Title

Study of Multilayered Cuprate Superconductors by
Electronic Raman Scattering

Author(s)Giulio, Vincini

Citation

大阪大学, 2018, 博士論文

Version Type VoR
URL

https://doi.org/10.18910/70715

rights
Note

Osaka University Knowledge Archive : OUKA
https://ir.library.osaka-u.ac.jp/
Osaka University

Osaka University – Graduate School of Science
Department of Physics

Doctor of Philosophy Dissertation

Study of Multilayered Cuprate
Superconductors by Electronic Raman
ScatteringbyGiulio Vincini
Osaka 2018

Index
1:Introduction .................................................................................................................................................... 1
2:Background ..................................................................................................................................................... 3
2.1 High temperature superconductivity ....................................................................................................... 3
2.2 Cuprates general concepts ....................................................................................................................... 5
2.3 Phase diagram of cuprates ....................................................................................................................... 8
2.3.1 Mott insulating phase and anti-ferromagnetism. ............................................................................. 9
2.3.2 Superconductivity............................................................................................................................ 122.3.3 Pseudogap ....................................................................................................................................... 15
2.3.4 Competing orders. ........................................................................................................................... 16
2.3.5 Superconducting fluctuation ........................................................................................................... 19
2.3.6 Strange metal .................................................................................................................................. 21
2.3.7 Overdoped regime .......................................................................................................................... 22
2.4 Multilayer cuprates ................................................................................................................................ 22
2.5 BSCCO ..................................................................................................................................................... 24
2.6 Previous Raman Experiments ................................................................................................................. 27
2.7 Previous Raman calculations .................................................................................................................. 29
2.8 Purpose of this work .............................................................................................................................. 31
3:Methods ........................................................................................................................................................ 33
3.1 Sample growth & annealing ................................................................................................................... 33
3.2 Raman..................................................................................................................................................... 34
3.3 Kubo calculations ................................................................................................................................... 41
3.4 ARPES...................................................................................................................................................... 43
3.5 Others: SQUID & XRD ............................................................................................................................. 47
4:Experimental Results and Discussion ............................................................................................................ 49
4.1 Sample Preparation ................................................................................................................................ 49
4.2 Raman Results ........................................................................................................................................ 53
4.3 Average and Layer doping determination.............................................................................................. 59
4.4 Doping dependence of the Raman peaks .............................................................................................. 61
5: Analysis based on ARPES .............................................................................................................................. 65
5.1 Bi2212 Analysis ....................................................................................................................................... 65
5.1.1: Calculation Input preparation ........................................................................................................ 65
5.1.2: Calculation Results and Discussion ................................................................................................ 74

5.2: Bi2223 Analysis ..................................................................................................................................... 85
5.2.1: Calculation Input preparation........................................................................................................ 85
5.2.2: Calculation Results and Discussion ................................................................................................ 91
6: Conclusions .................................................................................................................................................. 99
6.1: Bi2223 experimental Raman results ..................................................................................................... 99
6.2: Bi2212 Raman results analysis based on ARPES ................................................................................. 100
6.3: Bi2223 Raman results analysis based on ARPES ................................................................................. 101
6.4: Closing remarks .................................................................................................................................. 102
Publications ................................................................................................................................................... 103
Conference presentations ............................................................................................................................. 104
Acknowledgements ....................................................................................................................................... 105
References ..................................................................................................................................................... 107

1:Introduction
Since their discovery in 1985 the cuprates superconductors have attracted a huge attention fromthe community in the field of solid state physics, and a tremendous amount of work has been put
into clarifying the mechanism that gives to these superconductors such a high critical temperature,
however some of the fundamental questions still remain unanswered. The first of these is surely
the pairing mechanism, and therefore the driving force of superconductivity. Nevertheless thejoint work of the community took us much closer to understanding the rich physics of thesematerials. However while new experimental observation take us closer to understanding thecuprates, they also bring forth new questions that are sometimes are not easily solved.
A perfect example of these long standing issues in the research of cuprates superconductors is thedoping dependence of the superconducting gap. While in the overdoped regime the gap size is
proportional to the critical temperature TC, in the underdoped region the antinodal and nodal gaps
show different doping dependence, with the antinodal gap increasing monotonically[1] and thenodal gap staying constant or decreasing with lower doping, and this is accompanied by adeviation of the gap function from the simple d-wave symmetry.[2]–[4] Therefore in theunderdoped regime we have the highly unusual situation where neither the nodal nor theantinodal gap seem to be proportional to the critical temperature.
This behaviour is likely connected to the poorly understood pseudogap state, which dominates thephase diagram in the underdoped region. Even though from recent experiments results it seems
likely that the pseudogap state originates from a different order parameter than superconductivity,
the fundamental nature of the pseudogap state is still unclear. Additionally the relationship of thepseudogap with superconductivity is not fully understood. While it is true that these two states doseem to compete for the area of the Fermi surface close to the antinode, on the other hand theycoexist and it is not clear how superconductivity is influenced.
A further unclear point is that the different nodal and antinodal energy scale in the underdopedside is picked up in a different way by different momentum sensitive techniques such as Angle
Resolved Photoemission Spectroscopy ARPES and Raman. This apparent inconsistency needs to beaddressed to improve our understanding of the doping dependence of the pseudogap andsuperconductivity.
Another interesting topic of the field is the study of multilayer cuprates. The main reason for theinterest in these is that the Tc of the cuprates strongly depends on the number of Cu-O2 planes perunit cell n. Tc increases when n increases from n=1 to n=3, where it reaches its maximum, and thendecreases for n≥4. [5] Up to date the cause of this Tc enhancement is not clear, with several
possible factor being proposed, such as the tunnelling of Cooper pairs between different layers[6],the increased next-nearest neighbour hopping parameter t’[7] and the disorder protection of theinner Cu-O2 plane IP by the outer Cu-O2 planes OP.[8] Additionally for n≥3 an interesting situationarises, namely that Cu-O2 planes with different doping level coexist in the same sample, and the1

OP is more doped than the IP due to its proximity to the charge reservoir layer CRL.[9] How theselayers interact with each other, and how this affects TC is an open problem that should be solved
to understand the source of the high TC of the triple layer cuprates. Unfortunately the difficulty ofgrowing high quality single crystal is higher in the case of triple layer cuprates, and this held backthe research for long. However the recent improvement in sample quality now allows to carry out
new observations on these materials.
In this work we focused on Bi2Sr2Ca2Cu3O10 Bi2223 the triple layer member of the BSCCO family(Bi2Sr2Can-1CunO2n+4) of cuprates superconductors. Using Electronic Raman Scattering ERS, which isa powerful energy and momentum resolved technique, we investigated this triple layer cuprate.
We were able to observe a signature of the double superconducting gap of this material,
originating from the two inequivalent kind of Cu-O2 plane (IP and OP), which has never been
observed previously by Raman. The temperature and doping dependence of this double peakstructure was investigated, and a higher energy scale for this triple layer material, with respectwith other single and double layer cuprates, was observed. These results have been explained by a
combination of multilayer effects and the complex relationship between superconductivity andthe pseudogap. This could be a step forward in understanding the non-trivial physics of multilayer
cuprates.
Additionally in order to try to solve the apparent inconsistencies between Raman and ARPES, andto improve our understanding of the Raman spectra, we performed calculations of the Raman
spectra, starting from the ARPES data, using the Kubo formalism. This was done for the double
layer component Bi2Sr2Ca1Cu2O8 Bi2212 samples of three different dopings and for an optimally
doped Bi2223 sample. The doping dependent Bi2212 study allowed us to show how theinconsistencies between Raman and ARPES are likely to be only due to a difference in how these
two techniques pick up the effect of the coexistence between superconductivity and thepseudogap, and how the relationship between these two states affects the Raman spectra. The
Bi2223 calculation was successful, and constitutes a strong proof that the origin of theexperimental double peak structure, observed in this work, is truly the double superconducting
gap of this material originating from the two inequivalent Cu-O2 planes, the IP and the OP.

2

2:Background
2.1 High temperature superconductivity
The history of superconductivity begins in the early years of the 20 th century, when scientists were
wondering how the resistivity of metals would have been close to the absolute zero. Thanks to the
newly discovered Hampson–Linde cycle for the liquefaction of gases, investigation of the lowtemperature resistivity of materials had just became possible. Driven by this interest the Dutch
physicist Heike Kamerlingh Onnes was able in 1908 to produce liquid helium for the first time.
With this newly achieved technology Onnes and Jacob Clay started measuring the lowtemperature resistivity of platinum and gold. They later moved to mercury and in 1911 theyobserved an abrupt drop in the resistivity at 4.19 K. They observed that at this temperature theresistivity of mercury became almost zero. This observation marked the discovery ofsuperconductivity. Onnes was also able to show the persistence of the current in superconducting
rings without an applied voltage, and in 1913 he received the Nobel Prize for the discovery ofSuperconductivity. In the following decades several other superconductors were discovered, butthese had low critical temperature Tc (<20K).
A turning point in the history of superconductivity is when in 1957 John Bardeen, Leon N. Cooper,
and Robert Schrieffer formulated their theory of superconductivity, the BCS theory[10], for which
they earned the Nobel Prize in Physics in 1987.The BCS theory gave for the first time a successful
microscopic picture of the phenomenon. The fundamental idea is that electrons bind themselvesin Cooper pairs. Here a weak positive attraction between two electrons mediated by the couplingwith the lattice (phonon) can cause them to form pairs, despite the strong Coulomb repulsion
between the electrons. The so formed pairs could condense in the same way bosons condense in asuperfluid state. Prediction based on the BCS theory suggested that the pairing energy had to besmaller than the typical phonon energy, and therefore it was believed that Tc could not exceed
30K[11].
However in 1985 a new superconductor was discovered that exceeded this limit. In that year
Bednorz and Müller discovered the copper oxide perovskite La2-xBaxCuO4 which had a Tc of
35K.[12] This was the first of a new family of superconductors, which re-sparked interest in thefield, the cuprates. These had as common feature a layered structure and CuO2 planes separated
by different ionic layers named charge reservoir layers CRL. The cuprates were of great interest
not only because the maximum Tc at ambient pressure was quickly raised to 133K-138K in
HgBa2Ca2Cu3O8+δ [13], [14], but also because the BCS theory could not predict many of theirfundamental characteristics.
For some time the cuprates remained the only High Temperature Superconductors HTS, but thischanged in 2006, when Iron Based Superconductors IBS where discovered[15], [16]. Thesematerials contain a common structural unit of iron - pnictide conductive layers separated by an
insulating blocking layer. The discovery of IBS was surprising since iron, having a large magnetic
momentum, was believed to be harmful to superconductivity. IBS were believed to be the new3high temperature superconductor, and showing such a good promise, they re-sparked a hugeinterest in the field of superconductivity.
Surprisingly though the record Tc held by cuprates was not broken by IBS. Instead in 2015superconductivity was discovered in H2S with a Tc of 203 K at extremely high pressures (around
150 gigapascals)[17]. Even though actually the phase responsible for such high T c is likely to be H3S,
formed from H2S by decomposition under pressure. What is even more surprising is that unlike thecuprates or the IBS which show exotic properties and cannot be simply explained by the BCS
theory, the newly discovered H2S can be explained by the BCS theory and in fact numerous
calculation have predicted high transition temperatures for many hydrides.[18]Even though more than one century of research on superconductivity has been carried out, agreat part of its rich physics remains poorly understood, and many surprising results keep on being
uncovered. Although much work is still needed, the huge effort of many researchers got us closer
to understanding this fascinating phenomenon and allowed us to increase the T c enormously. As it
can be seen form Fig. 2.1 we went from the few kelvin of mercury to the 203K reached recently,
getting us closer to the dream of room temperature superconductivity.

Fig 2.1 Superconductors Tc plotted against the year of discovery. Taken from Ref [19]. Axes are notin scale for easier visualization.

4

2.2 Cuprates general concepts
Following the discovery of La2-xBaxCuO4 other copper oxide based superconductors where
discovered. These all have in common one or multiple CuO2 layers separated by different ionic,
electronically inert, buffer layers. The buffer layers can contain different ions such as lanthanum,
barium, strontium, or other atoms. These ions act as a stabilizer of the crystal structure and thedoping can be controlled by changing the chemical composition of this buffer layer, which istherefore usually referred as charge reservoir layer CRL.

Fig. 2.2 Crystal structure of some example cuprates superconductors. Taken from Ref [20]. All
cuprates have one or multiple CuO2 layers in common (bottom left) separated by different ionicbuffer layers.
The layered structure of cuprates, with weak interaction between the layers, makes cuprates
quasi-2D materials, and therefore gives them a quasi 2D electronic structure. Nevertheless forrealistic band dispersion calculations, and to introduce the material variability interaction out ofplane should be considered. [7], [21] A single band crosses the Fermi level in cuprates whichcomes mainly from the hybridization of Cu dx2-y2 and O px py states (shown in the bottom left of Fig.
2.2) and forms a large hole like fermi surface as it can be seen in Fig2.3 (e).

5Fig2.3 Taken form Ref[1]. a Superconducting gap anisotropy in cuprates, first observed in 1993 in
Bi2212 (Ref[22]) the A and N are the nodal and antinodal spectra respectively. b Schematic of a dwave superconducting order parameter. The gap is zero at the node A where it changes sign andreaches the maximum at the antinode B. c Bi2212 gap measured by synchrotron ARPES. d Bi2212
Gap measured by laser ARPES. e Three-dimensional ARPES data set, showing the quasi-particle
dispersions both perpendicular and parallel to the Fermi surface near the node, reproduced from
Ref [23].
As it will be discussed more in detail later on, the cuprates are antiferromagnetic Mott insulators
at zero doping. By doping electrons or holes superconductivity appears, and the superconducting
gap opens in the above mentioned band. In this work the discussion will be limited to hole doped
cuprates for simplicity. In contrast with the isotropic s-wave gap of conventional BCS
superconductors the gap in cuprates, was shown to possess d-wave symmetry [1] as it can be seenin Fig.2.3. The superconducting order parameter changes sign at the (0,0)-(π,π) axes of the
momentum space. These zones where the gap becomes zero are named nodes, while the zones
where the gap is maximum, along the (0,0)-(π,0) axes, are referred as antinodes. A schematic
representation of the d-wave (dx2-y2) order parameter can be seen in Fig.2.3 (b).
One feature of the conventional BCS superconductor, where phonon is the pairing interaction, is
the isotope effects. This is the dependence of Tc on the isotope mass M. Changing the isotope
mass changes the energy of the phonon and therefore Tc according to the empirical relations Tc
6∝M-α. The isotope coefficient α predicted form the BCS theory is 0.5. On the other hand as it canbe seen in Fig2.4 the cuprates show a non-trivial α which depend on the doping p and on thenumber of CuO2 planes per unit cell n. From the early days of the research on cuprates similar
observations on the isotope coefficient α suggested that the phonons had to be ruled out from thepossible pairing interactions. [24]Fig2.4 a Doping dependence of the isotope coefficient α. Taken from Ref.[25] b Dependence on
the number of layer per unit cell of the isotope coefficient α. Taken from Ref.[26]
Cuprates are all type II superconductors, meaning that due to their short coherence length ξ withrespect to the penetration length λ, if a strong enough magnetic field is applied, the filed will not
be completely expelled from the superconductor. Instead some lines of magnetic flux will passthrough the material, turning a region of the superconductor normal, these region are known as
vortex, or an Abrikosov vortex. The existence of type II superconductor had been predicted by the
Ginzburg-Landau theory[27], which predicted a negative energy of the interface between
superconducting and normal phases. Experimentally type II superconductors have two criticalfields, which separate the 3 regions of complete Meissner effect, vortex state and suppression ofsuperconductivity.
The hole doped cuprates feature a rich and complex phase diagram which can be seen in Fig2.5
and that will be treated more in detail later on. Different competing orders appear at low
temperature. Among these the pseudogap PG attracted a strong interest from the community.
This appears as a suppression of the density of states, in the underdoped and optimally doped
cuprates, at temperature much larger than Tc. The nature of the pseudogap was and still is acontroversial topic. Two main theories existed, one attributing the pseudogap to a precursor stateof superconductivity and the other attributing the pseudogap to a different competing order.

7

Recent experiments point to the latter as correct answer, but some issues still remain to beclarified.
One of the perquisite to achieve high Tc according to the BCS theory is a high density of states at
the Fermi level NF [28], however the cuprates, at room temperature above the superconducting
region, are such poor conductors that they can hardly be classified as metals. Additionally the
conductivity in this region exhibits frequency and temperature dependence which areincompatible with the conventional theory of metals. This led to this region of the phase diagram
to be referred as “strange metal” which can be seen in Fig 2.5. This phase and the Mott insulator
phase are a consequence of the strong correlation between electrons. Similar behaviour has been
observed numerous non superconducting materials [29] The cuprates and these nonsuperconducting materials, in which the interaction between the electrons is strong, are therefore
a new class of materials called “highly correlated electron systems” which cannot be welldescribed by the conventional quantum theory of solids.
The cuprates showed numerous inconsistencies with the conventional BCS superconductors, andtherefore earned the name of unconventional superconductors. The most prominent of thesedifferences is, most likely, the pairing interaction, and therefore the nature of the superconducting
mechanism. As stated before the phonons have been ruled out from the possible pairing
interactions and several other candidates have been proposed. These include charge or spin
mediated pairing. However no clear solution has been found and this fundamental point is still
under debate.

