt, L.
Braicovich and B. Keimer, Nat. Phys. 7, 725 (2011)
YBCO: doping dependence of c’’
Matthias Vojta, News and Views, Nature Physics 7, 674 (2011)
INS
RIXS YBa2Cu3O6.6
Energy-integrated c’’of the 20-site

Imaginary part of the spin susceptibility c’’(Q;w) resulting from exact cluster (normalized) for 7 accessible
diagonalization of the t–J model with J/t=0.3Giacomo
on small cluster.
Ghiringhelli 2016 (G. Khaliullin) non-equivalent Q vectors. (G. Khaliullin)
Peristent magnetic excits in overdoped cuprates
LSCO YBCO
p pol
M. P. M. Dean,, . G. Dellea, R. S. Springell, F. Yakhou-Harris, K. Kummer, M. Le Tacon, M. Minola, D. C. Peets, M. Moretti Sala, S. Blanco-Canosa,
N. B. Brookes, X. Liu, Y.-J. Sun, J. Strle, T. Schmitt, L. Braicovich, G. V. Hinkov, R. Liang, D. A. Bonn, W. N. Hardy, C. T. Lin, T. Schmitt, L.
Ghiringhelli, I. Bozovic, and J. P. Hill, Nat. Mater. 12, 1019 (2013) Braicovich, G. Ghiringhelli, and B. Keimer, Phys. Rev. B 88, 020501
Giacomo Ghiringhelli 2016 (2013)
Spin excitations in e-doped SC
Sr1-xLaxCuO2
h=0.43
0.40
0.37
0.30
0.26
0.22
0.18
0.14
0.09
0.05
W. S. Lee et al., Nature Physics 10,
0.00
883 (2014)
K. Ishii, M. Fujita, T. Sasaki, M. Minola, G. Dellea, C. Mazzoli, K.
0.0 0.5 1.0 Kummer, G. Ghiringhelli, L. Braicovich, T. Tohyama, K. Tsutsumi, K.
Energy loss (eV) Sato, R. Kajimoto, K. Ikeuchi, K. Yamada, M. Yoshida, M. Kurooka & J.
Mizuki, Nat. Comm. 5, 3714 (2014)
Individual cuprate layers
(Sr)
Nd
Cu2
Au
Amorphous
LSCO NBCO
LSAO STO
 La2-xSrxCuO4 (LSCO) opt. doped x=0.16  NdBa2Cu3O7 (NBCO) optimally doped

 Au capping (10÷15 nm thick)  Amorphous NBCO capping
(equivalent thickness of 2 u.c.)
 1 u.c. non-SC
 1 u.c. non-SC
 2 u.c. Tc ≈ 20 K
 2 u.c. Tc ≈ 93 K
 4 u.c. Tc ≈ 25 K
 80 u.c. Tc ≈ 93 K
 30 u.c. Tc ≈ 38 K
Grown by M. Salluzzo
Grown by G. Logvenov, G. Cristiani, F. Baiutti
Exceptional sensitivity of RIXS
La1.84Sr0.16CuO4 samples: NdBa2Cu3O7 samples
1800
T = 10 K 1 u.c., 30 min.
2500 T = 10 K
1600
q//=0.364 r.l.u. 2 u.c., 30 min. q// = 0.376 r.l.u.
1400 4.u.c., 30 min. 2000
1 u.c., 30 min.
30 u.c., 8 min.
Intensity (photons)
1200
Intensity (photons)
2 u.c., 30 min.
1500
1000 80 u.c., 8 min.
800
1000
600
400 500
200
Amorphous
Au
0 NBCO0
4 3 2 1 0 4 3 2 1 0
LSCO STO Energy loss (eV)
Energy loss (eV)
LSAO
300 NdBa2Cu3O7 n u.c.

