New perspectives in superconductors

E. Bascones
Instituto de Ciencia de Materiales de Madrid (ICMM-CSIC)
 Outline
 Talk I: Correlations in iron superconductors
 Introduction to correlations in single orbital systems and cuprates.
 Superconductivity in iron superconductors
 Correlations in multiorbital systems.
• Equivalent orbitals. The Hund metal
• Unequivalent orbitals. Iron superconductors
 The magnetic state phase diagram
 Comparison with experiments. Iron superconductors in a (U,JH) phase diagram

 Talk II: A few new superconducting materials

 Superconductivity and competing phases
• CrAs and MnP
• Ti-oxypnictides. Superconductivity emerging from a nematic state?
 New quasi-1D superconductors
 Hydrides. A new record for high-Tc?

E. Bascones [email protected]
 A bit of history

1911. Resistivity vanishes below Tc. Discovery of superconductivity

1933. Superconductors expel magnetic fields. Meissner effect

1950. Ginzburg-Landau phenomenological theory

1957. BCS theory. Cooper pairs and electron-phonon interaction

1957-59. Vortices

1962. Josephson effect

In the ‘70s many superconductors were known (Tc < 25 K)

and people thought that superconductivity was understood

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 High-Tc superconductivity in iron materials

FeAs/FeSe
materials
2008. Iron superconductors
The second family of
high Tc superconductors

1979. Superconductivity in 1986. Cuprates. High-Tc

Heavy Fermion compounds superconductivity

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 Unconventional superconductivity in correlated systems

Heavy Fermions Cuprates Iron superconductors

Magnetically mediated superconductivity?

Superconductivity not due to electron-phonon interaction

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 Cuprates and Mott physics

NdCuO4 LaCuO4 YBa2CuO6+x

Several families
CuO2 Planes

Fig: Dagotto, RMP 66, 763 (1993) The electronic properties are controlled by these planes

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 Cuprates and Mott physics

LaCuO4

Fig: Dagotto, RMP 66, 763 (1993)

Fig: Pickett, RMP 61, 433 (1989)
CuO2 band

Expected to be metallic, but it is an insulator.

Mott insulator: insulating character due to electron-electron interactions

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 Cuprates and Mott physics

Superconductivity appears when an antiferromagnetic

Mott insulator is doped with electrons or holes

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 Mott insulators. The Hubbard model at half-filling

H=Si,j,s t c iscjs
Kinetic energy

Atomic lattice with a single orbital per site and average occupancy 1 (half filling)

E
Simplification for
Band structure

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 Mott insulators. The Hubbard model at half-filling

H=Si,j,s t c iscjs + USj njnj

Kinetic energy Intra-orbital
repulsion
Atomic lattice with a single orbital per site and average occupancy 1 (half filling)

E
Hopping Double occupancy
saves energy t costs energy U Intra-orbital
Tight-binding (hopping)
repulsion
For U >> t electrons localize: Mott insulator
Mott transition at Uc

But away from half-filling the system is always metallic Correlated metal

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 The quasiparticle weight in the single-orbital Hubbard model
Z: a way to quantify the correlations Overlap between the elementary excitations
of interacting and non-interacting systems
0  Z 1
Z=1 Single-particle picture (U=0)
Simple Fermi liquid description:
Heavy electron Z-1  m*/m Z=0 There are no quasiparticles
Breakdown of single-particle picture

Z colour plot for the Hubbard model

Z vanishes at the Mott transition

Correlated metal as U is increased

or half-filled is approached
(only close to the Mott transition).

Half-filling

Electronic filling
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Quasiparticle weight, charge & spin fluctuations in the Hubbard model

Quasiparticle weight Z: CT =<n2>-<n>2= <(dn)2> CS =<S2>-<S>2= <S2>

0  Z 1 n= <n> + dn Cs larger when atoms are spin
polarized even if there is no
A way to quantify Localization long range order
correlations

Mott insulator: Localized spins

Suppression of charge fluctuations at each
atomic site
n= <n>
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 Weakly correlated electrons & localized spins

Quasiparticle weight Z:

0  Z 1
A way to quantify
correlations

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 Nature of instabilities: the case of antiferromagnetism
Fermi surface instability Antiferromagnetic exchange