2.3 Phase diagram of cuprates
The phase diagram of cuprates is packed with different phases, most of which have a rich physics
behind. An example of phase diagram of the cuprates can be seen in Fig.2.5. As stated before in
the underdoped side the strong correlation effects make the cuprates Mott insulators, and below
TN, antiferromagnetism kicks in (blue area in Fig.2.5). With increasing doping after the first critical
doping pmin superconductivity appears at low temperature. The superconducting phase is present
in a dome like area of the phase diagram (green area in Fig.2.5), where the maximum Tc is reachedat the optimal doping popt=0.16, and it disappears at the second critical doping pmax in theoverdoped side. In the underdoped side below T* the pseudogap phase is visible (yellow area in
Fig.2.5). As it can be seen in Fig.2.5 the pseudogap phase coexists with superconductivity at low
temperature, and this is indicated by the lighter green area. Above T* and above Tc atintermediate doping, the previously mentioned strange metal phase appears, which is indicatedwith the magenta area in Fig.2.5. At higher doping the anomalies of the strange metal phase
disappear, and are substituted by a Fermi liquid-like behaviour (white area in Fig.2.5). Additionallyto these phases a variety of different competing order are seen in the phase diagram, competingwith superconductivity. These include spin-density-wave SDW or stripe order, charge-density –wave CDW, electron-nematic phase and others. Some interesting aspects of these orders remain
8yet to be explained, but their existence and many of their main features were explained andanticipated by theory.[30]In the following sections the most relevant phases will be examined more in detail.

Fig.2.5 Phase diagram of cuprates taken from Ref.[31]2.3.1 Mott insulating phase and anti-ferromagnetism.
The zero doping curates accommodate an even number of electrons per unit cell, therefore theconventional band theory would predict them to be metallic. However strong correlation between
the electrons, and in particular strong Coulomb repulsion between the electrons, makes theunderdoped cuprates Mott insulators. Defining U as the on-site Coulomb repulsion and t as thetransfer integral between neighbouring atoms, in the case of half-filled band, when t > U a metallic
behaviour can be expected, but if on the other hand U > t a Mott insulator is expected. In this casethe lower energy state will be achieved by localized electrons around their respective ions, thatminimize the Coulomb repulsions energy term. These localized electrons cannot occupy the samesite unless they are given the on-site repulsion energy U, and therefore the material will be a Mott
insulator, with an energy gap of U (Hubbard gap).
The localized electrons spins interact between each other. If the spins of the two neighbouring
electrons are antiparallel they could penetrate in each other site without violating the Pauli
exclusion principle, even if this is prevented by the strong U. Therefore if the spins are antiparallel
there will be a gain in energy given by the exchange constant J, on the other hand if the spins are9parallel there will be no gain in energy since the Pauli exclusion principle prohibits the process.
Following these considerations there can be two possibilities. One is AFM long range order, whichis indeed observed as seen in the phase diagram in Fig.2.5. The other possibility is that theelectrons form paired singlet without requiring long range order. In this case even if the electrons
are localized the spins can move freely. This second possibility is the so called resonating valencebond or quantum spin fluid.[32]With increasing doping the AFM and Mott insulating phase disappears as it can be seen in thephase diagram in Fig.2.5. The Neel temperature TN decreases and the sample starts showing
metallic behaviour entering the strange metal phase, while at low temperature superconductivity
appears.

Fig.2.6 Taken from Ref.[33] a Crystal-field splitting and hybridization giving rise to the Cu-O bands.
b Crystal structure of La2CuO2 LCO
To understand the electronic structure of the underdoped cuprates the single layer La2-xSrxCuO2
LSCO can be discussed for simplicity. In particular, to examine the underdoped regime, the undoped La2CuO2 LCO can be used whose crystal structure is shawn in Fig.2.6 (b). The outer 3d shellof the Cu2+ atoms contains nine electrons, while the O2- ions have an outer 2p shell which is fully
filled with 6 electrons. Forming an octahedron with the 6 neighbouring O atoms splits the Cu 3dlevels in t2g and eg levels. The octahedron in LCO is distorted, with a longer Cu-O bonding directionin the c direction than in the ab planes. This is the so called Jahn-Teller distortion which splits
furtherly the 3d orbitals in dyx, dzx, dxy, dz2-r2 and dx2-y2. All of these are fully occupied except for the
dx2-y2 orbital which is the highest in energy and accommodates only a single electron. The oxygen p
orbitals separate in pσ pπ┴ and pπ║. Of these pσ is parallel to the Cu-O bonding directions while pπ┴
and pπ are perpendicular to the Cu-O bonding directions, with pπ║ being in plane and pπ┴ being outof plane. The oxygen pσ strongly hybridize with the copper dx2-y2 orbitals. The above described
splitting and hybridization can me seen in Fig.2.6 (a). With these considerations one of thesimplest way to treat the problem is to write a Hamiltonian for non-interacting electrons,
10considering only the Cu dx2-y2 orbital and the O pσ orbitals (px or py) and considering only thenearest neighbour hopping in the form:††
𝐻0 = 𝜖𝑑 ∑ 𝑛𝑑𝜎 (𝑖) + 𝜖𝑝 ∑ 𝑛𝑝𝜎 (𝑗) + ∑ 𝑉𝑖𝑗 (𝑑𝑖𝜎𝑝𝑗𝜎 + 𝑝𝑗𝜎
𝑑𝑖𝜎 )
𝑖𝜎

𝑗𝜎

(2.1)

<𝑖𝑗>𝜎

†
†
Here 𝑑𝑖𝜎creates a hole in the Cu dx2-y2 orbital, 𝑝𝑗𝜎creates a hole in the O px (or py), < 𝑖𝑗 >indicates the summation on nearest neighbour and 𝑉𝑖𝑗 = (−1)𝛼𝑖𝑗 𝑡𝑝𝑑 where 𝑡𝑝𝑑 is the hopping
integral between oxygen and copper orbitals and 𝛼𝑖𝑗 changes sign according to the relative
position of the O and Cu atoms. However this simple Hamiltonian will give metallic solutions, since
the conventional band theory always predict metallic band structure for half filled bands. To
improve the calculation, the correlation between the electrons must be considered. Adding the
Coulomb repulsion between electrons U and considering also the nest-nearest neighbour hopping
𝑡𝑝𝑝 we can write the Hamiltonian:[34]††𝐻 = 𝜖𝑑 ∑ 𝑛𝑑𝜎 (𝑖) + 𝜖𝑝 ∑ 𝑛𝑝𝜎 (𝑗) + 𝑡𝑝𝑑 ∑ (𝑑𝑖𝜎𝑝𝑗𝜎 + ℎ. 𝑐. ) + 𝑡𝑝𝑝 ∑ (𝑝𝑗𝜎𝑝𝑗′ 𝜎 + ℎ. 𝑐. )𝑖𝜎𝑗𝜎<𝑗𝑗 ′ >𝜎

<𝑖𝑗>𝜎

𝑝 𝑝
𝑑 𝑑
𝑑 𝑝
+ 𝑈𝑑 ∑ 𝑛𝑖↑
𝑛𝑖↓ + 𝑈𝑝 ∑ 𝑛𝑗↑
𝑛𝑗↓ + 𝑈𝑝𝑑 ∑ 𝑛𝑖𝜎
𝑛𝑖−𝜎
𝑖

𝑗

(2.2)

<𝑖𝑗>,𝜎Here the terms 𝑈𝑑 , 𝑈𝑝 and 𝑈𝑝𝑑 are the on site Coulomb repulsion between holes on the copper
site, on the oxygen site and the coulomb repulsion between holes on nearest neighbour site
respectively. This triple band Hubbard Hamiltonian can give a correct but approximate descriptionof the underdoped cuprates electronic structure. In cuprates since U>W (where W=8t is the typical
width of the band) from the metallic solution of the Hamiltonian in (2.1) where 3 bands arepresent (bonding non-bonding and anti-bonding), shown in Fig.2.7 (a), a Mott Hubbard gap opens
on the antibonding band, in the solution of the Hamiltonian in (2.2). Here there are 2 possibilities
depending on the values of Ud and Δpd, where Δpd = 𝜖𝑑 − 𝜖𝑝 is the anion cation charge transfer.In
case W<Ud< Δpd we have a Mott Hubbard insulator, shown in Fig.2.7 (b). The other possibility,
which is the case for cuprates, arises when W< Δpd <Ud , in this case the material is a chargetransfer insulator, shown in Fig.2.7 (c).

Fig.2.7 a Density of states for a calculation not considering the Coulomb repulsion U using a
Hamiltonian similar to Eq.2.2. Three bands appear, bonding non-bonding and antibonding band.
The result of this calculation is metallic. b Mott Hubbard insulator density of state. c Chargetransfer insulator density of state.
112.3.2 Superconductivity
As previously mentioned, doping hole in the material, anti-ferromagnetism is suppressed andsuperconductivity appears at low temperature. The superconducting phase has a dome-like shapein the phase diagram, starting at pmin in the underdoped side and ending and pmax in theoverdoped side. The maximal Tc is reached at the optimal doping popt=0.16. A widely usedapproximate formula to describe the shape of the superconducting dome in the phase diagram is:
Tc/Tc,max=1—82.6 (p-0.16)2 [35], [36]. However this is a rough approximation. For example, as it canbe seen in Fig.2.5 at p=0.12 there is a suppression of Tc. This doping is where the charge density
wave is strongest (maximum TCDW), and its competition with the superconductivity causes the
suppression of Tc.[37]The superconducting gap is anisotropic in the momentum space, and as stated earlier it was
shown to possess d-wave (dx2-y2) symmetry. This was understood in early studies using different
techniques including ERS[38], [39], ARPES[22], [40], penetration depth[41] and phase sensitive
measurements.[42] The gap can therefore be described by the d-wave (dx2-y2) function, where theamplitude of the gap in the momentum space is given by: ∆(𝒌) = ∆0 |cos 𝑘𝑥 𝑎 − cos 𝑘𝑦 𝑎|/2
However this function is a good representation of the superconducting gap only in the overdopedside of the superconducting dome. In the underdoped samples towards the antinode a deviationfrom the d-wave function was identified by ARPES. [43], [44] As it can be seen from Fig.2.8 in theantinodal side there is a deviation from the d-wave gap profile extrapolated from the nodal gap,

Fig.2.8 Deviation of the gap from the d-wave function in Bi2201 taken from Ref.[44]. In the upper
panels the gap value is shown below and above Tc. In the lower panes the spectral weightassociated with the superconducting gap WCP is compared to the one associated with thepseudogap WPG.
12

and this deviation becomes stronger in the underdoped samples. This deviation is commonly
associated with the pseudogap, which coexists with the superconducting gap, and is usuallyreferred as two gap behaviour. However the source of this deviation is controversial. There havebeen works reporting absence of any deviation in a wide range of doping, suggesting that thedeviation may be due to cation substitution that it is sample specific.[45]One of the problems that come with the two gap behaviour is the doping dependence of thesuperconducting gap. In the framework of the BCS theory there should be a simple proportionality
relationship between the critical temperature and the gap value Tc∝Δ. However while this relation
could hold in the overdoped side, it is not true in the underdoped side. In the underdoped side theantinodal gap increases with lower doping while the Tc decreases and this can be seen in Fig.2.9. In
the strongly underdoped side showed in Fig.2.9 the antinodal gap increases with lower doping,while the nodal gap decreases. This opposite doping dependence is sometimes referred as twoenergy scale, and it also observed by other techniques such as Raman. [46]–[49] One may thinkthat in the underdoped side the Tc is determined not by the antinodal, but by the nodal gap.
However ARPES reported that in a wide range of doping the nodal gap is in fact constant. [2] As it
can be seen from Fig.2.10 (d) the nodal gap is almost constant between p = 0.076 and p = 0.19,
and it only decreases outside of this interval in the strongly underdoped and overdoped side. Thisfurtherly complicates the problem, since in this region it seems that neither the nodal nor theantinodal gap follow the doping dependence of Tc, and it is therefore unclear what determines thecritical temperature.

Fig.2.9 Doping dependence of the nodal and antinodal gaps in Bi2212 taken from Ref.[43]Another antinodal effect in underdoped samples that is associated with the pseudogap is theconfinement of Cooper pairs in the antinodal region with underdoping.[50] Here the idea is that
due to the competition between superconductivity and the pseudogap, with decreasing doping
the Cooper pairs are suppressed and then expelled from the antinode and this is consistent withthe tunnelling[51], [52] and the ARPES data[53]–[55]. In this case, in the underdoped side thesuperconductivity is confined in the nodal and intermediate region.
13

Fig.2.10 Taken from Ref.[2]. a-c Bi2212 ARPES gap profiles for samples of doping ranging fromstrongly underdoped to strongly overdoped. d Doping dependence of the nodal gap.
An important parameter for superconductivity is the superfluid density ρS. The ability of thesuperconductor to expel magnetic fields and the rigidity of the phase of the superconducting orderparameter are determined by the superfluid density. The temperature over which the phase starts
fluctuating is given by Tϑ = ρS/m*. Where m* is the effective mass. In BCS superconductors ρS isequal to the density of electrons and therefore Tϑ>>TC, meaning that as soon as the Cooper pairform the phase is stable, and that the fluctuation of the phase are irrelevant. On the other hand incuprates it was soon understood that the superfluid density is low. Additionally in the underdopedside it was shown to scale with Tc in the so called Uemura plot. [56] Since ρS is not so high, incuprates the phase stability temperature Tϑ and the pair formation temperature are comparable
and therefore phase fluctuation should be relevant.[57] Indeed superconducting fluctuations areobserved above TC, as it will be discussed in section 2.3.5, but it is not established if these are
driven by fluctuation of the phase or of the amplitude of the superconducting order parameter.
As it was previously mentioned the nature of the pairing interaction in cuprates is currently
unknown and object of debate. The previously mentioned observations regarding the isotope
coefficient α (Fig.2.4, Ref[24]–[26]) seem to suggest that the phonon mediated coupling should beruled out. However there are evidence that both ARPES and STS (Scanning Tunnelling
Spectroscopy) spectra are affected by phonons[58] and strong anomalies are observed in thephonon spectra,[59] therefore electron phonon interaction cannot be completely ruled out.
A purely repulsive interaction could also lead to pairing, though this is not trivial. This can be seenin the framework of the Hubbard model in the unrealistic weak coupling limit (U<<W=8t, where U
is the on-site electron repulsion W is the band width and t is the hopping parameter) as shown in
Ref [60].Here a renormalized two particles vertex function Γ(k) is used as interaction. In the case ofpurely repulsive interaction if Γ(k) is sufficiently momentum dependant, a sign changing
superconducting order parameter (where Δ(k) and Δ(k+Q) have opposite sign) results. In this,interactions with small momentum transfer are pair breaking, but the one with large momentum
14

transfer (near Q) promote pairing. Interestingly in the case of antiferromagnetism a peak in Γ at
the antiferromagnetic ordering vector Q = QAF is expected, [61] and this vector is also the perfectvector for scattering between the antinodal regions where the gap is the largest. This is striking
even if the antiferromagnetic order disappears with doping. The reason being that even if thesuperconducting order disappears with doping it does survive in the form of dynamical magnetic
fluctuations, as it was shown by inelastic neutron scattering and resonant X ray scattering.[62]–[65] However as stated earlier the source of pairing is still controversial.

2.3.3 Pseudogap
The pseudogap was firstly discovered by nuclear magnetic resonance as a reduction of the low
frequency spin excitations, and was therefore initially thought to be a spin gap.[66], [67] It was
subsequently observed by multiple techniques including c-axis optical conductivity[68], STS[69]and ARPES.[40], [70] Since its discovery the pseudogap was object of intense debate.[71] Twomain kind of opposite theories existed at the center of the discussion, one attributing thepseudogap to a precursor state of superconductivity, where pairs are formed but lack long range
coherence,[57] and the other attributing the pseudogap to a different order parameter thansuperconductivity.[72]–[74]Fig.2.11 Pseudogap as seen by ARPES. Taken from Ref[75] and Ref. [44]15

The pseudogap as seen by ARPES is shown in Fig.2.8 and Fig.2.11. Above TC a gap persists in theantinodal region. The first particular feature of the pseudogap is that the Fermi surface is notcompletely gapped: only the antinodal region is gaped. The ungapped nodal region was named
Fermi arc. [70] The concept of Fermi arc is highly unusual in classical physics, where the Fermi
surface were considered to be a closed contour, that, no matter how complicated, could notterminate abruptly.
The pseudogap is an antinodal phenomenon and is stronger in the underdoped side. As seen in
Fig.2.5 the pseudogap onset temperature T* increases with lower doping. Additionally with lower
doping the maximum value of the pseudogap gap increases and the pseudogap expands towards
the node, making the Fermi arc shrink,[2] and this can be seen in Fig.2.8 and Fig.2.11
More recent experimental ARPES studies seem to suggest that the pseudogap origin is to be
attributed to a different order than superconductivity,[1], [76] and not to the formation of pairs,
even though it is still unknown exactly what kind of order can be associated to the pseudogap.
These experimental observations include the previously mentioned deviation from the d-wave gap[43], [44] or more generally the so called nodal-antinodal dichotomy [1], the non-monotonic
temperature dependence of the size of the antinodal gap[76] and the breaking of particle holesymmetry.[77], [78] However this controversial issue is not yet resolved since contrasting andopposite results have also been reported. These include absence of deviation from the d-wave gap[45], [79] (which, as said before, is attributed to cation substitution, and regarded as material
dependent), a smooth evolution of the pseudogap into the superconducting gap[69] and particlehole symmetry.[80]–[82] In Fig.2.12 (d) the particle-hole symmetry breaking in Bi2201 is shown.
Here the band dispersion is extracted above T* and below TC and the back-bending momenta kG
below TC is shown to be different from the Fermi vector kF above T* indicating that the particlehole symmetry is broken. Additionally, from this figure the coexistence of superconductivity withthe pseudogap can be seen. The multiple features observed in the antinode below TC (green andblue dots in Fig.2.10 (a) and (c)) cannot be explained by a superconducting gap alone. Instead theauthors were able to reproduce these multiple features in calculations assuming coexistence of dwave superconductivity and checkboard density wave, as shown in Fig.2.12 (e).
The relationship between the pseudogap (considered as a different order than SC) and thesuperconducting gap is commonly believed to be of competitive nature.[44], [83] In this picture
superconductivity and the pseudogap coexist below TC[84] and with decreasing doping thepseudogap becomes stronger in the antinode confining the Cooper pairs in the intermediate andnodal region.