300 La1.84Sr0.16CuO4 n u.c.
250
250
Energy (meV)
Energy (meV)
200
200
150
150
30 u.c. 100 80 u.c.
100
4 u.c. 2 u.c.
50
50 2 u.c. 1 u.c.
1 u.c. 0
0 0.0 0.1 0.2 0.3 0.4 0.5
0.0 0.1 0.2 0.3 0.4 0.5 q// (r.l.u.)
q// (r.l.u.)
Experiment at ADRESS beam line of SLS: M. Minola, G. Dellea, M. Salluzzo, V. Bisogni, T. Schmitt, M. Le Tacon,
G. Logvenov, G. Cristiani, F. Baiutti, B. Keimer, L. Braicovich, G. Ghiringhelli, unpublished
Small effect of thickness on J
Dynamics at BZ border (meV)
300 La1.84Sr0.16CuO4 n u.c.
0 50 100 150 200 250 300
250
40
30 u.c.
Energy (meV)
La1.84Sr0.16CuO4 n u.c.
200
150 30 4 u.c.
30 u.c. ÷2J 2 u.c.
Tc (K)
100
4 u.c. 20
50 2 u.c.
1 u.c.
0 10
0.0 0.1 0.2 0.3 0.4 0.5 1 u.c.
q// (r.l.u.)
non-SC
0
300 NdBa2Cu3O7 n u.c.
0 20 40 60 80 100 120 140
250
J (meV) from fittings
Energy (meV)
200
150 Linear spin-wave theory fittings

100 80 u.c. J decreases at lower film
2 u.c.
50
1 u.c.
thickness, but only by 20% from
0
0.0 0.1 0.2 0.3 0.4 0.5
bulk to 1 uc
q// (r.l.u.)
RIXS revealed Charge Order in HTcS
NBCO Tc=65K
V pol, T=15K
-0.18 rlu
-0.22 rlu
-0.26 rlu
-0.30 rlu
-0.34 rlu
-0.37 rlu
-3 -2 -1 0
Energy loss (eV)
Max intensity at Tc: CO compete with SC
G. Ghiringhelli, M. Le Tacon, M. Minola, S. Blanco-Canosa, C. Mazzoli, N.B. Brookes, G.M. De Luca, A.

Frano, D. G. Hawthorn, F. He, T. Loew, M. Moretti Sala, D.C. Peets, M. Salluzzo, E. Schierle, R. Sutarto,
G. A. Sawatzky, E. Weschke, B. Keimer, L. Braicovich, Science 337, 821 (2012)
RXS (at Cu L3 and O K) in combination with STM, XRD and NMR has
demonstrated that CO is ubiquitous in cuprates
UD Bi2201, Bi2212, Hg1201 and OPD Bi2212
Bi2201 and Bi2212 underdoped Bi2212 optimally doped
R. Comin et al, Science 343, 390 (2014;

Eduardo H. da Silva Neto et al, Science 343, 393 (2014)
Hg1201 underdoped
W. Tabis et al, Nat. Comm. 6875 (2014) Giacomo Ghiringhelli 2016 M. Hashimoto, G. Ghiringhelli et al, PRB 89 220511 (2014)
ENERGY RESOLUTION: progress in the
last 20 years
La2CuO4
Cu 2p  3d
DE ~1.6 eV Photon energy ~ 931 eV
K. Ichikawa et al., J. Electron Spectrosc. Relat.
Phenom.78, 183 (1996).
DE ~1.2 eV
L. C. Duda et al., J. Electron Spectrosc.
Relat. Phenom. 110–111, 275 (2000). 2000 Uppsala
DE ~0.8 eV
AXES @ ID08, 2003. G. Ghiringhelli et al., Phys
Rev Lett. 92, 117406 (2004).
2003
DE ~0.45 eV ESRF + AXES
AXES @ ID08, 2007. L. Braicovich et al.,
2007
arXiv:0807:1140v1, (2008).
DE ~0.13 eV
SAXES @ SLS, 2008. G. Ghiringhelli, L.
2008 SLS + SAXES
Braicovich, T. Schmit et al., unpublished
-4 -3 -2 -1 0 1 2
DE ~0.050 eV 2015
Energy loss (eV)
DE ~0.030 eV 2016 ESRF + ERIXS
Combined resolving power has increased by a factor 30

Soft x-ray RIXS instrumentation
High resolution mono, small x-ray spot on the sample

Grating spectrometer: optimized efficiency, high resolution
The main limiting factor is INTENSITY!!!!