- Delocalized electrons. Energy - Localized electrons. Spins localized in

bands in k-space and Fermi surface real space
good starting point to describe
the system. -Kinetic energy favors virtual hopping
of electrons (t2/DE ~ t2/DE ).
-The shape of the Fermi surface
presents a special feature (nesting) -Virtual hopping results in interactions
between the spins. Magnetic Exchange
Spin models

-In the presence of small - Magnetic ordering appears if frustration

interactions antiferromagnetic (lattice, hopping, …) does not avoid it.
ordering appears.
- Commesurate ordering
- Ordering can be incommensurate

Spin Density Wave Magnetism driven by kinetic energy

Magnetism driven by interactions
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 Cuprates and Mott physics

Undoped (Cu d9) dx2-y2 orbital is half filled. Mott insulator

Described in terms of a localized electron /spin at each Cu site

Antiferromagnetic order. Neel state

Interaction between localized spins
Exchange J ~t2/U

H = J Si Sj
(Heisenberg model)

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 Cuprates: From a Mott insulator to a high-Tc superconductor

Unconventional
physics

Fermi liquid
(bands and
Fermi surface)

Which is the role of Mott physics

1 electron in 1 orbital:
In High-Tc superconductivity?
half-filling
Do we need localized moments
Mott insulator
to explain it?
Antiferromagnetism
described in terms of
Localized moments

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 Fe superconductors: FeAs-FeSe layers

Layered materials
(FeAs/Se planes)

Fe square
lattice

Kamihara et al, JACS 130, 3296 (2008)

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 Fe superconductors: families
Intercalated 11-Se
122-As 245-Se

BaFe2As2
KxFe2-ySe2
11-Se 111-As
1111-As
LiFeAs
LaFeAsO
FeSe

1048-As Perovskite
11-derived 1111-Se 112-As
Blocking
layer-As

Fig:Hosono & Kuroki, Phys. C (2015), arXiv: 1504.04919

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 Fe superconductors: phase diagram

Undoped: 6 e- per Fe
Doping with electrons Doping with holes

Zhao et al, Nat. Mat. 7, 953 (2008), Rotter et al, Angew. Chem. Int. Ed.
47, 7949 (2008)‫‏‬

Undoped iron pnictides/chalcogenides are (not always) AF

Superconductivity appears when doping with electrons or holes

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 Fe superconductors: phase diagram
Iron superconductors Cuprates

Superconductivity appears when an antiferromagnetic phase

is suppressed with electron or hole doping

Fig: Nature 464,183 (2010)

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 Fe superconductors: phase diagram
Iron superconductors Cuprates

In iron superconductors
superconductivity also appears
when pressure is applied

Alireza et al,
J. Phys. Cond. Matt 21,
012208 (2008)
Fig: Nature 464,183 (2010)
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 Fe superconductors: phase diagram

De la Cruz et al, Nature 453, 899 (2008), Zhao et al, Nature Materials 7, 953 (2008)
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 Fe superconductors: phase diagram
Isovalent substitution

Jiang et al, J. Phys. Cond.

Double stripe
Mat. 21, 382203 (2009)
ordering

Zhuang et al,
Sci. Rep. 4 7273 (2014)
FeTe FeSe
Hole doping Electron doping

Avci et al, Marty et al, Fujiwara et al, LaFeAsO1-xHx

Phys. Rev. B 88, 094510 (2013) Phys. Rev. B 83, 060509 (2011) Phys. Rev. Lett 111, 097002 (2013)

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 Fe superconductors: Metallicity of parent compounds

Contrary to cuprates undoped

iron pnictides
are NOT Mott insulators

Chen et al, PRL 100, 247002 (2008)

Zhao et al, Nat. Mat. 7, 953 (2008),

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 Fe superconductors: Metallicity of parent compounds
Iron superconductors Cuprates

Antiferromagnetic Metal
Are there local magnetic moments? AF Mott Insulator
Are iron superconductors strongly Local magnetic moments
correlated systems? Strongly Correlated Electron
System
Can we get high-Tc without local moments?
E. Bascones [email protected]
 Correlations in iron superconductors