2.3.4 Competing orders.
Several different competing orders have been observed in the phase diagram of cuprates, which
break the symmetry of the crystal. The first of these that was discovered was the stripe order in
16

Fig.2.12 Taken from Ref.[78] a, b Antinodal and nodal Bi2201 ARPES spectra divided by the Fermi
Dirac function. c Energy of the observed features. d Dispersion of the observed antinodal features.
e Calculated band dispersion assuming coexistence of d-wave superconductivity and checkboard
density wave

the La2-xSrxCuO4 LSCO family.[85] Doping the AFM Mott insulator produces holes on the Cu sitesthat can move through different Cu sites, but, doing so, they produce frustration of the spins of
the electrons. To avoid this, the stripe order shown in Fig.2.13 (b) is formed. Here both charge andspin are modulated. The stripes are local AFM domains in which the order is reversed from stripe
to stripe. The holes accumulate at the boundaries between stripes to reduce the spin frustration.
Due to the reversal of the AFM order between stripes the spin modulation has double theperiodicity of the charge modulation. The stripe order was shown to be stabilized by the Low
Temperature Tetragonal LTT phase.[85]The stripe order competes with superconductivity and this can be seen from the right panel in
Fig.2.13 showing the phase diagram of LSCO. Here the maximum onset temperature Tm of the
stripe order corresponds to the drop of TC observed at x=1/8, indicating competition between thetwo orders.

17Fig.2.13 Taken from Ref. [85] and from Ref.[86] Representation of the stripe order in: a the parent
compound La2NiO4 and in b LSCO. Only the Cu sites are shown and the holes are represented withfilled circles. left panel The phase diagram of LSCO.
A highly unusual feature of the stipes is that, even if they involve crystallization of the electrons,
they stay metallic and even superconduct at low temperature. The material can be therefore
viewed as a highly unusual crystallized superconductor.[87], [88]For years the stripe order seemed to be confined in the LSCO family, until charge ordering was
discovered in YBCO,[89] bismuth and mercury based cuprates.[90]–[92] Using X-ray scattering ashort range incommensurate charge modulation was found, and it was shown to appear gradually
between 200K and 100K. [93], [94] Unlike LSCO, here only charge is modulated, and there is nosign of spin modulation. This charge density wave was shown to compete with superconductivity,
as the stripe order does, and, as in LSCO case, the dip where TC is suppressed at p=0.12
corresponds to the maximum onset temperature of the CDW, as it can be seen in Fig.2.5. The
modulation appears along two perpendicular directions along a* and b* axis. STM measurements
showed that the CDW organizes in disordered domains where the modulation along a* or b*
direction prevails.[95].
Another interesting and fundamental difference between the stripe order in LSCO and the CDW inother cuprates is that the modulation wavevector has an opposite doping dependence of the.[96]In LSCO the wavevector increases with doping, as it would in a real space driven behaviour, while
in YBCO and Bi-based cuprates it decreases with doping, as expected in a reciprocal space picture
involving vectors on the Fermi surface.
Theoretically a CDW with modulation in 2 directions is expected to cause reconstruction of the
Fermi surface, where the Fermi arc could be half of the electron pockets that would form from thereconstruction. This has never been observed. However In YBCO with p=0.1, with magnetic field,
quantum oscillation in Hall signal, with period 1/B were observed.[97] These point to a definedFermi surface, and are not consistent with truncated Fermi arc. It is possible that this signal could
18

originate from a reconstruction of the Fermi surface caused by a biaxial CDW, though this was notconfirmed.
The so called “quantum nematic liquid crystal” is yet another order that was reported in cuprates.
Unlike the stripe order and the CDW order, nematicity does not break the translational symmetry,
but breaks only the four-fold rotational symmetry. This nematic order was shown by transportmeasurements[98], [99] and by inelastic neutron scattering measurements.[100]Interestingly some STS studies were also able to pick up nematicity. Here the O site STS sub-image
shows, alongside the charge modulation, a d-wave form factor dFF-DW.[95], [101] Here according
to the author, nematicity causes the oxygen sites along x and y directions to be inequivalent, andthis gives a phase difference of π between the modulation on the Ox and Oy sites giving the dFFDW. The obtained O site STS sub-image and the schematic of the dFF-DW are shown in Fig.2.14.

Fig.2.14 Taken from Ref.[101] e O site STS sub-image showing the dFF-DW in BSCCO and NaCCOC.
f Schematic of the dFF-DW, the colour of the oxygen orbital represents the phase of themodulation. A phase difference of π exists between the modulation on the Ox and Oy sites.
Lastly a new exotic order may be present in cuprates. This would be the magnetic analogue of thecharge nematicity, involving magnetic moments on the oxygen sites. Like nematicity this novel
order would break rotational but not translational symmetry.[102]2.3.5 Superconducting fluctuation
Signatures of pairing above TC have been observed by many different techniques includingtransport and thermodynamical studies[103]–[106] and more recently by spectroscopic
studies.[76], [107], [108] As discussed before, it is commonly believed that due to the low
superfluid density of cuprates, pairing appears at a higher temperature than Tc, but that pairs lack
long range phase coherence. Therefore these superconducting fluctuations are believed to bedifferent than the normal BCS superconducting fluctuations, where the amplitude of the19superconducting order becomes zero at TC causing the fluctuations. Instead in cuprates theamplitude of the pairing order would be non-zero above Tc and the phase disorder would be
responsible of the absence of macroscopic superconductivity.[109] However it is still controversial
whether the fluctuations in cuprates differ from the conventional fluctuations or not. Perhaps themost convincing evidence phase disorder scenario comes from the upper critical field deduced
from Nernst effect[109] and torque magnetometry.[104] The upper critical field is supposed to
become zero at Tc in case of vanishing pairing amplitude, but in these studies it was shown thatthe upper critical field remains large at Tc and above Tc, and this hints to the phase disorderscenario.
As previously mentioned, the pseudogap was interpreted as a state of performed pairs by somegroups, and these studies showing pairing above Tc were thought to be supporting this idea.
However the onset temperature of pairing was found to be smaller than T* and in some cases a
different doping dependence (decreasing in the underdoped side) was shown, and this can beseen in the phase diagram of LSCO and Bi2Sr2-yLayCuO6 obtained from torque magnetometry and
Nernst effect measurements in Fig.2.16.

Fig.2.16 Taken from Ref.[104] Doping dependence of the onset temperature of superconductivity
in LSCO and Bi2Sr2-yLayCuO6 where Tν comes from Nernst effect and TM from torque magnetometry
measurements.
Pairing above TC is inconsistent with the Fermi arc: if pairing exists a d-wave gap should beobserved. However early studies showed a linear dependence of the Fermi arc length withtemperature[110] and this was interpreted as effect of the strong scattering that exist above T chiding the d-wave gap.[111] If the scattering rate exceeds the value of the gap, the ARPES spectra
appear ungapped, hiding therefore the d-wave gap at the nodes where it is smaller, and creating a
false Fermi arc. Quantitative analysis of ARPES data proved instrumental in solving this issue,[76],20[107] showing that below the pair formation temperature Tpair there is indeed a fully opened dwave gap while at Tpair<T<T* only the antinodal region is gapped and real ungapped Fermi arc arepresent.
An exceptional case of pairing at extremely high temperature is constituted by the pump andprobe experiments in YBCO shown in Ref.[112] Here using laser pulses, superconductivity was
induced far above Tc, and up until room temperature. Here the doping dependence of the onset
temperature of this induced superconductivity is increasing with lower doping, and follows thepseudogap T*doping dependence. This study may constitute a case in favour of theories thatsuggest pairing as the origin of the pseudogap, or could point to some kind of connection between
the pseudogap and superconductivity, though this is controversial.

2.3.6 Strange metal
The strange metal phase appears at intermediate doping in the “normal” state of the cuprates, as
indicated by the violet area in the phase diagram in Fig.2.5. Because of strong correlation effects,
even though metallic behaviour is observed, the quasiparticles are absent, and this was shownwith in-plane resistivity[113] and Hall resistivity measurements.[114] In normal metals theresistivity saturates at high temperature since the mean free path l of the electron, determined byelectron phonon coupling, can decrease as low as the atomic spacing. However in cuprates the inplane resistivity remains linear up until as high temperature as measured (800K) [113]. At suchhigh temperature the calculated l would be smaller than the de Broglie electron wavelength λ andthis would violate the Heisenberg uncertainty principle.
A theory that was partially successful in describing these experimental anomalies is the “marginalFermi liquid” theory.[115] The idea is that the electron in the Fermi gas are coupled to acontinuum of excitation. This continuum of excitation is assumed as spatially featureless and has aspectral density that is constant for ω>T but proportional to T for ω<T. This was indeed confirmed
by ARPES measurements but only in the nodal region, while the antinodal region behavesincoherently.[116]Another idea that was proposed to explain the strange metal is that the strange metal phaseoriginates from a quantum critical wedge associated with a quantum critical point QCP under thesuperconducting dome and this is shown in the phase diagram in Fig.2.5. The QCP is associatedwith a phase transition between an ordered state and a disordered phase, as a function of a tuning
parameter (doping pressure etc.). In the phase diagram with the tuning parameter andtemperature, above the QCP a wedge should open, and the strange metal phase was proposed to
be originating from this wedge. One problem of this idea is that the quantum critical wedge should
disappear at high temperature but the strange metal phase is observed up to extremely hightemperature.

21

2.3.7 Overdoped regime
Increasing the doping until the overdoped regime, signatures of a real Fermi liquid, consistent withthe one electron band theory, start to appear. This is shown in the phase diagram in Fig.2.5 by thewhite area. In this region quantum oscillations are consistent with a large Fermi surface.[117]
ARPES shows that a coherent peak is present on the whole fermi surface, including in theantinodes which are incoherent at lower doping, supporting the recovery of a real Fermi
liquid.[118], [119]Interestingly in this regime inelastic neutron scattering indicates that the spin fluctuation
disappear gradually. The intensity of the spin excitation peak was shown to decrease linearly with
Tc with increasing doping,[120] indicating that superconductivity and spin fluctuations may have acooperative relationship and this could be a point in favour to the idea of spin fluctuation as
pairing glue.

2.4 Multilayer cuprates
The multilayer cuprates are another fascinating aspect of the field. The main reason for this is that
the Tc of the cuprates strongly depends on the number of Cu-O plane per unit cell n. In Fig.2.16 thecrystal structure of some example families of multilayer cuprates is shown. Going from the left n isincreased from one, in the single layer member of the family, to five. Here the difference in crystal
structure with increasing number of layers can be seen. In the single layer component the copper
atom forms an octahedron with the neighbouring oxygen atoms. The double layer component has
two identical CuO2 layers in which the copper atoms are in pyramidal configuration with theneighbouring oxygens. Finally for n ≥3 the interesting situation where unequal CuO2 layers arepresent arises. The layers next to the charge reservoir layer have coper atoms in the pyramidal
configuration, as in the double layer component, and these layers are named Outer Planes OP. On
the other hand the layers that are not adjacent to the CRL are called inner planes IP, and thesehave the copper atoms in planar configuration with no apical oxygen. The two kinds of planes are
chemically inequivalent. The fact that the inner planes are not directly adjacent to the CRL makes
it more difficult for carrier coming from the dopant atoms in the CRL to reach them. As a result the
inner planes are less doped than the outer planes which are adjacent to the CRL. Therefore for n≥3 the interesting situation where layers with different doping coexist in the same samples arises.
In this situation one difficulty is to determinate the layer doping of the two kind of planes OP and
IP, which is different from the average sample doping. One way to measure this layer doping
comes from the Cu NMR Knight shift peaks, which is sensible to the carrier concentration in thesurrounding of the copper atom. A linear empirical relation between the hole concentration p andthe temperature dependent spin part of the Knight shift Ks was proposed.[9]22Fig.2.16 Taken from Ref.[9] Examples of crystal structure of families of cuprates with different
number of copper plane n per unit cell. a MBa2Can−1CunO2n+2+δ (M=Hg, Tl, and Cu) M12(n-1)n crystal
structure. b Ba2Can−1CunO2n(FyO1−y)2 02(n-1)n crystal structure.
Multilayer band splitting is another effect that is expected to arise with increasing number of CuO 2
layers. According to t−t′−t''−J model calculations, the bands of different layers should hybridize
forming a number of bands equal to the number of copper layers.[121] Therefore in the double
layer cuprates, two bands should appear: a bonding and an antibonding band, and this was indeed
observed by ARPES. [122] In the case of n ≥3 the doping imbalance between the OP and IP is themain source of band splitting. In the case of the triple layer for example a large splitting exists
between the OP and IP bands.[123] Here only two band were observed, but the OP band wasshown to be much broader than the IP band, and therefore two OP bands could be overlapping
and not resolved.
The critical temperature of the cuprates strongly depends on the number of CuO2 layers per unit
cell. Tc increases when n increases from n=1 to n=3, where it reaches its maximum, and thendecreases for n≥4 [5] and this trend is shown in Fig.2.17. Up to date the cause of this Tc
enhancement is not clear, with several possible factors being proposed. Firstly the tunnelling of
Cooper pairs between different layers could enhance TC.[6] The next-nearest neighbour hopping
parameter t’ was also shown to correlate with TC. This correlation is valid both considering only
single layers cuprates and considering cuprates with different number of layers, since t’ increases
with the number of layers.[7] Finally another factor that could greatly enhance TC is the disorderprotection that the OP offers to the IP.[8] Disorder next to the apical oxygen was shown to be a
drastic cause of TC suppression, causing buckling of the OP. Disorder coming from the dopant
could appear in principle anywhere in the unit cell, however the absence of any apical oxygen in
the IP makes disorder next to this layer much less severe than disorder next to the apical oxygenof the OP layer. In n≥4 cuprates with increasing n the AFM order becomes stronger[9] and this
could be the reason why TC decreases after n=3.

23

Since the doping level of the OP and IP is different it is possible that two different T C may be
associated with the two kinds of layers. It is therefore unclear if superconductivity appears at thesame temperature on the IP and on the OP or not. It is possible that the superconductivity
originates on one of the two kind of layers and then propagates in the other layer or drives it to besuperconductive by proximity effects.[9], [124]Fig.2.17 Taken from Ref.[9] Relationship between TC and n for different families of multilayer
cuprates.

2.5 BSCCO
The bismuth strontium calcium copper oxide, or BSCCO (pronounced "bisko"), are a family of highTC cuprate superconductors. They share a common chemical formula Bi2Sr2Can-1CunO2n+4 where nis the number of CuO2 layers per unit cell. n can go from 1 to 3, from the single to the triple layercomponent. The three component of the family are summarized in Table 2.1 and their crystal
structure can be seen in Fig.2.18.

Chemical formula
Bi2Sr2CuO6
Bi2Sr2CaCu2O8
Bi2Sr2Ca2Cu3O10

Notation
Bi-2201
Bi-2212Bi-2223

Max. TC (K)
20
95
110

n
1
2
3

Crystal structure
Tetragonal
Tetragonal
Tetragonal

Table 2.1 Summary of the BSCCO
In the present work we focused on the double layer Bi2212 and on the triple layer Bi2223.