From AXES (ESRF, ID08) to SAXES (SLS, ADRESS)
SAXES
INFM Politec nic o di Milano
Ad va nc e d X -Ra y Em issio n Sp e c tro sc o p y
Since 1994: AXES at beam line Since 2007: SAXES at beam line
ID08 of the ESRF ADRESS of the SLS
L = 2.2 m L = 5.0 m
Design: E/DE = 2,000 at Cu L3 (930 eV) Design: E/DE = 12,000 at Cu L3
2010: E/DE = 5,000 at Cu L3 2011: E/DE = 11,000 at Cu L3
C. Dallera et al. J. Synchrotron Radiat. 3, 231 (1996) G. Ghiringhelli, et al Rev. Sci. Instrum. 77, 113108 (2006)
G. Ghiringhelli et al., Rev. Sci. Instrum. 69, 1610 (1998) V. Strocov, T. Schmitt, L. Patthey et al, J. Synch. Rad., 17, 631 (2010).
M. Dinardo et al., Nucl, Instrum. Meth A 570, 176 (2007)

New ID32 at the ESRF
ERIXS
1
Old experimental hall

New experimental hall
ID32

ЄRIXS spectrometer at the new ID32
FEATURES: ESRF Upgrade program,
• E/DE > 20,000 below 1000 eV from day one N.B. Brookes, F. Yakhou,
(50 meV at Cu L3) and E/DE > 30,000 ultimate
GG et al
• continous variation of scattering angle,
• full control of sample orientation (almost a
diffractometer),
• measurement the linear polarization of the
scattered photons (when needed)
• optionally in high magnetic field
• flexible sample enviroment: possibility of
liquid and gas phase experiments
Commissioning:
Beamline: started operations in Dec 2014
ERIXS: first experiment 1st July 2015
Giacomo GhiringhelliFull
2016 ERIXS user operation – fall 2015
ERIXS@ID32, ESRF, 27/04/2014
Lucio Braicovich
Nick Brookes

ERIXS, 27/04/2014

ERIXS Spectrometer
In-vacuum Huber
Continuously rotating diffractometer
scattering arm
Speed
x8.6
Sample chamber
CINEL – Italy
ESRF
ERIXS: Expected resolving power
Medium-resolution grating: 1400 mm-1
High resolution grating: 2400 mm-1
Medium-resolution grating: 1400 mm-1

NBCO magnetic spectra
Resolution: 55 meV
20 NdBa2Cu3O6 AF (hkl)
(hkl)
(0.48
(0.48
0.00
0.00
0.85)
0.85)
k
100nm film on STO (0.28
(0.28
0.28
0.28
1.18)
1.18)
40 15 min acquisition
15
Intensity (ph s eV )
55 meV BW
-1
p polarization
-1
10 h
20
0
0
-0.6
-3.0 -0.5
-2.5 -0.4
-2.0 -0.3
-1.5 -0.2-1.0-0.1-0.50.0 0.00.1
Energy (eV)

ERIXS: ultra-high resolving power (Nov 2015)
Resolution: 31 meV
Phonons
Elastic peak

A polarimeter for RIXS spectrometer
The CCD was rotated

AXES@ID08
when the ML was inserted
in the beam. One ML
could cover limited energy
range (Ni and Cu L2,3).
L. Braicovich, M. Minola, G. Dellea, M. Le Tacon, M. Moretti Sala, C. Morawe, J.-Ch. Peffen, R. Supruangnet, F.
Yakhou, G. Ghiringhelli, and N. B. Brookes, Rev. Sci. Instrum. 85,115104 (2014)
AXES Polarimeter
YBCO6.6 s
p
s
p
M. Minola, G. Dellea, H. Gretarsson, Y. Y. Peng, Y. Lu, J. Porras, T. Loew, F. Yakhou, N. B. Brookes,