Weak correlations Localized electrons

(properties, origin of magnetism (properties, origin of magnetism
and of superconductivity and of superconductivity
described in terms of itinerant described in terms of localized
electrons. Fermi surface physics) electrons. Spin models)

Yildirim, PRL 101, 057010 (2008),

Raghu et al, PRB 77, 220503 (2008), Si and Abrahams, PRL 101, 057010 (2008)
Mazin et al, PRB 78, 085104 (2008),
Chubukov et al, PRB 78, 134512 (2008),
Cvetkovic & Tesanovic,EPL85, 37002 (2008)

E. Bascones [email protected]
 Iron superconductors :multi-orbital character

Iron superconductors

Cuprates
LDA: Fe bands at the Fermi level.
Several orbitals involved
Undoped: 6 electrons in 5 orbitals

In cuprates a single band

crosses the Fermi level
Undoped: 1 electron in 1 orbital

Fig: Pickett, RMP 61, 433 (1989)

E. Bascones [email protected]
 Correlations in iron superconductors

Weak correlations Localized electrons

(properties, origin of magnetism (properties, origin of magnetism
and of superconductivity and of superconductivity
described in terms of itinerant described in terms of localized
electrons. Fermi surface physics) electrons. Spin models)

Hund metal
(Correlations due
to Hund’s coupling) Correlations can be different for
different orbitals leading even to
Shorikov et al, arXiv:0804.3283 a description in terms of the
Haule & Kotliar NJP 11,025021 (2009) coexistence of localized
6 electrons in 5 orbitals and itinerant electrons
Werner et al, PRL 101, 166404 (2008), Average doping n=1.2
de Medici et al, PRL 107, 255701 (2011) Like doped Mott insulators Yin et al, Nature Materials 10, 932 (2011)
Yu & Si, PRB 86, 085104 (2012) Bascones et al, PRB 86, 174508 (2012)
Ishida& Liebsch, PRB 82, 1551006 (2010)
Yi et al, PRL 110 067003, (2013)
Fanfarillo & Bascones, arXiv:1501.04607 Werner et al, Nature Phys. 8, 331 (2012)
Calderon et al, PRB 90, 115128 (2014) de Medici et al, PRL 112, 177001 (2014)

Multiorbital character may play an important role

E. Bascones [email protected]
 Correlations in iron superconductors

Weak correlations Localized electrons

(properties, origin of magnetism (properties, origin of magnetism
and of superconductivity and of superconductivity
described in terms of itinerant described in terms of localized
electrons. Fermi surface physics) electrons. Spin models)

Hund metal
(Correlations due
to Hund’s coupling) Correlations can be different for
different orbitals leading even to
a description in terms of the
coexistence of localized
6 electrons in 5 orbitals and itinerant electrons (OSMT)
Average doping n=1.2
Like doped Mott insulators

Review: Bascones et al,

arXiv:1503.04223, CRAS in press
E. Bascones [email protected]
 Iron superconductors: multi-orbital systems

The 5 Fe d-orbitals are necessary Several Fe bands

to describe the electronic properties cross the Fermi level

xy
Undoped compounds
yz/zx
Small crystal field Compensated FeAs layer
3z2-r2 6 electrons in 5 Fe orbitals
x2-y2

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 Iron superconductors: multi-orbital systems

Several Fe bands
cross the Fermi level

Undoped compounds

Not enough!
Compensated FeAs layer
6 electrons in 5 Fe orbitals

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 Hubbard-Kanamori Hamiltonian for multi-orbital systems

Intra-orbital
Tight-binding (hopping)
repulsion

Inter-orbital Hund’s
repulsion coupling

Pair hopping Crystal field

U’=U – 2JH J’= JH
Two interaction parameters: U, JH Local Interactions

E. Bascones [email protected]
 Hubbard-Kanamori Hamiltonian for multi-orbital systems

U’=U – 2JH J’= JH U – 3JH JH/U <0.33

Two interaction parameters: U, JH
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 Hubbard-Kanamori Hamiltonian for multi-orbital systems

Spin flip

Pair-hopping
Only density-density terms
Included. Hund treated as Ising term

U’=U – 2JH J’= JH Equivalent orbitals

No hybridization
Two interaction parameters: U, JH No crystal field
E. Bascones [email protected]
 Electronic correlations in multi-orbital systems: Hund metals