24

The BSCCO are hole doped cuprates and their hole content can be modified by adding excess
oxygen. In this case the chemical formula becomes Bi2Sr2Can−1CunO2n+4+δ where δ is the excess
oxygen content. One advantage of the BSCCO is that their oxygen content is stable at room
temperature and ambient pressure. As other cuprates the BSCCO are almost 2D materials, andtheir layers are only weakly bound to each other by Van der Waals forces. This makes thesesamples extremely easy to cleave, and therefore they have the advantage that it is easy to obtaina clean surface. As described in the previous section, going from the single to the triple layermaterial the configuration of the copper atoms with the neighbouring oxygen changes, and thiscan be seen in Fig.2.18. The copper atom form octahedron with the neighbouring oxygen in the
single layer Bi2201, are in pyramidal configuration in the double layer Bi2212 and are in pyramidal
configuration or in planar configuration, on the OP and IP respectively, in the triple layer Bi2223.
The crystal structure of the BSCCO is tetragonal, and they belong to the D4h group (I4/mmm). The
BSCCO unlike other cuprates do not undergo structural transitions at low temperature. The a andb axis have the same length 5.4Å, which is also common for all the BSSCO from the single to thetriple layer. The c-axis on the other hand increases with n and is 30.8 Å and 37.1 Å in Bi2212 andBi2223 respectively.[125]–[127] The BSCCO are rather inhomogeneous materials as compared forexample to YBCO. The BiO layer are buckled and periodically modulated along the b axis, with anincommensurate period of 4.8b. [128] This modulation causes ghost images of the bands toappear in the ARPES spectra of BSCCO.[129]
ARPES and Raman share the requirement of a good sample surface and therefore the BSCCO,
being extremely easy to cleave, are suitable samples for these techniques. The surface in thesesamples is non-polar which is a requirement for ARPES. The inhomogeneity of these samples

Fig.2.18 Crystal structure of a the double layer BSCCO Bi2212 and b the triple layer BSCCO Bi2223
25

however, is a disadvantage and may broaden the spectral features. The modulation of the BiO
layer is also a disadvantage.
Bi2212 and Bi2223 are multilayer cuprates and, as discussed in the previous section, multilayerband splitting is expected to occur. In the double layer Bi2212 the two identical layer bands
hybridize, forming a bonding and an antibonding band.[122] The triple layer Bi2223 has
unidentical CuO2 layers, two OP and one IP, who do not contain the same amount of carrier. The
doping imbalance between the two kind of layer has been investigated by NMR and the layer
doping has been extracted (p(OP)≈0.203 and p(IP)≈0.127).[130] Here the doping imbalance
between the layers was found to be much larger than the one in other triple layer cuprates like
Hg1223. The band splitting in Bi2223 was observed by ARPES,[123] and a large splitting was
revealed between the IP and OP bands, however only a single OP band was found, which was verybroad and was therefore suggested to be composed of 2 unresolved OP bands. More importantly
the superconducting gaps of the two bands were found to have two distinct values, and this isshown in Fig.2.19. The difference in the value of the superconducting gaps is reasonableconsidering the different doping in the two layers.

Fig.2.19 Taken from Ref. [123] a,b ARPES cuts at 10K going from the node (1) to the antinode (2),in a and b a different photon energy is used. c OP and IP extracted gap value momentum
dependence.
The gap is larger in the underdoped IP than in the OP, additionally the IP gap shows a larger
deviation from the d-wave function extrapolated from the nodal gap (dashed line leading to Δ0 in
Fig.2.19.) The greater gap deviation in the IP is consistent with the one found in the underdoped
double layer components, that was discussed in section 2.3.2.
One particularity of Bi2223 is that TC does not decrease in the overdoped side. This was uncovered
by determining the c-axis of samples with various doping by X-ray diffraction XRD.[131] Since thec-axis of the BSCCO decreases with increasing oxygen content this parameter is a good indicator of
the sample doping. Here it can be seen that with decreasing c-axis (increasing doping) the TC of
Bi2223 does not decrease from the optimally doped sample, unlike the TC of Bi2212. The TC
reaches the maximum value at the optimally doped sample and then saturates. Up to date it isunclear what causes the constant TC in the overdoped side of Bi2223, however this is most likely amultilayer effect. Unfortunately many factors may come into play in the determination of thetriple layer cuprates TC, like the protection of the IP from disorder, the tunneling of Cooper pairs
26between layers etc., and additionally it is not certain that the triple layer gaps have the same
doping dependence shown by the double layer. Therefore this problem cannot probably be solved
until more clarity is made regarding the triple layer cuprates.

Fig.2.20 Taken from Ref. [131] Renormalized TC potted against the c-axis variation from theoptimally doped sample for Bi2212 and Bi2223 samples with various doping.

2.6 Previous Raman Experiments
The cuprates have been extensively studied by Raman spectroscopy. Raman was one of thetechniques that were instrumental in determining the d-wave gap function in the early days of theFig.2.21 Taken from Ref.[132] Temperature dependence of the Raman spectra. a and b Raman
spectra, of Bi-2212 single crystals for several doping levels in B1g (antinodal) and B2g (nodal)
geometries.
27

cuprates. [38], [39] In these early studies it was shown that if the gap has a d-wave symmetry, theintensity of the B2g nodal probe has a linear dependence in ω, while the antinodal B1g probe has a
cubic dependence in ω.
In Fig.2.21 the B1g and B2g Bi2212 Raman spectra are shown for samples of various doping. By
cooling the sample below TC a gap appears at low frequency and a peak at higher frequency, andthese are the Raman signatures of superconductivity. The loss of spectral weight at low frequency
is caused by the opening of the superconducting gap, while the peak is a pair breaking peak,associated with the breaking of a Cooper pair and a transition across the superconducting gap.
The nodal B2g and antinodal B1g superconducting pair breaking peaks in Raman have a different
doping dependence that can be seen in Fig.2.22. This different doping dependence is also
observed in other techniques like ARPES, and is commonly known as two energy scale[46]–[49].
However there are differences in the two energy scale seen by ARPES and Raman. The antinodal
B1g Raman peak monotonically increases going towards lower doping. This same doping
dependence is found in the antinodal ARPES gap Δ* as seen in Fig.2.9. However the antinodal
ARPES gap is not commonly associated with superconductivity, since it is in fact a deviation fromthe d-wave function normally associated with the pseudogap, in the two gap pictures discussed
previously. The nodal ARPES gap Δ0 , which is associated with superconductivity, stays constant fora wide range of dopings. Therefore an interesting question is why the pair breaking antinodal B 1g
Raman peak energy increases with lower doping while the nodal ARPES gap Δ0 remains constant?
One possibility is that the energy of the superconducting gap is partially enhanced by thepseudogap, however this is just a speculation at this point. One way in which the pseudogap
certainly influences the B1g Raman peak is by suppressing its intensity in the underdoped region, as
it can be seen in Fig.2.22 (b). This is due to the fact that the pseudogap confines the Cooper pairs
in the nodal region at low doping[50] and this causes the gradual disappearance of the B1g peak.
The nodal B2g peak intensity on the other hand stays constant. The B2g Raman peak energy doping
dependence follows the superconducting dome, as shown in Fig.2.22. However the nodal ARPES
gap Δ0 does not follow precisely the dome, since, as said before, it is constant in a wide range of
dopings, and decreases only in the strongly overdoped or underdoped side, as seen in Fig.2.10.
This is therefore another discrepancy between the nodal Raman and ARPES probes, and one may
wonder why the former follows the superconducting dome even if the gap is constant. In theunderdoped side this may also be due to the confinement of Cooper pairs in the nodal region
caused by the pseudogap. If superconductivity is confined more and more towards the node theeffective gap that must be considered for the Raman B2g peak may decrease, even if the gap slope
Δ0 does not change.
Bi2212 [48], [49], [133]–[135] and the other double or single layered cuprates [46], [47], [136]have been studied extensively by Raman, however this is not the case for the triple layer cuprates.
Previous works on the triple layered cuprates are mostly quite old [137]–[141], but mostimportantly, no signature of the double superconducting gap due to the two inequivalent layer IP
and OP has been found so far. The difference in energy between the IP and OP reported by ARPES
in Bi2223 is quite large, [123] and therefore a signature of the double gap should be observed in28

Fig.2.22 Taken from Ref. [47], [142] a Renormalized nodal B2g and antinodal B1g energy of thesuperconducting pair breaking peak seen by Raman, for various single and double layer cuprates. b
Doping dependence of the intensity of the B1g and B2g Raman pair breaking peak.
principle, however no such signature has been previously found. This may be due to sample
quality and instrumental resolution limits.
In Ref. [47] it was shown that dividing the peak energy by the maximum sample T c causes thedoping dependence of many single and double layer cuprates B1g and B2g peak energies to collapse
on a universal doping dependence, which is shown in Fig.2.22 (a). In this plot no triple layer
cuprates have been inserted. A signature of the double gap of the triple layer cuprates has not yet
been shown by Raman, therefore even if the triple layer were added in this plot, it would be oflittle significance to plot an energy that is a mixed contribution of two gaps of different values
coming from two layers with different doping. However if a signature of the double gap was to beobserved by Raman and if the correct layer doping was to be used, it would be interesting to know
if the triple layer Raman energy does scale or not on this universal doping dependence.

2.7 Previous Raman calculations
Previous Raman calculations are mostly base on the kinetic theory, and were quite successful inreproducing the ERS spectra of cuprates. The early calculations showed that the B1g peak appears
at 2Δ, where Δ is the maximum gap. Additionally, as mentioned before, these calculation proved
instrumental in showing the d-wave gap anisotropy, and showing how this gap function gives a B2g
intensity linear in ω and a B1g cubic in ω.[38], [39]29One challenge for the following calculations was to reproduce the two energy scale that was
discussed in the previous section. Sacuto group was quite successful in this. [47], [49], [142], [143]In these calculations the Raman susceptibility was calculated as:𝜒𝐵′′1𝑔𝐵2𝑔 (Ω) =2𝜋𝑁𝐹 2Δ2 (𝜙)〈𝛾𝐵1𝑔𝐵2𝑔 (𝜙)(𝑍Λ)2 (𝜙)〉Ω√Ω2 − Δ2 (𝜙)(2.3)

Where 𝑁𝐹 is the sensity of states at the Fermi level, 𝛾 is the B1g or B2g Raman vertex, 𝜙 is the angle
in the momentum space, and the braket describes the integration on the Fermi surface. Here thegap shown in Fig.2.23 was assumed. In these calculations the assumptions on the quasiparticle
spectral weight 𝑍Λ are fundamental to obtain the two energy scale correctly. Following theconsideration of the confinement of the Cooper pairs in the nodal region with lower doping the𝑍Λ profile shown in Fig.2.23 bottom left panel is assumed. This assumed profile gives more
intensity to the nodal area and suppresses the antinodal intensity. This assumption gives the twoenergy scale as it can be seen in the results in Fig.2.23 right panels. Here the energy doping
dependence is opposite for B1g and B2g and the B1g intensity decreases with lower doping, as in theexperimental spectra. However additional assumptions on the gap doping dependence must be
made. In this work in Ref.[142] a simple d-wave gap, increasing with lower doping was assumed.
The increasing antinodal gap is a requirement to obtain an increasing B1g energy, and this isconnected to the problem of the ARPES antinodal gap discussed in the previous section: if Δ* isconnected with the pseudogap, why is it necessary to assume its doping dependence (increasing

Fig.2.23 Taken from Ref.[142] On the left the assumed gap function and quasiparticle spectral
weight is shown. On the right the calculated B1g and B2g Raman spectra.

30

with lower doping) to calculate correctly the pair breaking (superconducting) peak position in B 1g
Raman configuration? As discussed before a possible explanation is that the pseudogap may
influence the superconducting energy, though this is just a speculation at this point.
Previous calculation were performed to reproduce mainly single or double layer cuprates, So far
no Raman experimental evidence of the double superconducting gap of triple layer cuprates has
been presented, and therefore there was no need to calculate the Raman spectra of a triple layer
cuprates with a double superconducting gap. It would be therefore interesting to calculate a triple
layer cuprate Raman spectra originating from a double superconducting gap.

2.8 Purpose of this work
Since, as discussed in the previous section, the double superconducting gap of Bi2223 wasobserved by ARPES,[123] but not by Raman. Therefore the center of this work is the Raman
measurement of Bi2223 samples, with the main goal of finding a Raman signature of this double
gap. This would be the first observation of a Raman signature of the double gap, not only in Bi2223,
but also in cuprates. Such a observation could help clarify the complex situation of the multilayer
cuprates, and give us hints on how the layers interact with each other, or which parameter
enhances the TC, or how the pseudogap modifies in the case of multiple layer cuprates and how it
affects superconductivity. Since it is possible to study easely the temperature dependence of theRaman spectra, it would be interesting to observe if one of the two gaps opens at a higher
temperature due to the different doping of the layer, or if some intereaction between the twolayers occurs, giving superconductivity at the same temperature. An added bonus in exploringsuch a triple layer cuprate is that we have the additional advantage that we can study multiple
doping levels in one sample.
The second goal of this work is to reproduce Bi2212 and Bi2223 samples Raman spectra using theexperimental ARPES data as an input. Starting from experimental ARPES data could help giving abetter reproduction of the Raman spectra whose experimental shape are not well reproduced byprevious calculations using the kinetic theory. In addition this could help to clarify the differencesin how Raman and ARPES wiew the two energy scale and understand if there are inconsistencies
between the two probes. Finally, studying multiple Bi2212 samples allows us to establish thecalculation method, and verify its validity, so that we may apply it on the triple layer Bi2223, whichis the main focus of the experimental part of this study.
For the Bi2223 calculation case, since a double superconducting gap is observed by ARPES on the
IP and OP bands, we are interested, not only in reproducing the experimental spectra, but also in
calculating the separate contribution of these two bands, and investigate if these two band should
give a different contribution to the calculated Raman spectra or not, and therefore understandbetter the origin of each part of the Raman spectra.

31

32

3:Methods
3.1 Sample growth & annealing
The double layer Bi2212 can be grown with different methods, like self-flux or KCl flux method.
However the method that gave the best sample quality and allowed to grow successfully large
Bi2223 sample is the Travelling Solvent Floating Zone method. This method advantage consists in
the high temperature spatial gradient that can be reached. This allows growing the crystal in a
fixed point in the temperature-composition phase diagram, making it possible to grow materials
with a narrow crystallization field like Bi2223.[126] An additional advantage of the TSFZ method isthat it does not use a crucible, and this allows to avoid contaminations of the sample and thedelicate procedure of removing the grown sample from the crucible without breaking it.

Fig.3.1 Taken from Ref.[144] On the left schematic of the TSFZ principle. On the right picture of therods during the growth process.
In Fig.3.1 a schematic of the TSFZ set-up is shown. The method is based on the use of halogen
lamps that emit IR radiation. This IR light is focused by ellipsoidal mirrors on the feed rod whichmelts and the crystal grows on the seed rod. The mirrors or the rod is moved slowly so that thefocusing point of the mirrors, and therefore the molten zone, scans the entire length of the rod. To
maintain the temperature uniform the feed and seed rods are rotated in opposite directions.
The first step in the growth process of BSCCO samples is the preparation of oxide powders of Bi2O3,
SrCO3, CaCO3 and CuO of high purity (99.99%). These must be weighted and added in the rightproportions to obtain Bi2212 and Bi2223 samples. The desired chemical reactions are:
𝐵𝑖2 𝑂3 + 2𝑆𝑟𝐶𝑂3 + 𝐶𝑎𝐶𝑂3 + 2𝐶𝑢𝑂 + 𝑂2 → 𝐵𝑖2 𝑆𝑟2 𝐶𝑎𝐶𝑢2 𝑂8+𝛿 + 𝑂2

(3.1)

𝐵𝑖2 𝑂3 + 2𝑆𝑟𝐶𝑂3 + 2𝐶𝑎𝐶𝑂3 + 3𝐶𝑢𝑂 + 𝑂2 → 𝐵𝑖2 𝑆𝑟2 𝐶𝑎2 𝐶𝑢3 𝑂10+𝛿 + 𝑂2

(3.2)
33

for Bi2212 and Bi2223 respectively. In the above chemical relationship oxygen is not balanced, acontrolled mixed gas flow (for example in Ref.[126] for Bi2223: 80% Ar, 20% O2) is set to supply
oxygen during the growth process. The BSCCO are stable in a non-stoichiometric, slightly Bi richcomposition, therefore a slightly Bi rich ratio for the oxide powders is used. Usually Bi2O3 andSrCO3 are weighted to obtain a Bi/Sr ratio of 2.1/1.9. The obtained mixture is then grinded andcalcinated at high temperature (≈800°C) for 12-24 hours. After the first calcination the compoundis reground and calcinated again. The obtained mixture is grinded again and then hydrostaticallypressed to form a rod. This rod is then sintered at ≈850°C for 48 hours. The obtained sintered rod
is polycrystalline. This polycrystalline rod is fed to the TSFZ system. First the rod is pre-melted at ahigher speed of 20-70 mm/hour. After the first fast scan a much slower scan is performed at
speeds ranging from 0.05 to 0.2 mm/hours, and the single crystal is grown in the seed rod. Here acontrolled flow of oxygen controls the initial sample doping. The Bi2212 samples were grown in
Tajima group at Osaka University while the Bi2223 samples where grown by our collaborators in
Watanabe group at Hirosaki University. The readers interested in further details about the sample
growth may consult Ref.[127], [145], [146] for the Bi2212 samples and Ref.[125], [126] for the
Bi2223.
To change the sample doping, by tuning the oxygen content, the annealing procedure can be
performed. This is done by heating the sample in a furnace, and using a controlled atmosphere,
usually of oxygen in our case. The temperature, the annealing time and the content of thecontrolled atmosphere are the parameters that control the final sample doping. The time ofcooling after the annealing is finished should be kept as short as possible in order to avoid
modifying the oxygen content desired and broadening the sample superconducting transition. To
avoid this, quenching can be performed, by immersion in liquid nitrogen or by contact with acopper plate. For further details about the annealing conditions we suggest Ref.[147], [148] for
Bi2212 samples and Ref.[125], [131] for Bi2223.