Y. B. Huang, J. Pelliciari, T. Schmitt, G. Ghiringhelli, B. Keimer, L. Braicovich, and M. Le Tacon, Phys. Rev. Lett.
114, 217003 (2015)
ERIXS Polarimeter
2 identical
CCDs
Covering with 2 ML
mirrors most of the 520-
1000 eV range
An evolution of the
prototype made for
AXES@ESRF that was used
for real measurements
L. Braicovich, M. Minola, G. Dellea, M. Le
Tacon, M. Moretti Sala, C. Morawe, J.-Ch.
Peffen, R. Supruangnet, F. Yakhou, G.
Ghiringhelli, and N. B. Brookes, Rev. Sci
Instrum. 85, 115104 (2014)

ERIXS Polarimeter: first spectrum
s = ss  sp NBCO - AF
scatt angle 149°
hkl = (-0.10, 0.00, 1.63)
NORMAL EMISSION
sigma incidence k
Magnon: 100% sp
-3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0

Commissioning has
just started, not
energy loss (eV)
open to users yet.
ERIXS and the other HR soft-RIXS projects
SR FACILITY E/DE (combined) Length YEAR NOTES

ESRF, ERIXS@ID32 30,000 11 m 2015 With Polarimeter
DIAMOND, IXS 40,000 14 m 2017

MAX IV, Veritas 40,000 ? 2017 Rowland Geometry
NSLS II, 70,000 15 m 2017 Hettrick-Underwood, 50 nrad

slope error, 1 um spot on sample
Centurion@SIX
European XFEL 20,000 5m 2018 For non linear RIXS and pump-
probe time-resolved RIXS

Heisenberg RIXS: SCS beam line of European
XFEL

Unique performance of XFEL in brillance and time
structure
+ Average brillance/brightness:
ESRF ID32: 5x1015 ph/s

NSLS II: 6-8x1015 ph/s
XFEL SASE3: 5x1017 ph/s
→ energy resolution
→ polarization analysis
→ rapid data acquisition
→ 3D-momentum-transfer
+ peak brillance
+ femtosecond time structure:
→ Driven and transient phases
→ Chemical pathways
→ Non-linear X-ray science
Pump-Probe RIXS

Stimulated emission
N. Rohringer, D. Ryan, R.A. London, M. Purvis, F. Albert, J.

Dunn, et al., Atomicinner-shell X-ray laser at 1.46 nanometres
pumped by an X-ray free-electronlaser, Nature 481 (2012) 488–
491
M. Beye, S. Schreck, F. Sorgenfrei, C. Trabant, N. Pontius, C.

Schüßler-Langeheine, et al., Stimulated X-ray emission for
materials science, Nature501 (2013) 191–194,
RIXS at XFEL: beyond 1 photon at a time
• Short pulses: TR RIXS we can look

at the fs-ps evolution of orbital,
magnetic, charge and phonon
Cu L3(provided
excitations, and at CDW RXS
Diamond, 7.3 keV
Non resonant we have the right pump)
SACLA • Coherent pulses: multi-photon
processes, stimulated emission,
multiple excitations

hRIXS: boundary conditions

hRIXS: boundary conditions
5-6 m scattering arm

Continuous rotation in backscattering (2q = 60° - 150°)
Possibility of full forward scattering (2q = 0° - 20°)
stim-RIXS
89 hr-RIXS, tr-RIXS
We privilege flexibility
hRIXS will have to work with

• different source size (defocusing on sample to reduce beam damage in
some cases)
• different detector resolution (from 10 micron for high resolution CCD to
100-200 micron for pixelated fast detectors)
• 5 m maximum length, that gives at least 5 mrad horizontal acceptance
with 1” detectors
Therefore we abandoned the option of the collimating/refocusing mirror,
to keep strictly 1 OE, the spherical VLS grating.