6 electrons in 5 orbitals Colour plots: Quasiparticle weight Z

1

0.8
Hund metal small Z
0.6 (strongly correlated, even for small U/W)

0.4

0.2 n=6 Mott insulator

0.0

Weakly correlated metal

Boundary (crossover):
different dependence
on interaction parameters
than the Mott transition

Slave spin. Only density-density terms included Fanfarillo & EB, arXiv:1501.04607
E. Bascones [email protected]
 Electronic correlations in multi-orbital systems: Hund metals

6 electrons in 5 orbitals Colour plots: Quasiparticle weight Z

1

0.8
Hund metal
Suppression of Z
0.6 associated to the
0.4 atomic spin polarization

0.2 n=6 Mott insulator

0.0
U=W
Enhancement of
Spin fluctuations

Loss of kinetic energy to

satisfy Hund’s rule

Slave spin. Only density-density terms included Fanfarillo & EB, arXiv:1501.04607
E. Bascones [email protected]
 Electronic correlations in multi-orbital systems: Hund metals

6 electrons in 5 orbitals Colour plots: Quasiparticle weight Z

1

0.8
Hund metal
Suppression of Z
0.6 associated to the
0.4 atomic spin polarization

0.2 n=6 Mott insulator

0.0
JH/U=0.3
S=2

JH/U=0.15
Mott insulator
Hund metal JH/U=0.015

JH/U=0.01

Slave spin. Only density-density terms included Fanfarillo & EB, arXiv:1501.04607
E. Bascones [email protected]
 Hund metals: Screening of magnetic moments
1 4 S=2
Hund metal
High spin 0.8
Strong correlations 3
0.6

0.4 1.8
Hund metal Mott insulator
Low spin High spin 0.2
0.6
Moderate correlations 0.0
0.0
0 0.5 1.0 1.5 2.0 2.5
U/W

E. Bascones [email protected]
 Electronic correlations in multi-orbital systems: Hund metals

6 electrons in 5 orbitals Colour plots: Quasiparticle weight Z

1

0.8
Hund metal
0.6

0.4

0.2 n=6 Mott insulator

0.0
Charge
fluctuations
Fanfarillo & EB, arXiv:1501.04607

Different behavior
of charge and
Quasiparticle
quasiparticle weight
weight

Slave spin.
Only density-density terms included
E. Bascones [email protected]
 Hund metals: Screening of magnetic moments
1
Hund metal
High spin 0.8
Strong correlations
0.6

0.4
Mott insulator
High spin 0.2 Experimental technique
which probes long time scales
0.0 (neutron diffraction t~ 10.15 fs)
0 0.5 1.0 1.5 2.0 2.5
U/W

Experimental technique
which probes long time scales
(X-ray PES t~0.1-1 fs)

Hansmann et al, PRL 104, 197002 (2010)

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 Hund metals: Finite temperature behaviour

Quasiparticle weight Z Metal. Small Quasiparticle Weight

1
Hund metal
High spin 0.8
Strong correlations
Fermi liquid only at low temperatures (T*)
0.6
Incoherent behavior above T*
0.4
Mott insulator
High spin 0.2

0.0
0 0.5 1.0 1.5 2.0 2.5 Spectral weight
in ARPES (Quasiparticle
Spin susceptibility. Spin freezing lost above T*)

Bad metallic behavior

at above T*

Haule & Kotliar, NJP 11, 025021 (2009)

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 Hund metals: Doping dependence

6 electrons in 5 orbitals Colour plots: Quasiparticle weight Z

Hund metal

Half-filling
Mott insulator
Electron-hole asymmetry
around n=6

Strong correlations
linked to avoiding
double occupancy
Fanfarillo & EB, arXiv:1501.04607
E. Bascones [email protected]
 Correlations in multi-orbital systems

Weak correlations Localized electrons

(properties, origin of magnetism (properties, origin of magnetism
and of superconductivity and of superconductivity
described in terms of itinerant described in terms of localized
electrons. Fermi surface physics) electrons. Spin models)