3.2 Raman
The name Raman comes from the Indian physicist C.V. Raman (Nobel Prize 1930) who first showed
the Raman effect experimentally. The Raman effect is an inelastic scattering of light, in which theincident photon excites an electron to a higher (often virtual) state, and the scattered photon isemitted by the electron decaying back to a lower state. Here the final state can be a vibrational
state at a higher, lower or at the same energy as the initial one giving rise to Stokes anti-Stokes orRayleigh lines. In the first two cases a vibrational mode is excited to a higher or lower vibrational
level. Therefore Raman is a photon in photon out technique, unlike for example ARPES which is aphoton in electron out technique. Due to its sensibility to phonon states Raman spectroscopy was
widely used to investigate phonon vibration in all sorts of materials.

34

Fig.3.2 Taken from Ref.[149] Characteristic Raman scattering spectrum YBCO. Light scattering
contributions from phonons, magnons, and electrons are plotted in blue, green, and red,respectively.
However the Raman effect may occur with excitation different from the phononic ones, as seen in
Fig.3.2, excitation of electronic states and of magnons are also possible and these different
contribution overlap in cuprates. In contrast to phonon excitations, which originate from distinct
vibrational levels that give sharp peaks, the electronic contribution is broad, since a continuum ofstate is available for the excitation, as it can be seen in Fig.3.2.
Electronic Raman scattering ERS has multiple advantages such as being sensible to both occupied
and unoccupied states, being momentum resolved and sensible to the bulk of the sample. For
these reasons it is a powerful technique to study the electronic states in cuprates superconductors.
As in the case of phononic excitation, ERS involves a transition to a higher level caused by theincident light and the emission of a scattered photon when the electron decays to a lower level,

Fig.3.3 Taken from Ref.[143] Electronic Raman scattering process (Stokes process): a crystal isirradiated by a monochromatic wavelength of a laser beam and the scattered light is collected.
The difference in frequency between the laser and scattered frequencies (ΩL and ΩS respectively)
is called the Raman shift, ΩR and corresponds to the energy of an electron-hole pair excitation
around the Fermi level.
35and this is shown in Fig.3.3 in the case of a Stokes process. The difference between the incident
and scattered light frequencies (ΩL and ΩS respectively) is called the Raman shift, ΩR. In the
superconducting state the final and initial state can be states across the superconducting gap andthis can cause the breaking of a Cooper pair, with the creation of Bogoliubov quasi-particles. This
gives a contribution to the Raman spectra at the energy of the superconducting gap.
Being a two photon process ERS is a second order process in the electromagnetic field. This meansthat in the interaction Hamiltonian between electron and the radiation originates both from thesecond order term and from the first order term perturbation up to the second order. It was
shown[150] that both these terms can be gathered in a single effective second order Hamiltonianin the form:
𝐻𝑅 =𝑒2〈𝐴 𝐴 〉𝑒 −𝑖Ω𝑡 𝜌̂𝑞
𝑚 𝑆 𝐿

(3.3)

Where 𝐴𝑆 and 𝐴𝐿 are the scattered and laser (incident) light vector potentials and the bracket
indicates the proper matrix element over the photon states. Ω indicates the Raman shift (= ΩL - ΩS)
and q the difference between the photon momenta is q = kL−kS. The operator 𝜌̂𝑞 is given by:𝜌̂𝑞 = ∑ 𝛾𝑛𝑓 ,𝑛𝑖 ,𝑘 𝑐𝑛+𝑓 ,𝑘+𝑞 𝑐𝑛𝑖 ,𝑘(3.4)

𝑛𝑓 ,𝑛𝑖 ,𝑘Here k is the initial electronic momentum, and 𝑛𝑓 and , 𝑛𝑖 indicate the final and initial electronic
states respectively. 𝛾𝑛𝑓 ,𝑛𝑖 ,𝑘 is the Raman vertex and is given by:
𝛾𝑛𝑓 ,𝑛𝑖 ,𝑘 = 𝑒𝑆∗ ∙ 𝑒𝐿 𝛿𝑛𝑓 ,𝑛𝑖1+ħ𝑚⟨𝑛𝑓 , 𝑘 + 𝑞|𝑒 −𝑖𝑘𝑆 ∙𝑟 𝑒𝑆∗ ∙ 𝑝|𝑛𝑚 , 𝑘 + 𝑘𝐿 ⟩⟨𝑛𝑚 , 𝑘 + 𝑘𝐿 |𝑒 −𝑖𝑘𝐿 ∙𝑟 𝑒𝐿 ∙ 𝑝|𝑛𝑖 , 𝑘⟩∑𝜀𝑛𝑖 ,𝑘 − 𝜀𝑛𝑚 ,𝑘+𝑘𝑙 + Ω𝐿 + 𝑖𝜂𝑛𝑚

+ (𝐿 ↔ 𝑆)(3.5)

𝑒𝐿 and 𝑒𝑆 are respectively the incident and scattered field polarization and 𝜀𝑛,𝑘 are the electronic
states energies.
The Raman vertex in (3.5) depends on the band structure of the material and is difficult to
calculate explicitly. However some simplifications can be made. The photon momentum transfer 𝑞
in the visible range is much smaller than the electronic momentum and it can therefore usuallyneglected. Under this approximation the Raman vertex can be decomposed using the grouptheory. This is extremely useful to highlight the momentum dependence of ERS and to show how
this depends on the chosen incident and scattered light polarization. In the case of cuprates, since
they have a slightly distorted tetragonal phase they belong to the D4h space group and the Ramanvertex can be decomposed on the irreducible representation of this group:𝛾̃(𝑞 → 0) = ∑ 𝛾𝜇 Φ𝜇
𝜇

36

(3.6)

Geometry𝒆𝑳𝒆𝑺xx, yy

x̂,ŷ

x’x’
x’y’

Basis Function 𝚽𝝁 (k)x̂,ŷR𝑅𝐴1𝑔 + 𝑅𝐵1𝑔

0.5[cos(𝑘𝑥 𝑎) − cos(𝑘𝑦 𝑎)] ± 0.5[cos(𝑘𝑥 𝑎) − cos(𝑘𝑦 𝑎)](x̂+ŷ) / √2(x̂+ŷ) / √2

𝑅𝐴1𝑔 + 𝑅𝐵2𝑔

0.5[cos(𝑘𝑥 𝑎) + cos(𝑘𝑦 𝑎)] + sin(𝑘𝑥 𝑎)sin(𝑘𝑦 𝑎)(x̂-ŷ) / √2ŷ𝑅𝐵1𝑔 + 𝑅𝐴2𝑔

0.5[cos(𝑘𝑥 𝑎) − cos(𝑘𝑦 𝑎)] [1 + sin(𝑘𝑥 𝑎)sin(𝑘𝑦 𝑎)]xy(x̂+ŷ) / √2x̂𝑅𝐵2𝑔 + 𝑅𝐴2𝑔

sin(𝑘𝑥 𝑎)sin(𝑘𝑦 𝑎){1 + 0.5[cos(𝑘𝑥 𝑎) − cos(𝑘𝑦 𝑎)]}LR(x̂+iŷ) / √2(x̂+iŷ) / √2

𝑅𝐵1𝑔 + 𝑅𝐵2𝑔

0.5[cos(𝑘𝑥 𝑎) + cos(𝑘𝑦 𝑎)] + sin(𝑘𝑥 𝑎)sin(𝑘𝑦 𝑎)(x̂-iŷ) / √2ẑ

0.5{cos(𝑘𝑥 𝑎) + cos(𝑘𝑦 𝑎) + [cos(𝑘𝑥 𝑎) − cos(𝑘𝑦 𝑎)]sin(𝑘𝑥 𝑎)sin(𝑘𝑦 𝑎)}xz(x̂+iŷ) / √2x̂𝑅𝐴1𝑔 + 𝑅𝐴2𝑔
𝑅𝐸1𝑔

sin(𝑘𝑥 𝑎)sin(𝑘𝑧 𝑐)

yz

ŷ

ẑ

𝑅𝐸1𝑔

sin(𝑘𝑦 𝑎)sin(𝑘𝑧 𝑐)

zz

ẑ

ẑ

𝑅𝐴(2)

cos(𝑘𝑧 𝑐)

LL

1𝑔

Table 3.1 Taken from Ref.[149] Elements of the transition rate R for experimentally usefulconfigurations of polarization orientations 𝑒𝐿 and 𝑒𝑆 (given in Porto notation) along with thesymmetry projections for the D4h point group relevant for the cuprates. Here we use notations inwhich x and y point in directions along the Cu-O bonds in tetragonal cuprates, while x’ and y’ aredirections rotated by 45°. L and R denote left and right circularly polarized light, respectively.
Where 𝜇 represents the irreducible representation of the point group of the crystal and Φ𝜇 are
the basis functions of said irreducible point group of the crystal. This means that the contraction of
the Raman vertex tensor 𝑒𝑆∗ ∙ 𝛾̃ ∙ 𝑒𝐿 will depend only on the terms in the summation in (3.6) thatare selected by the scattered and incident light polarization vector. Table 3.1 summarizes the mostcommonly used incident and scattered light configurations in cuprates. Here the x and y are along
the Cu-O bonds, while x’ and y’ are directions rotated by 45°. Additionally here the basis function
Φ𝜇 relative to each scattering configuration is shown. The configurations mainly used in this study
are 𝑧̅(𝑥’𝑦’)𝑧 and 𝑧̅ (xy)z in the Porto notation. In this notation A(BC)D, A and D indicate thedirection of the incident and scattered light wavevector respectively and B and C indicate theincident and scattered light polarization direction. These two configurations mainly probe the B1g
and B2g modes respectively, with a small A2g contamination, and are for simplicity referred as B1g
and B2g configurations in Raman studies. As it can be seen from Table 3.1 and Fig.3.4 these two
configurations probe mainly the antinodal and nodal region respectively.

Fig.3.4 Taken from Ref.[149] Schematic weighting of the light-scattering transition for polarization
orientations probing B1g and B2g for a D4h crystal. High-symmetry points are indicated. Here a37

typical Fermi surface for optimally doped cuprates is represented by the solid line, and theorientations of the incident and scattered polarization light vectors are shown with respect tocopper-oxygen bond directions.

Raman probes directly the Fourier transform of the density-density correlation function called the“dynamical structure factor” which is given by: [151]𝑆(𝑞, Ω, 𝑇) = ∫𝑑𝑡 𝑖Ω𝑡 †𝑒 〈𝜌̂ (𝑞, 𝑡)𝜌̂(𝑞, 0)〉 𝑇
2𝜋

(3.7)

where the bracket denotes the thermal average. According to the fluctuation dissipation
theorem,[152] 𝑆(𝑞, Ω, 𝑇) is related to the imaginary part 𝜒′′(𝑞, Ω, 𝑇) of the response function
𝜒(𝑞, Ω, 𝑇) as follows
𝑆(𝑞, Ω, 𝑇) =ħ
(1 + 𝑛(Ω, 𝑇))𝜒 ′′ (𝑞, Ω, 𝑇)𝜋

Here 𝑛(Ω, 𝑇) is the Bose Einstein factor given by 𝑛(Ω, 𝑇) = (𝑒

−

ħΩ
𝑘𝐵 𝑡

(3.8)
−1

− 1) . The imaginary part of

the response function is related to the electronic density fluctuations induced by the electric fieldof the incident light into the crystal, and is therefore the wanted signal. For this reason theexperimental spectra is usually divided by (1 + 𝑛(Ω, 𝑇)).
In Fig.3.5 a schematic of a typical experimental electronic Raman scattering set-up is shown. The
incident Radiation is produced by a laser, in our case an Ar+-Kr+ gas laser is used. This laser canemit light at different frequency, and for the present work the emission line that produces green
radiation with a wavelength of λ = 514.5 nm was selected. Different choices of incident lightenergy influence the intensity of the phonons in the spectra, and in general light energies thatstrongly enhance the phonon peaks should be avoided when interested in the electronic
contribution. The emitted light is reflected and passes through different optical components on its
way to the sample space. These include pinholes to decrease the radial dimension of the laser
beam and polarizers to select the incident radiation polarization direction. The sample space isequipped, in our case, with an oil pump and a turbomolecular pump that allows to obtain avacuum in the sample space, with pressures as low as 𝑃 = 5 ∗ 10−6 𝑡𝑜𝑟𝑟. The vacuum is notneeded for Raman spectroscopy, since the emitted photons can travel through air, unlike forexample ARPES where the emitted electrons need vacuum to propagate. The vacuum is needed
for cooling the sample at low temperature, as low as 5K, to avoid the deposition of all sort ofparticle and the formation of ice. The lower the sample space pressure, the longer the sample
surface will maintain clean even at low temperature, allowing the experiment to last longer
without the need to cleave the sample. Cooling of the sample is done with a cryostat connected toa helium compressor. The PID controller of the cryostat stabilizes the sample temperature to thedesired value. Even though we ideally desire to measure in the back-scattered configuration, thisshould be avoided, since the reflected laser light would enter the spectrometer directly and this38

Fig.3.5 Taken from Ref.[149] Schematic of the light path in a typical ERS spectrometer.
could cause damage to the detector. Instead quasi-back scattered geometry is used with theincident radiation at about 30-45° with the c-axis of the sample. The sample is mounted with the caxis along the Z direction in Fig.3.5, and the a and b axis (which correspond to x’ and y’ in Table
3.1) are oriented along the X or Y direction when measuring the B1g configuration and at 45°
degrees with the X and Y axis when measuring the B2g configuration. The first polarizer sets theincident light polarization to be along the Y direction and therefore the second polarized must be
set to collect the scattered light with a polarization along the X direction in order to measure theB1g and B2g configurations. However the sensitivity of the grating is highest in the Y direction,
therefore a λ/2 wave plate is used to rotate the collected scattered light polarization from the X
direction to the Y direction. As mentioned before ERS is a bulk technique. The penetration lengthin cuprates is of the order of 100 nm, spanning therefore numerous unit cells of the sample, unlike
other techniques such as ARPES where the electron penetration length can span only few atomic
layers. The laser spot size on the sample has a diameter of approximately 50-100 μm. To avoid
local heating of the sample the power of the incident laser was kept as low as P=3mW. Local
heating of the sample can, not only foul the measurement by changing the local temperature, but
it can also damage the sample surface, and therefore it must be avoided.
The spectrometer used for the present study is a Jobin-Yvon T64000 located at the Graduate
school of Science at Osaka University. This spectrometer is equipped with a triple monochromatorsystem with a grating density of 1800 gr/mm. The first two grating of the system can be coupled in
two different ways in the additive or subtractive mode shown in Fig.3.6. In the additive mode all of
the gratings separate the different wavelengths, and this allows reaching extremely high energy
resolution, as good as 0.1 cm-1, however this will allow measuring only a small spectral window. In
39

Fig.3.6 Taken from Ref.[153] Schematic sketch of the additive and subtractive mode for triple
monochromators
the subtractive mode the first grating splits the different wavelengths, which are filtered in thefirst intermediate slit, and then the second grating recomposes the different frequencies. This
allows having a very efficient rejection of the frequency outside the window selected by the firstintermediate slit and therefore a very good rejection of the Rayleigh scattering is obtained. The
resolution of the subtractive mode can be as good as 0.3 cm-1. In this study, since a good rejectionof the elastically scattered light is needed, but high resolution is not, the subtractive mode is used.
The electronic features are extremely broad as seen in Fig.3.2, therefore the highest resolution of
the subtractive mode is also not needed. Opening the entrance slit and the second intermediate
slit can increase the signal at the cost of losing resolution. In our study these slits were set to 500
μm which is a good trade off between signal intensity and resolution, giving a resolution of
approximately 5 cm-1. This may seem large, but it is not as compared to the scale of the electronic
features.
After passing through the monochromator the light enters the detector, a Charge Coupled Device
CCD, which is cooled by liquid nitrogen. The CCD can be damaged if exposed to the strong Rayleighscattering radiation and therefore rejection of this strong contribution is extremely important. Thisis achieved, as said before, by the subtractive mode of the triple monochromator, but, additionally,a good sample surface is also needed. If the sample surface is degraded strong scattering
originates from the surface defects preventing the measurement. In those cases it is necessary tocleave the sample and obtain a good surface with few defects.