Optimization of grating parameters
A (1:1) B (1:2) C (1:5)

S1=10 μm S1=5 μm S1=20 μm
S2=10 μm S2=10 μm S2=100 μm
D (1:20) E (5:1)
S1=5 μm S1=50 μm
S2=100 μm S2=10 μm
Parameter optimization
Operational end 2017 (?)

YY Peng, GG, hRIXS optical design report (2015)
Bibliography
Insights into the high temperature superconducting

cuprates from resonant inelastic X-ray scattering
M.P.M. Dean
Journal of Magnetism and Magnetic Materials
Volume 376, 15 February 2015, Pages 3–13

Inelastic and Elastic Scattering and RIXS at Synchrotron Sources

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Inelastic and Elastic Scattering and RIXS at Synchrotron Sources

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School on Synchrotron and Free-Electron-Laser

Based Methods: Multidisciplinary Applications and

Introducing resonant x-ray inelastic scattering

Giacomo Ghiringhelli 2016

Giacomo Ghiringhelli 2016

Energy Loss w w'

Absorption coefficient (arb. u.)

Edges are univocally element specific

And often are dressed with a

Giacomo Ghiringhelli 2016

640 645 650 655 660

Giacomo Ghiringhelli 2016

Resonant Inelastic w, l w', l'

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3d Transition Metal oxides: a lucky coincidence for soft x-rays

K edge (4.5-9.0 keV) 1s Hard x rays

Giacomo Ghiringhelli 2016

Giacomo Ghiringhelli 2016

1m 10m 100m 1 10 100 1k 10k 100k

hnin hnout De- excitation s

Resonant scattering without relaxation of intermediate s

3dn: elastic, magnetic and phonons

Giacomo Ghiringhelli 2016

In cuprates Cu is divalent: Cu2+ 3d9 CuO

This makes XAS almost trivial: 1 peak only

RIXS can be calculated even by hand:

Even for magnetic excitations (spin waves),

600 All final states

CuO Cu-O distances:

Giacomo Ghiringhelli 2016

M. Moretti Sala, et al New J. Phys. 13, 043026 (2011)

M. Moretti Sala, et al New J. Phys. 13, 043026 (2011)

M. Moretti Sala, et al New J. Phys. 13, 043026 (2011)

CASSCF: complete-active-space self-consistent-field method

[14] M. Moretti Sala, et al New J. Phys. 13, 043026 (2011) 2016

Very weak signal

J. Schlappa et al NATURE 485, 82 (2012) L.A. Wray et al arXiv:1203.2397v1

G. Ghiringhelli, A. Piazzalunga, X. Wang, A. Bendounan, H. Berger, F.

Giacomo Ghiringhelli 2016

852 853 854 855 856 857 NiO

Energy loss (eV)

852 853 854 855 856 857 858 0 25 50 75 100

Interatomic exchange splitting : ~115 meV

Energy loss (eV) Energy loss (eV) Energy loss (eV)

15 Mn2+ and Mn3+

Giacomo Ghiringhelli 2016

Ground state: 3d5, high spin (6S for 10Dq=0)

G. Ghiringhelli et al, PRB 73,

Giacomo Ghiringhelli 2016

Giacomo Ghiringhelli 2016

DIRECT SPACE RECIPROCAL SPACE

G (0,0) (p,0) N. S. Headings, S. M.

La2-xSrxCuO4 (LSCO) YBa2Cu3O6+d (YBCO)

Eduardo Fradkin and Steven A.

Giacomo Ghiringhelli 2016

J.M. Tranquada, in Handbook of High-Temperature

V. Hinkov et al, Eur. Phys. J. Special Topics 188, 113–129 (2010)

1m 10m 100m 1 10 100 1k 10k 100k

3d9 2p53d10 3d9

The 3d spin must not

2p3/2 2p3/2 2p3/2

2p1/2 2p1/2 2p1/2

Giacomo Ghiringhelli 2016