Hund metal
(Correlations due
to Hund’s coupling)

6 electrons in 5 orbitals
Average doping n=1.2 Increase of correlations
Like doped Mott insulators towards half-filling
(note differences with single
orbital doped Mott insulator)

E. Bascones [email protected]
 Correlations in iron superconductors
5 band model for iron superconductors 5 band model (Equivalent orbitals)
6 electrons (undoped) 6 electrons

Correlations enhanced
Towards half-filling
(hole-doping)

Yu & Si, PRB 86, 085104 (2012), Ishida & Liebsch PRB 81, 054513 (2010) Review: EB et al, arXiv:1503.04223
E. Bascones [email protected]
 Correlations in iron superconductors
5 band model for iron superconductors
6 electrons (undoped)
Drop of quasiparticle
weight (crossover)

Orbital differentiation
(some orbitals more
correlated than other)

At finite temperatures the

most strongly correlated
orbitals can be incoherent
while the other ones remain
metallic

Figs: Si & Yu, PRB 86, 085104 (2012), Review: EB et al, arXiv:1503.04223
E. Bascones [email protected]
 Correlations in iron superconductors
5 band model for iron superconductors
6 electrons (undoped)
Drop of quasiparticle
weight (crossover)

Orbital differentiation
(some orbitals more
correlated than other)

Correlations enhanced
Towards half-filling
(hole-doping)

Yu & Si, PRB 86, 085104 (2012), Ishida & Liebsch PRB 81, 054513 (2010) Review: EB et al, arXiv:1503.04223
E. Bascones [email protected]
 Correlations in multi-orbital systems

Weak correlations Localized electrons

(properties, origin of magnetism (properties, origin of magnetism
and of superconductivity and of superconductivity
described in terms of itinerant described in terms of localized
electrons. Fermi surface physics) electrons. Spin models)

6 electrons in 5 orbitals Orbital differentiation

Hund metal Average doping n=1.2 (some orbitals more
(Correlations due Correlations increase towards correlated than others)
to Hund’s coupling) Half-filling (hole-doping) Localized+itinerant

E. Bascones [email protected]
 The (p,0) magnetic state of iron superconductors
High spin

Low spin
S=2

Double exchange-like magnetism

with localized (xy and yz) and
itinerant (zx, 3z2-r2, x2-y2) orbitals

Behavior like J1-J2 Heisenberg

model (magnetization, orbital
filling, competition between
different magnetic states)

Violates Hund’s rule

EB et al, PRB 86, 174508 (2012)
(low spin)
E. Bascones [email protected]
 The (p,0) magnetic state of iron superconductors
High spin

Low spin
S=2

EB et al, PRB 86, 174508 (2012)

E. Bascones [email protected]
 The (p,0) magnetic state of iron superconductors
High spin

Low spin
S=2

EB et al, PRB 86, 174508 (2012)

E. Bascones [email protected]
 Iron superconductors in the (U,JH) phase diagram
FeP compounds m*/m~1.4-2

FeAs compounds
• m*/m~ 2-3 (122, 1111)
up to 5-6 (111)
• mordered~ 0.07-1 mB
mX-ray~ 1.3-2 mB
• Neutrons: Moments at high T
& spin waves up to high energy
• Electron-hole asymmetry in
correlations (K-Rb-Cs-122
Hund metals)
• c increases with T
• Sign of resistivity anisotropy FeSe, FeTe KxFey-xSe2
not expected from double • Double stripe ordering in FeTe • m~3 m B
exchange not compatible with nesting • Orbital selective
• Compatible with ab-initio • m*/m~3.5-7 incoherence at finite T
• Orbital selective incoherence
at finite T
• c decay with T above T* (180 K-FeSe, 70 K-FeTe)
Review: EB et al, arXiv:1503.04223
E. Bascones [email protected]
 My collaborators

María José Calderón Belén Valenzuela

Laura Fanfarillo
ICMM-CSIC ICMM-CSIC ICMM-CSIC
(now at SISSA, Trieste
& La Sapienza-Rome)

EB et al, PRB 86, 174508 (2012) Fanfarillo & EB, arXiv:1501.04607 Review: EB et al, arXiv:1503.04223
E. Bascones [email protected]