40

3.3 Kubo calculations
To calculate the Raman spectra an equation much simpler than the one presented in the previous
section can be used, and this is the Kubo formula given by: [149]
′′
𝜒𝛾Γ
=

∞
2
Δ2𝒌
′′
′′
∑ 𝛾𝒌 𝛤𝒌 ∙ ∫ (𝑓𝜔 − 𝑓𝜔+𝛺 ) 𝐺𝒌,𝜔 𝐺𝒌,𝜔+𝛺 (1 −)(𝜔 + 𝜉𝒌 )(𝜔 + 𝛺 + 𝜉𝒌 )
𝜋𝑉
−∞

(3.9)

𝒌

′′
′′
that gives the Raman susceptibility 𝜒𝛾Γ. In this equation 𝑓𝜔 is the Fermi Dirac function, 𝐺𝒌,𝜔is theGreen function, Δ𝒌 is the superconducting gap, 𝜉𝒌 is the bare band in the normal state and 𝛾𝒌 and𝛤𝒌 are the bare and renormalized Raman vertices. The goal of the calculation performed in thiswork is to obtain more realistic calculated spectra by using the experimental ARPES intensity as an
input. Therefore, we want to obtain the Green function from the ARPES intensity. This can be doneusing the formulas:𝐼𝒌,𝜔 = 𝐼0 ∙ 𝑀𝒌 ∙ 𝑓𝜔 ∙ 𝐴𝒌,𝜔′′𝐺𝒌,𝜔= −𝜋𝐴𝒌,𝜔

(3.10)(3.11)The equation (3.10) gives the ARPES intensity where 𝐴𝒌,𝜔 is the spectral function and 𝑀𝒌 is thematrix element. The equation (3.11) gives the relationship between the Green function and thespectral function. Here to directly obtain the Green function from the ARPES intensity we makethe approximation that the matrix element does not depend on the momentum k. Calculation of
the ARPES matrix element is complicated, however it was shown that it has often a weak
momentum dependence, and therefore the approximation can be justified
As it will be discussed more in detail in the next section the ARPES spectra have a background thatoriginates from the inelastically scattered electrons during their propagation through the sample,
and this contribution must be subtracted. One way to do so is to use the empirical Shirley
background which is given by:∞

𝑏𝑔𝑆ℎ𝑖𝑟𝑙𝑒𝑦 (𝜔) = 𝑐 ∫ 𝑃(𝜔′) 𝑑𝜔′(3.12)

𝜔

Here 𝑃(𝜔′) is the spectrum after the background subtraction. The calculation of the Shirley
background is done in an iterative way assuming that the signal at 𝜔 = ∞ is completely
background and using an initially small 𝑐, this Shirley constant is gradually increased until the
spectrum at the highest binding energy is all composed by background, and this iterative
procedure is shown in Fig.3.7
In the case of band splitting, to calculate separately the contribution of each band to the Raman
spectra the ARPES intensity of these bands must be separated. This can be done by fitting theEnergy Distribution Curves (EDC) with multiple Gaussian functions. This is done using 3 Gaussian
peaks: one for each band and an additional one for the incoherent part at higher binding energy.
41

Fig.3.7 Example of iterative Shirley background subtraction on an EDC in optimally doped Bi2223
The bare-band can be obtained from tight binding fitting using the equation:
𝜉𝒌 = −2𝑡(cos 𝑘𝑥 𝑎 + cos 𝑘𝑦 𝑎) + 4𝑡 ′ cos 𝑘𝑥 𝑎 cos 𝑘𝑦 𝑎 − 2𝑡 ′′ (cos 2𝑘𝑥 𝑎 + cos 2𝑘𝑦 𝑎) − 𝜇(3.13)

Here 𝑡, 𝑡 ′ and 𝑡 ′′ are the nearest, the next nearest and the next-next nearest hopping integral and𝜇 is the chemical potential. Here we are interested in the normal state band dispersion, but toperform the fit it is still possible to extract the fitting points from the superconducting low
temperature data. This is done by using as fitting points the Fermi vector kF at zero energy. The kF
position does not change in the case of a superconducting gap opening, which is particle-holesymmetric. An additional fitting point used in the fit is the experimental band bottom at Γ. For
simplicity and in order not to add too many free parameters 𝑡 ′′ is fixed to be half of 𝑡 ′ . Therefore
the fitting free paramethers are 𝑡, 𝑡 ′ and 𝜇. In the case of multilayer band splitting multiple bands
must be fitted. In the case of Bi2223 the OP and IP bands have been fitted separately but in thecase of Bi2212 a multilalyer splitting term was added to (3.13) to fit simultaneously the antibonding band AB and the bonding band BB:
𝐸𝑏𝑖 = −

𝑡⊥2
(cos 𝑘𝑥 𝑎 − cos 𝑘𝑦 𝑎)4(3.14)

This is the simplest form of bilayer splitting term, and is not ideal for realistic calculations,[21]however it can be used in this case, since we are simply interested in a small momentum region
where the superconducting gap opens. This tight binding fitting is not only used in (3.9) but is also
used to calculate the gap size Δ𝒌 in the ARPES cut between kF and the momentum where the gap
starts opening.
As shown in the previous section, explicit calculations of the Raman vertex is not trivial, and thecalculation of the renormalized Raman vertex is not trivial either, with several possible correlation
terms contributing. For simplicity, in the present work we use the Raman vertices calculated from42the assumption of single band given by the tight binding formula in a tetragonal lattice. These areused both for the bare and renormalized Raman vertex and are given by:
𝛾𝐵1𝑔,𝒌 = 𝜞𝐵1𝑔,𝒌 = 𝑚𝑎2 𝑡(cos 𝑘𝑥 𝑎 − cos 𝑘𝑦 𝑎)(3.15)

𝛾𝐵2𝑔,𝒌 = 𝜞𝐵2𝑔,𝒌 = 4𝑚𝑎2 𝑡′ sin 𝑘𝑥 𝑎 sin 𝑘𝑦 𝑎

(3.16)

for B1g and B2g, respectively. The assumption of identical bare and renormalized Raman vertex islikely a poor approximation for strongly correlated cuprates, but we expect it to be sufficient forthe present study.

3.4 ARPES
Angle Resolved Photoemission Spectroscopy (ARPES) is the best technique to experimentallyobserve the band dispersion, since it can directly image the occupied electron band with
momentum and energy resolution. ARPES is a photon-in and electron-out technique and since theelectron must diffuse out of the sample in order to be detected, the probed area is limited by theelectrons mean free path to a few atomic layers making ARPES surface sensitive. ARPES, unlike
Raman, can only probe occupied electronic states. Regardless these two limitations, the direct
momentum and energy resolved image of the electron bands makes it an extremely valuable
technique.
The ARPES process can be described in the framework of the three step model where the stepsare:
1. An incident photon is absorbed by an electron in the sample which is excited to the final
free electronic state.
2. The excited electron travels without losing energy nor changing momentum to the surfaceof the sample.
3. The electron escapes from the sample by overcoming the work function 𝜙 and enters thevacuum states.
However, this is an approximation since the excited electrons do interact sometimes with thelattice and other electrons, losing energy. Nonetheless, a good amount of electrons will notinteract with anything as postulated by the three steps process and in that case conservation ofenergy applies and is given by:
𝐸𝑘𝑖𝑛 = ℎ𝜈 − 𝜙 − |𝐸𝐵 |(3.17)

where ℎ𝜈 is the incident photon energy and 𝐸𝐵 is the emitted electron former binding energy, andthis is shown in the schematic in Fig.3.8 (b). From this conservation of energy comes the energy
resolution of ARPES, while the momentum resolution comes from the momentum conservation.

43

Fig.3.8 Taken from Ref.[33] a diagram of the ARPES process. b Schematic the conservation ofenergy in the ARPES process. cNormally the electron momentum is much larger than the photon momentum which can be
therefore neglected. The momentum along the sample plane is conserved according to:𝑘∥ =√2𝑚𝐸𝑘𝑖𝑛 sin(𝜗)ℏ(3.18)

Where 𝜗 is the angle between the vector normal to the sample surface and the electron trajectory.
However the momentum normal to the sample surface is modified by the sample surface
potential step, called inner potential 𝑉0. Therefore the momentum of the electron in the direction
normal to the plane surface is given by:𝑘⊥ =√2𝑚𝐸𝑘𝑖𝑛 𝑐𝑜𝑠 2 (𝜗) + 𝑉0ℏ

(3.19)

Using the hemispherical analyser in the configuration in Fig.3.8 (a), 𝐸𝑘𝑖𝑛 , can me measured and theelectron emission angles are known. Therefore considering the equation from (3.17) to (3.19) we
can obtain the original binding energy and the momentum of the electron in the sample, and thismakes ARPES a extremely viable momentum and energy resolved technique.
In the sudden approximation, where the emitted electron does not interact with the sample, the
ARPES intensity can be written as:
𝐼𝒌,𝜔 = 𝐼0 (𝒌, 𝜈, 𝑨) ∙ 𝐴𝒌,𝜔 ∙ 𝑓𝜔

(3.20)

where 𝑨 is the vector potential, 𝐴𝒌,𝜔 is the spectral function and 𝑓𝜔 is the Fermi-Dirac distribution.
This shows how ARPES is sensible only to occupied states. Here the intensity 𝐼0 (𝒌, 𝜈, 𝑨) is
proportional to:

44

2

2

𝐼0 (𝒌, 𝜈, 𝑨) ∝ |𝑀𝒌f,i | ∝ |⟨𝜙𝒌𝑓 |𝑒 ∙ 𝑟|𝜙𝒌𝑖 ⟩|(3.21)

2𝒌where |𝑀f,i| is the squared module of the matrix element, 𝜙𝑓𝒌 and 𝜙𝑖𝒌 are the the initial and final

electronic state and 𝑒 is the unit vector of the incident light polarization. Here it can be seen, by discussionof parity of these functions, how ARPES sensibility is influenced by the parity of the initial state 𝜙𝑖𝒌 orbitals

Fig.3.9 Taken from Ref.[33] the mirror plane in the ARPES experiment. The parity with respect of
this plane can be considered to make prediction on the matrix element intensity.
and this is the orbital selectivity of ARPES. The parity with respect to the mirror plane, which isdefined by the incident light and the scattered electron trajectories as seen in Fig.3.9, can beconsidered to evaluate quickly the intensity of the matrix element. Here the final state 𝜙𝑓𝒌 can beapproximated with the wavefunction of a free electron in vacuum 𝑒 𝑖𝒌⋅𝒓 and will always be evenwith respect to the mirror plane since 𝒌 is in plane. The parity of 𝜙𝑖𝒌 depends on the orbital
character of the band the electron is in, and the parity of 𝑒 ∙ 𝑟 can be selected by choosing theincident photon polarization, where with in-plane polarization the term will be even and with outof plane polarization it will be odd. Therefore by observing the dependence of the ARPES intensity
on the polarization of the incident light one can guess the parity of the initial state of the electron,and make guesses on the main character of the electron band.
In order to obtain the precise energy value of the Fermi level EF the sample is usually connected
electronically to a metal, often gold, and the ARPES spectrum of this metal is measured. The
spectrum of this reference metal is dictated by the Fermi Dirac function near the Fermi level,
whose value can be therefore extracted.
There are various possible source of the exiting radiation. In the field of cuprates, recently themost popular choices are synchrotron radiation and laser radiation. The latter has the advantagethat high momentum resolution can be obtained. Since the electrons cannot propagate in air, thewhole electron path from the sample to the detector must be in vacuum. Usually the sample canbe cleaved in vacuum in order to obtain the best possible sample surface, free fromcontaminations. The emitted electrons pass through electrostatic lenses and are collected by ahemispherical analyser usually equipped with a CCD detector. The hemispherical analyser can
45

collect electron with different momentum direction, which are allowed through a slit elongatedalong one direction, the analyser separates the electrons according to their energy in theperpendicular direction. Therefore the CCD collects a 2D image in which one direction is
proportional to the energy and the other to the angle of emission, which is related to themomentum. Therefore the ARPES data are usually 3D, the dimension being momentum, energy
and intensity, and represent cuts along a certain curve in the momentum space of the 5D space

Fig.3.10 Example of ARPES cut for the Bi2212 overdoped sample OD85K. An ARPES cut can beviewed as a 2D image where the colour scale is associated with intensity and one axis (verticalhere) is associated with binding energy and the other with momentum (angle of emission of theelectron). These images can be furtherly cut at a certain momentum, obtaining the EDC on the left,or at a certain energy, obtaining the MDC in the bottom of the figure.
constituted by momentum, energy and spectral function. These cuts can be viewed by 2D images
where the colour is associated to the intensity, or can be furtherly cut restricting to a specified
energy or momentum and viewed as spectra, and these are called Momentum Distribution Curves
MDC and Energy Distribution Curves EDC respectively. The EDC are generally used to extract theenergy value of a certain band or the value of an energy gap and the MDC are generally used toestablish the momentum position of a certain band or spectral feature.
The ARPES Bi2212 data for the samples UD75K and OP92K, used as an input in the Kubo
calculations in this study, have been carried out at Stanford Synchrotron Radiation Lightsource
beamline 5-4 using 22.7 eV photons with an energy resolution of 5 meV and an angular resolutionof 0.1° degrees, with polarization along the Cu-O directions (out of the mirror plane). The ARPES
Bi2212 data for the sample OD85K were measured at Institute for Solid State Physics at Tokyo
University, using a He lamp with a photon energy of 21.2 eV without polarization. For these the46energy resolution was 10 meV and the angular resolution was 0.1° degrees. These experiments
have been carried out by a colleague of my same laboratory. (Tajima Lab. Osaka University)
Bi2223 ARPES data where obtained on a slightly underdoped (but almost optimal doped) sample(TC=108K) grown by Uchida group in Tokyo University. The experiment was performed at UVSOR
facility beamline number 7 in the National Institute for Molecular Science in Japan. Radiation withenergy of hν=8eV was used. The data were taken at a sample temperature of T=12K. The
polarization of the incident radiation was outside of the mirror plane (S polarization) and theenergy resolution was ΔE=7meV. These experiment have been carried out by S.Ideta (National
Institute for Molecular Science)

3.5 Others: SQUID & XRD
To evaluate the sample critical temperature the susceptibility of the sample can be measured. Thiswas done using a Quantum Design Magnetic Property Measurement System (MPMS) located atTajima group at Osaka University. This is a SQUID (Superconducting QUantum Interference Device)magnetometer. The SQUID magnetomer employs a superconducting ring with two Josephson
junctions and detects the variations in magnetic flux through this ring. This can be used tomeasure the magnetic susceptibility of the sample, and the onset of the diamagnetic signal due tothe Meissner effect marks the onset of superconductivity. A magnetic field of 10 Oe was appliedalong the c-axis of the sample and the temperature dependence of the susceptibility wasmeasured. Here both Field Cooling FC and Zero Field Cooling ZFC susceptibility was measured,
where in ZFC the sample is cooled and then the magnetic field is applied, and in FC the opposite
order is used, by cooling with an already applied magnetic field. Here the TC of the sample wasdefined by the onset temperature of the Meissner effect, additionally the sharpness of thesuperconducting transition was defined as the difference between the onset temperature and thetemperature where the 90% value of the low temperature FC susceptibility was reached. Good
samples where the oxygen content is homogeneous are expected to have sharp superconducting
transitions.
X-ray diffraction is a powerful technique for determining the structure of a crystal. By illuminating
the sample with a monochromatic beam of X-rays, the photons will be scattered by the atoms of
the sample and will produce a diffraction pattern. This diffraction pattern is named Laue image
and since it originates from the spatial Fourier transform of the scattering centers is a way toimage the reciprocal lattice of the crystal. In this study a four-axis X-ray diffractometer located in
Osaka University was used. The Laue image can be used to locate the orientation of the crystal axis.
The BSCCO sample break more easily along crystallographic axis, therefore the sample borders areusually crystallographic axis, however these can be both the a and b axis or the axis rotated 45°(along the Cu-O bonds). Measuring the Laue image gives a more precise esteem of the axis
orientation and solves this uncertainty. Additionally the X-ray diffraction pattern can be used todetermine the crystal parameters. Since a decrease in oxygen content increases the c-axis, the c47

axis length is a measure of the sample doping.[131] Therefore in this study X-ray diffraction wasused to obtain the c-axis length of the Bi2223 samples, using the formula of the d-spacing formulafor a tetragonal crystal given by:1ℎ2 + 𝑘 2 𝑙 2
=
+ 2
𝑑2
𝑎2
𝑐

(3.22)

Where h k and l are the Miller indices, a and c are the a and c-axis length respectively. Using the(00l) peaks, knowing the l indices and given the Bragg law that connects the scattering angle to the𝑑 spacing, the value of the c-axis can be determined. This was done, in this work, for the Bi2223
samples, in order to estimate the average sample doping of the overdoped Bi2223 sample. Since,
as discussed before, the TC of Bi2223 does not decrease in the overdoped side, and therefore therelationship between the hole doping and TC, valid for most cuprates, cannot be used in this case.

48

4:Experimental Results and Discussion
4.1 Sample Preparation
The Bi2223 sample received from our collaborators in Hirosaki University were multiple samples of
two different doping levels: optimally doped and underdoped samples with TC of ≈109K and ≈88K,
respectively. However, to study the doping dependence of the Raman spectra, having more than
two sample doping is preferred. Therefore, we performed annealing to obtain samples withdifferent doping levels. The annealing conditions for the samples we received from ourcollaborators were: 40 hours under O2 flow at 600 ˚C[131] for the optimally doped sample and 1-3
hours under PO2≈2Pa at 600°C[125] for the underdoped sample.
Since the underdoped sample was quite strongly underdoped, our first goal was to produce aslightly underdoped crystal with a doping intermediate to the doping levels of the samples
received. Since there was no previous laboratory expertise in doping Bi2223 sample, few steps
with trial and error where involved. Annealing in a mixed argon and oxygen flow is a possible way
to change the oxygen content of the samples. However, annealing in air can also be used.[154]Therefore, for simplicity, starting from one of the underdoped samples received from the sample
grower, we firstly annealed in air, at 400°C for 40 hours. The TC increased to 97 K, however thesuperconducting transition was found to be broad (37K). As discussed in the previous section, theTC was obtained from the onset of the Meissner effect, while the broadness was obtained by theFig.4.1 Magnetic susceptibility of the slightly underdoped sample after each of the annealing steps.
49difference between TC and the temperature where the 90% value of the low temperaturesusceptibility was reached.
To try improving the sharpness and slightly increase TC we annealed again in air, for longer time, 3days, at a lower temperature, 370°C. However the TC increased by just one degree and the
sharpness got just slightly better. We therefore decided to anneal in oxygen atmosphere, at 700°C,
for 5 days, and quenched by immersing the sample in liquid nitrogen at the end of the process.
After this anneal we obtained a TC of 105K and a quite sharp transition (13K). A slightly
underdoped sample was therefore obtained, whose susceptibility can be seen in Fig.4.1.
To investigate also the overdoped side of Bi2223, we attempted to obtain an overdoped sample.
Firstly an optimally doped sample was obtained from the underdoped sample received from thesample grower, by annealing in O2 atmosphere at 500 ˚C for 40 hours. Then the annealing wasdone in two other steps, always in O2 atmosphere, but at lower temperature to increase theoxygen content: firstly at 450°C for 3 days and lastly at 400°C for 5 days. In this case, since theannealing temperature was lower to begin with, and the needed time to modify the oxygen
content is long at lower temperature, the quenching process is not strictly needed, and wastherefore skipped. In Fig.4.2 the magnetic susceptibility after these 2 annealing steps is shown
together with the one of an optimally doped sample obtained from the sample grower. As it canbe seen the TC of the 3 is almost identical, and this is expected, since as said before, the T C of
Bi2223 does not decrease in the overdoped side.[131] The superconducting transition (values in
Fig.4.2) is sharp in both cases, indicating that the sample quality is preserved and that the oxygen

Fig.4.2 Magnetic susceptibility of the overdoped sample after each annealing step, compared withthe one of an optimally doped sample received from the sample grower in Hirosaki University.
50content is homogeneous enough. However, since the TC does not change from the optimally
doped sample, to make sure that the doping level is changed, a separate measurement with adifferent technique is needed, and this will be confirmed later with the XRD and Raman results.
With this, Bi2223 samples with four different doping levels were obtained, ranging from theoverdoped to the underdoped side. The magnetic susceptibility of all the samples is shown in
Fig.4.3, and the TC and the final annealing condition are summarized in Table 4.1. The TC wasdetermined from the onset temperature of the Meissner signal as 109K for the slightly overdoped
and optimally doped samples, 105K for the slightly underdoped sample and 88K for the strongly
underdoped sample.
These samples will be referred as OvD109, OpD109, UnD105 and UnD88, respectively, from now

Fig.4.3 Magnetic susceptibility of all the Bi2223 samples measured. The susceptibility values havebeen normalized by the low temperature ZFC value. In the legend the chosen nomenclature forthe samples is used.

Sample NameOvD109
OpD109
UnD105
UnD88

TC (K)
109
109
105
88

ΔTc (K)89
13
18

TANNEALING (°C)
400
500
700
600

O2
100%
100%
100%
PO2≈2PaAnn. Time
5 days
50 hours
5 days
1-3 hours

Table 4.1 Summary of the Bi2223 samples measured. The assigned sample names together with TC,
broadness of the transition and annealing condition are shown.
51

on. The superconducting transition is sharp for the OvD109, OpD109 and UnD105 samples, but it isa little broader in the more strongly underdoped sample UnD88, and this can be seen in Table 4.1.
The broadness increases monotonically from the overdoped to the more underdoped sample andthis may be due to the difficulty in obtaining homogeneous underdoped sample.[125]Fig.4.4 Shows the XRD pattern for all the samples examined. The visible peaks correspond to theBi2223 peak previously reported in the literature [125], [126] and are all assigned to (0 0 l) peaks.
The more intense peaks are labelled on the optimally doped sample XRD spectrum in the second
panel of Fig.4.4. From these spectra using the formula (3.22) the c-axis length can be extracted.
The value was extracted from the 4 most intense peaks: (0 0 10), (0 0 12), (0 0 14) and (0 0 24)
peak. These give slightly different values of the c-axis length; therefore the value was averaged
between them. The obtained c-axis length for each peak and the averaged value for each sample
are summarized in Table 4.2. As it can be seen, the value monotonically increases in the four
samples for all of the examined peaks and therefore also in the average value. Since the c-axis
length increases with decreasing oxygen content,[131] these values testify that the doping levelFig.4.4 XRD diffraction pattern for all the Bi2223 samples examined, going from the overdoped
sample above to the most underdoped one on the bottom.
52

Sample NameOvD109
OpD109
UnD105
UnD88(0 0 10) (Å)(0 0 12) (Å)(0 0 14) (Å)(0 0 24) (Å)

Mean c-axis (Å)

37.23637.25137.31337.34037.15437.16837.23037.23737.12737.14337.20137.22237.09237.10237.15737.20237.15237.16637.22537.250

Table 4.2 Extracted c-axis values, for all the samples, from the different peaks and average c-axis
value obtained.
truly decreases as expected from the annealing condition and the magnetic susceptibility
measurement. In particular, the overdoped sample c-axis is shorter than the optimally doped
sample one. Therefore, even though the TC of these two samples is the same, the oxygen content
and the doping level is different. The obtained mean c-axis length range from 37.152 Å in theoverdoped sample to 37.250 Å in the underdoped sample and these values are roughly consistent
with the previous reports for Bi2223. [125], [126], [131] A more detailed analysis of the XRD
pattern is outside of the goal of this work and has already been done by the sample grower, [125],[126] therefore we will not discuss a more precisely peak assignment and the width of the peaks.

4.2 Raman Results
The ERS spectra for the optimally doped sample are shown in Fig.4.5 (a,b). Here as explained
before, the electronic and phononic contributions overlap, with sharp peaks being due to phonons
and the electronic contribution giving the background. In the following discussion, the phonon
peaks observed are of little interest. Phononic peaks are observed in both configurations. In B 1g wehave the phonon peaks at ≈110 cm-1, 255 cm-1 (which is the most intense) and 590 cm-1, while in
B2g we have the phonon peaks at ≈115 cm-1, 380 cm-1, 460 cm-1and 580 cm-1. The lower frequency
ones are associated with the heavier Sr or Ca ions vibrations, while the higher frequency ones areassociated with the oxygen vibrations.[155]Moving on to the electronic contribution, for the antinodal B1g configuration in Fig.4.5 (a), goingfrom room temperature (RT) to lower temperature there are two ways the spectrum modifies. The
first is a suppression of spectral weight at low frequency below ≈600 cm-1, and the second is theappearance of the two peaks at higher frequency (≈560 cm-1 and ≈800 cm-1). As to the former,
going from RT to 115K, we have the loss of spectral weight between 200 and 600cm-1 that iscaused by the pseudogap opening.[134], [143], [156], [157] The pseudogap manifests itself in thismanner in the Raman spectra, which is a subtle suppression of the spectral weight in the antinodal
B1g configuration starting from the pseudogap energy value ωPG. Since this suppression is so
minute, in this study we cannot draw strong conclusions on the value of the pseudogap energy.
The suppression is evident at ≈600 cm-1, but it could start at higher energy such as 800 cm-1. For abetter discussion on the pseudogap value by Raman, spectra with better signal to noise ratio must
be taken at temperatures above and below T*, but this is outside the scope of this work.
53

Fig.4.5 Bi2223 Raman spectra for the OpD109 sample with TC=109K. a Antinodal B1g spectra. At
low temperature a double pair breaking peak is visible. b Nodal B1g spectra. At low temperature asingle pair breaking peak is visible.
At T<Tc(=109K), a more dramatic suppression is observed below 500cm-1, which is due to thesuperconducting gap opening.
The second change in the spectra is the appearance of the two peaks at ≈560 cm-1 and ≈800 cm-1
below TC. As discussed before this kind of peaks are associated with the Cooper pair-breaking into
two Bogoliubov quasiparticles with a transition across the superconducting gap, and are therefore
associated with superconductivity. The new observation in this work is that, not one but, two pairbreaking peaks are visible, and we attribute this to the double superconducting gap of Bi2223.
Basing on the other techniques that found a signature of the double gap in Bi2223, which are
ARPES[123] and NMR[130], the peak at lower energy is assigned to the pair-breaking peak in the54

outer plane (OP) and the one at higher energy is assigned to that of the inner plane (IP). Such a
double peak structure has never been reported so far in Raman spectra, and is in clear contrast
with the single peak shown by the double layered Bi2Sr2CaCu2O8 Bi2212, [48], [49], [133]–[135]and the other double or single layered compounds[46], [47], [136]. As discussed in section 2.6,
triple layer cuprates have been examined before by Raman,[137]–[141] but no signature of adouble gap has been reported. Most of these work are quite old, therefore this may be due tosample quality issues or instruments limitations. However we note that in some recent data on the
triple layer Hg1223 a double pair braking peak could be visible, although it was not identified by
the authors[138].
Unfortunately the oxygen phonon present at ≈590cm-1 is quite close to the OP superconducting
peak at ≈560 cm-1 and this may create some confusion. For example it may mislead to think that
the OP pair-breaking peak does not disappear above TC, even though this is not the case. Also it
could lead to the idea that the double peak is an artefact, and that the lover peak is in fact just aphonon peak. However we strongly believe that this is not the case for multiple reasons. Firstly,
the difference in frequency between the phonon peak above TC and the peak at low temperature
is quite large, too large to be a simple phonon shift induced by temperature. Secondly, the peak at
low temperature is too broad (≈100 cm-1) to be a phonon peak. In general, phonons become
sharper, not broader with lower temperature. Finally the intensity of this peak is too big withrespect to the small phonon peak above TC and this is even more evident in the overdoped sample,
which is discussed later and shown in Fig.4.6 (a).
We have carefully measured the temperature dependence of the spectra to check whether thetwo peaks start to develop at different temperatures or not (see Fig.4.5 (a)). However, within our
measurement resolution, no clear difference was observed in the onset temperature for the peakdevelopment. The density of Cooper pairs at temperature just below TC is low, making the signal
weak, and therefore no peak is visible at 100K, and at 80K the two peak are both visible even if
extremely weak. This assessment is furtherly complicated by the oxygen phonon at ≈590cm-1
which may conceal the appearance of the OP peak. Therefore the simultaneous appearance of
these two peaks may be an artefact created by experimental limitation; however it may also be
the real behaviour of the sample. In that case it indicates that the two superconducting gaps open
simultaneously, although the doping is different in the IP and in the OP. In NMR data on different
multilayer samples it seems that even though the TC of the two layer is different, the layer withhigher TC drives the other layer to superconductivity.[9] However, since these data are on powder
samples, and not single crystal, it is still an open problem to understand if superconductivity
appears at the same temperature on the two layers.
On Fig.4.5 (a) the peak position is marked with red and blue dashed lines for the OP and IP
respectively. These peak positions have been extracted from the subtracted intensity plot, which
will be discussed later on, in Fig.4.7. These energy values found for the B1g peak positions in the
optimally doped sample are roughly in good agreement with the ARPES data from Ref. [123].
The nodal B2g spectrum for the optimally doped sample is shown in Fig.4.5 (b). Here at 10K adouble pair–breaking peak is not visible. Instead a single, very broad peak appears. It is expected55

Fig.4.6 B1g and B2g Raman spectra of Bi2223 for OvD109 (a,b), OpD109 (c,d), UnD105 (e,f) and
UnD88 (g,h) samples. The OP and IP peak positions are indicated by blue and red dashed lines,
respectively in panels a, c and e. The single peak observed in the B2g configuration is indicated by agreen dashed line in panels b, d, f and h. The precise peak positions have been extracted by thesubtracted intensity plot in Fig.4.7
that due to the smaller values of the superconducting gaps in the nodal region and the originallybroad feature for B2g, the two peaks, even if they exist, overlap with each other, forming a single
broad peak.
In Fig.4.6 the B1g and B2g Raman spectra for all the samples examined are shown, going from theoverdoped sample (OvD109) on the left to the strongly underdoped one (UnD88) on the right. In
Fig.4.6 (a) the antinodal B1g spectra for the OvD109 sample is shown. Here the double pairbreaking peak structure is observed and is even more intense and clearer than the one in the
optimally doped sample. When the doping level slightly increases, the double B1g peaks areobserved at slightly lower energies than the ones of the optimally doped sample (see Fig.4.6 (a)dashed lines compared with Fig.4.6 (c) dashed lines). The pseudogap opening is still visible in theoverdoped sample going from RT to 115K, as a small suppression of the low energy spectral
weight. In B2g configuration also in the overdoped sample a single pair breaking peak appears, andthis is visible in Fig.4.6 (b). In contrast with the B1g peaks, the B2g peak appears at almost the sameenergy or a slightly lower energy than in OpD109, as shown in Fig. 4.6 (b). The differences56between the spectra of OpD109 and OvD109 proves, together with the differences in the c-axis
length extracted from XRD, that the doping levels of these two samples are different although theTc values are almost the same.
Next, in Fig. 4.6 (e) and (f), the spectra for the slightly underdoped sample (UnD105) are shown. In
the low temperature B1g spectrum in Fig. 4.6 (e), the double peak feature is still visible, eventhough not as clearly as in the optimally and overdoped sample. Again the pseudogap opening isvisible as a suppression of spectral weight between 200 and 500cm-1, going from RT to 115K. In
the B2g configuration in Fig. 4.6 (f), a strong but broad single peak is visible at 10K.
Figures 4.6 (g) and (h) show the spectra for the strongly underdoped sample (UnD88). Here in the
B1g configuration in Fig.4.6 (g) no pair breaking peak seems visible. This is likely to be due to the
suppression of the B1g Raman intensity in the underdoped region which was reported in the othercuprates and particularly in the previous reports for Bi2212[47]–[49], [135]. It can be explainedwith the confinement of Cooper pairs in the nodal region with underdoping[50] which, as
discussed previously is likely to be caused by the pseudogap. This is consistent with thetunnelling[51], [52] and the ARPES data[53]–[55]. Here the pseudogap opening is clearly visible
when the temperature decreases. Contrary to B1g, the pair-breaking peak in nodal B2g
configuration is clear and intense, as it can be seen in Fig.4.6 (h), and this was also shown by
previous reports for the other single and double layer cuprates, and is visible in the right panel of
Fig.2.22. Since the pseudogap is an antinodal phenomenon it is expected that the suppression with
underdoping influences mainly the antinodal B1g peak but little the nodal B2g Raman pair breaking
peak.
To better view the redistribution of spectral weight due to superconductivity, we subtract the
spectra just above Tc from the 10K spectra. This is shown in Fig.4.7(a) and (b) for the B1g and B2g
configuration, respectively. In Fig.4.7 (a) for the B1g spectra the double peak structure can be seen
more clearly for most of the samples. For the slightly underdoped sample the double peakstructure, which was not so clear from the raw spectra in Fig.4.6 (e), becomes evident. For thestrongly underdoped sample although a peak was too weak to be seen in the raw data, it becomesvisible in Fig.4.7 (a). On close inspection this peak is visible also in Fig.4.6 (g) even though it isextremely weak. We attribute this to the pair-breaking peak of the outer plane OP. Consideringthat the inner plane IP should be more underdoped than the OP and therefore suppressed more,
it is reasonable that the IP pair-breaking peak does not appear, and only the OP peak is visible.
From this figure we can extract the peak positions more precisely, since we are cancelling thephonon contribution, almost entirely, with the exception of their modifications due to the change
in temperature, and we are eliminating the electronic contribution not caused bysuperconductivity. The extracted peaks positions are indicated by the dashed lines. For the B1g
configuration the maximum of the subtracted spectra was taken as the peak position, whereas forB2g configuration this approach would lead to big uncertainty due to the broad peak. Therefore forB2g configuration we defined the peak position as the middle point between the two frequencies
where the intensity is half the maximum value. From this figure we also defined error bars for the57

Fig.4.7. Low temperature Raman spectra of all samples after the subtraction of the spectra justabove TC. The peaks positions are extracted from this figure and indicated by the dashed lines. a
Antinodal B1g high-T subtracted spectra. The double peak structure becomes clear for the OvD109
sample, OpD109 sample and the UnD105 sample. The peak of the OP becomes visible for the
UnD88 sample. b Nodal B2g high-T subtracted spectra.
peaks positions, as the frequency where the 50% and 75% of the maximum intensity value of thepeak is reached, for B1g and B2g respectively. While the B1g peak monotonically shifts to higher
energy and loses intensity with lower doping, both for IP and OP, the B2g peak shifts to lower
energy when going from the optimal to the underdoped samples. This opposite doping
dependence of the peak position in the underdoped regime is consistent with the previous reports
for the double and single layer cuprates and is commonly referred as two energy scale
behaviour,[46]–[49] which was discussed in the previous sections. However, to better discuss thedoping dependence, we need to determine the actual layer doping for each of the IP and OP, andthis will be discussed in the next section.

58

4.3 Average and Layer doping determination
As discussed in the previous sections, in multilayer cuprates with 3 or more Cu-O layers the IP and
OP layers doping levels are different and do not correspond to the average sample doping. In
order to visualize the doping dependence of the two energy gaps, we need to estimate the doping
level of the IP and OP for all the samples. For the optimally doped sample the available NMR
data[130] provide an estimate of the IP and OP doping levels, basing on the Cu Knight shift, which
depends on the carrier concentration around the Cu atoms. A linear relationship between doping
and Cu Knight shift was observed and calibrated for the other cuprates of known doping.[9] This
relationship was used to calculate the layer doping of the IP and OP in the optimally doped Bi2223,
finding the values of p(OP)=0.203 and p(IP)=0.127, respectively. Therefore for the optimally doped
sample these two experimental values can be used.
For the other samples, since such measurements are not available, a way to evaluate the layer
doping is needed. For this we start by estimating the average sample doping. For the underdoped
samples this can be done from the decrease of TC. The parabolic relationship between TC and theaverage sample doping p, was used since the early days of the research on cuprates and is
expected to be valid, even if it could be a rough approximation, especially for triple layer cuprates.
This is given by: Tc/Tc,max=1—82.6 (p-0.16)2 [35], [36]. From this formula, assuming that the
optimally doped sample average doping is pAVERAGE,OpD=0.16 we can obtain the average sample
doping for the two underdoped samples pAVERAGE,UnD. To obtain the layer doping, we assume thatthe doping shift of each layer from the average doping of the sample does not change with thesample. Therefore we can calculate this shift for the optimally doped sample as: 𝛥𝑝𝑂𝑝𝐷 (𝑂𝑃) =0.203 − 0.16 = 0.043 and 𝛥𝑝𝑂𝑝𝐷 (𝐼𝑃) = 0.16 − 0.127 = 0.033. Assuming that 𝛥𝑝(𝑂𝑃 ) and𝛥𝑝(𝐼𝑃) are constant, we can calculate the layers dopings as:
𝑝𝑈𝑛𝐷 (𝑂𝑃) = 𝑝𝐴𝑉𝐸𝑅𝐴𝐺𝐸,𝑈𝑛𝐷 + 𝛥𝑝𝑂𝑝𝐷 (𝑂𝑃 )(4.1)

𝑝𝑈𝑛𝐷 (𝐼𝑃) = 𝑝𝐴𝑉𝐸𝑅𝐴𝐺𝐸,𝑈𝑛𝐷 − 𝛥𝑝𝑂𝑝𝐷 (𝐼𝑃)

(4.2)

This may be a rough way to determine the layer doping, but we expect it to be valid as a first
approximation.
For the slightly overdoped sample, since the Tc is the same as the optimum value, we cannot use
this method to estimate the doping level. As an alternative way, we can use the c-axis lattice
parameter determined by XRD. Assuming that the c-axis length is linearly proportional to thedoping level (oxygen content), we can determine the average doping also for the overdoped
sample. We firstly plot the pAverage value versus the c-axis length for the optimally doped sample
and the two underdoped sample, and this is shown in Fig.4.8 (blue dots). By fitting these known
points with a linear function (red line in Fig.4.8), we can extrapolate the obtained function to thec-axis length of the overdoped sample, obtaining the average doping of the overdoped sample(red dot in Fig.4.8). With this estimated value (pAverage,OvD ≈ 0.1697) we can calculate the layers

59

Fig.4.8 Average doping of the samples versus the c-axis length. The 3 blue point represent the
optimally doped and underdoped samples where the average doping was obtained from theparabolic relationship between TC and p. The red line is the linear fit of these 3 points. The red dot
is the average doping of the overdoped sample obtained assuming the linear fit.

Sample NameOvD109
OpD109
UnD105UnD88

pAVERAGE

p(OP)

p(IP)

0.16970.16
0.13890.1117

0.213
0.203
0.182
0.155

0.137
0.127
0.106
0.079

Table 4.3 Summary of all the assumed or calculated dopings for all the samples, including the
average doping, the OP and IP layers dopings.
dopings for the overdoped sample using the same formulas (4.1) and (4.2) for the OP and IP,
respectively. The doping levels determined for all samples, both the average and the layer dopings,
are summarized in Table 4.3. As it can be seen, according to our doping estimation, the outerplane is overdoped in all samples, except for the strongly underdoped one, where it becomesslightly underdoped. The inner plane is underdoped in all samples. In the strongly underdoped one
the doping value p(IP)= 0.0787 is close to the minimal doping where superconductivity disappears
pmin=0.05, therefore, it is reasonable that superconductivity is confined in the nodal region and nosuperconducting IP peak is observed in the antinodal B1g Raman spectra of this sample.

60

Using these layer doping values we can discuss properly the doping dependence of the double
superconducting peak structure observed in the Raman spectra.

4.4 Doping dependence of the Raman peaks
We use the layer doping values determined in the previous section (and summarized in Table 4.3)
to plot the B1g pair-breaking peak energy as a function of the Cu-O layer doping in Fig.4.9. Since
the double peak structure is not observed in B2g, we can only plot the energy value of the single
B2g peak as a function of the average sample doping and not of the layer one.
Both IP and OP B1g peak energies increase with decreasing doping, as expected from the previous
reports on different cuprates. [46]–[49] However, here the striking result is that, when the
difference in doping between the two layers is taken into account, the B1g peak energies of the IP
and OP align on a single line. This is surprising since the two layers are chemically inequivalent, but
the peak energy does not seem to be affected by these differences basing on this result. In otherwords it seems that the doping level is the only parameter determining the peak energy. However
this conclusion is based only on the doping values examined here, and a more solid evidence
would come if overlapping doping levels for the two layers were available. Nonetheless thisunifying picture of the behaviour of both layers is surprising and may not be incidental.
The B2g peak energy seems to be following the superconducting dome, which is the expectedbehaviour of the single and double layer compounds as discussed in section 2.6. However, this
could be an artifact and not the real behaviour for multiple reasons. Firstly, since the double peakstructure is not resolved, we cannot separate the IP and OP peaks energies. The different doping
levels of these two layers mean that two different doping dependences could be overlapping,giving an artifact doping dependence. Additionally the originally broad B2g peak gives strong
uncertainty on the peak position determination, and this can be seen in the large error bars in
Fig.4.9. Finally it must be considered that we did not examine a large doping window with our four
samples, which is necessary to reveal a clear dome shape in the case of other single and double
layer cuprates. For all the above reasons we believe that we cannot draw strong conclusions on
the B2g doping dependence.
The present result is, to our knowledge, the first doping dependent spectroscopic study on the
triple layer Bi2223. The doping dependence found here is qualitatively consistent with the reportson the single and double layer cuprates [46]–[49]. Namely, the two energy scale behavior
discussed in section 2.6 has been confirmed also in the triple layer compound. As discussed in
section 2.6, the continuous increase of the superconducting B1g peak energy with decreasing
doping is strange, if we consider that the nodal ARPES gap, which is commonly associated withsuperconductivity, was found to be constant over a broad range of doping[2] (see Fig.2.10). This
problem is common for the triple layer and the single and double layer cuprates, since the same
doping dependence has been found. A possible explanation for this inconsistency is to assume a61

FIG. 4.9 Doping dependence of the pair breaking peak energy. The antinodal B1g energy is plottedusing the estimated OP and IP doping. The B2g peak energy is plotted as a function of theestimated average doping. The dashed line and curve are the doping dependence curves takenfrom Fig.2.22 taken from Ref. [47] where the peak energy of single and double layer cuprates
collapse when divided by Tc,max .
certain degree of positive interaction between superconductivity and the pseudogap or strong
correlation called “Mottness”. The deviation from d-wave gap in the antinodal region is normallyassociated with the pseudogap and, as discussed previously, this deviation and therefore theantinodal gap increases with lower doping, as indicated by ARPES[43], [44]. However, since thisdeviation is assumed to be due to the pseudogap, it should not influence the superconducting
Raman peak energy, and this is supported by the fact that with decreasing doping the B1g peak
disappears gradually, due to the competitive relationship with the pseudogap. If, on the other
hand, we assume some degree of interaction between superconductivity and the pseudogap, eventhough superconductivity is suppressed, the superconducting gap value could be enhanced by theincreasing pseudogap in the antinodal region, and this could explain the increasing B1g peak energy
with lower doping. In this picture superconductivity and the pseudogap do compete with eachother, explaining the loss of the B1g peak intensity, but at the same time they have some degree of
positive interaction, explaining the increasing B1g peak energy.
Here we also introduce another scale in the right axis of Fig.4.9, the peak energy (PE) divided bykB*Tc,max , which should be close to 3.5 in a BCS superconductor if the PE corresponds to a doubleof the gap energy Δ. In Ref. [47], it was demonstrated that this ratio of various single and double
layer compounds collapse on a universal doping dependence, and this plot is shown in Fig.2.22.
This universal doping dependence is plotted with dashed lines in Fig.4.9 both for B 1g and B2g
configurations. It is clear from this figure that for both B1g and B2g the PE/kB*Tc,max ratios are larger62

in Bi2223 than the ones for the other single or double layered cuprates. This suggests a larger
energy scale of the pair-breaking peak, compared with Tc in Bi2223.
The characteristic feature of Bi2223 with respect to the other single and double layer cuprates ofFig.2.22 is the coexistence of different doping layers in a unit cell, where the lower doping CuOlayer (IP) is sandwitched by the higher doping CuO-layers (OP) as discussed in the previous
sections.
The high Tc value and the large gap energy could be attributed to this feature, and are therefore
likely to be multilayer effects. Experimentally we observe only a single superconducting transition,
but not a double step transition, with the two Raman peaks appearing at the same temperature. Itmeans that the IP and OP are not completely independent but interact with each other, although
the result in Fig.4.9 seems to suggest that each layer behaves independently, showing nodifference in their doping dependence which seemingly collapse on a single line.
Both of the high Tc (as previously discussed in section 2.4) and the large pair-breaking energy ofBi2223 can be discussed in terms of the multilayer effect. Firstly a high Tc value could be achievedon the IP due to the protection from the blocking layer disorders[8] or due to the appropriate
next-nearest-neighbor hopping parameter t’[7], which originally gives a large gap value of the IP ina whole doping range. The IP gap might be further enhanced due to the previously proposed
positive interaction with pseudogap, which should be strong on the IP due to the low doping levelof this layer. In addition the OP gap could be also enhanced through the interlayer tunneling of
Cooper pairs.[158] This effect may increase the OP gap value and decrease the IP gap value whichis enhanced by the effects discussed above, and this would average out the two gaps value, giving
two enhanced IP and OP gaps that align on a single doping dependence as seen in Fig.4.9. Anothereffect of this interlayer coupling may be the enhancement of the superfluid density of theunderdoped IP, and the combination of these effects may lead to the high Tc of Bi2223, and othertriple layer cuprates.
In doing these considerations on the TC, in addition to these positive effects, we need to consider anegative effect of the pseudogap on superconductivity. Since the TC is suppressed by thepseudogap in general, it is likely that the bulk TC of Bi2223 is lowered by the pseudogap whichshould be strong in the underdoped IP. The combination of these two kind of effects, namely theenhanced gap energy together with the suppressed TC can explain why the ratio of PE/kB*Tc,max
observed in Fig.4.9 is much larger in Bi2223 than in the other single and double layer cuprates ofFig.2.22.

63

64

5: Analysis based on ARPES
5.1 Bi2212 Analysis
5.1.1: Calculation Input preparation

To calculate the Raman spectra starting from the ARPES data using the Kubo formalism, describedin section 3.3, the first step is the treatment of the ARPES raw data. The samples that wereanalysed, both by ARPES and Raman, are one overdoped (TC=85K), one optimally (TC=92K) and one
underdoped (TC=75K) sample named OD85K, OP92K and UD75K, respectively. The ARPES data are
obtained by synchrotron radiation ARPES for the optimally doped and underdoped samples and by
He lamp ARPES for the overdoped sample. The ARPES and Raman experiments for the Bi2212
samples were performed by my colleagues from my same laboratory (Tajima Lab. Osaka
University). The experimental details of said ARPES experiments have been reported in section 3.4
and will not be repeated here.
Firstly the Fermi vector kF must be identified, and this was done by inspection of the momentum
distribution curves MDC for as many ARPES cuts as possible. This procedure can be successfully
performed only in the nodal and intermediate region, since the band is dispersive in these areas ofthe momentum space. On the other hand this cannot be done in the antinodal ARPES cuts, since
the band becomes flat and non-dispersive in these areas of the momentum space due to strong
correlation effects, and this can be seen clearly for all the samples ARPES cuts in Fig.5.2, Fig.5.4
and Fig.5.6. For these antinodal cuts the kF position was obtained later through the tight binding
fits. The experimental ARPES angles of acquisition, which determine the positon of the data in the
momentum space, are subject to experimental errors, therefore these must be corrected, throughthe procedure of ARPES mapping. For this procedure a large fast scan over the one whole Brillouinzone was taken, and the angles were corrected by ensuring the correct symmetry of the kF
positions. The higher resolution data which are used for the calculation are corrected to beconsistent with the kF positions of the faster scan.
The result of our ARPES Fermi surface mapping can be seen in Fig.5.1, Fig.5.3 and Fig.5.5 for the
optimally doped, underdoped and overdoped samples, respectively. Thanks to the symmetry of
the cuprates, only half of a Brillouin zone quadrant must be measured for the calculation, and thepresent data span this area almost entirely, with only a small area missing close to the nodal
region and the Γ point in the dataset for the optimally and underdoped sample.
In Fig.5.2, Fig.5.4 and Fig.5.6 we show all of the ARPES cuts for the optimally, underdoped andoverdoped sample, respectively. Here the profile of the bands along the cut, starting from the Γ-Mline can be seen, and the evolution of the band from the nodal to the antinodal region is visible.
The opening of the superconducting gap can be clearly seen going from the ungapped nodal cuts
to the antinodal cuts where the gap is the largest. As discussed earlier, ghost bands which are
created by the modulation of the Bi-O layers are present in the ARPES data of Bi2212,[129] and arealso observed here. The ghost band intensity must be avoided, and this is easily done by the65Fig 5.1 ARPES data mapping for the optimally doped sample, the extracted Fermi vectors are
represented by the purple diamonds.

Fig.5.2 ARPES cuts for the optimally doped Bi2212 sample, going from the node in C1 to theantinode in C866

Fig.5.3 ARPES data mapping for the underdoped sample, the extracted Fermi vectors are
represented by the purple diamonds.

Fig.5.4 ARPES cuts for the underdoped Bi2212 sample, going from the node in C1 to the antinode
in C9

67

Fig.5.5 ARPES data mapping for the underdoped sample, the extracted Fermi vectors are
represented by the purple diamonds for the antibonding band AB and by the red diamonds for thebonding band BB.

Fig.5.6 ARPES cuts for the overdoped Bi2212 sample, going from the node in C1 to the antinode inC10. Two bands are present due to the multilayer band splitting: the bonding BB and antibonding
AB bands.

68

correct choice of BZ quadrant. Additionally, some of the well-known anomalies of the bands areobserved here, like the kinks in the band dispersions and higher energy features below the mainband in the antinodal region.[159]–[161] These anomalies are likely to be due to strong correlation
effects, and, in the case of the kinks, to electron phonon interaction. These present an obstacle forthe calculation since: firstly the tight binding cannot model them, and second since the highenergy intensity in the antinodal region will be a mixture of ARPES background and real signal thatshould contribute to the Raman spectra and these two must be separated for the calculation.
In the overdoped sample the previously discussed band splitting is visible, as it can be seen in
Fig.5.5 and Fig.5.6. The lower energy band is the bonding band (BB) while the higher energy bandis the antibonding band (AB). Both bands should contribute to the Raman spectra, therefore in thiswork their contribution to the spectra was calculated separately and then summed up.
Using the kF determined experimentally from the MCD inspection, we performed a tight binding
fitting of the bands. The tight binding function can be used as a rough approximation of the bareband of the superconductor in the normal state above TC. As previously discussed, the anomaliesof the bands caused by strong correlations, like the kinks and the flat dispersionless bands in theantinodal region, cannot be modelled by the tight binding function. However, we expect it to bevalid as a first approximation. Recalling here the formula used for the tight binding fit:𝜉𝒌 = −2𝑡(cos 𝑘𝑥 𝑎 + cos 𝑘𝑦 𝑎) + 4𝑡 ′ cos 𝑘𝑥 𝑎 cos 𝑘𝑦 𝑎 − 2𝑡 ′′ (cos 2𝑘𝑥 𝑎 + cos 2𝑘𝑦 𝑎) − 𝜇 (5.1)
Here the free parameters are 𝑡, 𝑡 ′ and 𝜇 while the next-next nearest neighbor hopping parameter𝑡 ′′ was fixed for simplicity to be half of the next nearest neighbor hopping parameter𝑡 ′ . To fit bothband in the overdoped sample the simpliest band splitting term was used:
𝐸𝑏𝑖 = −

𝑡⊥2
(cos 𝑘𝑥 𝑎 − cos 𝑘𝑦 𝑎)
4

(5.2)

The points used for the fitting are the experimentally determined kF and a band bottom value at Γ
taken from literature. The resulting fit parameters are summarized in Table 5.1.
The obtained band functions are shown along the ARPES cuts in Fig.5.7, and the obtained Fermi
surface are shown together with the experimental kF in Fig.5.8. The obtained fitting parameters
are roughly consistent with the previous reports.[21] The bilayer splitting term is quite large
compared to the values found in literature. The experimental kF position is quite well reproduced

UD fit02
OP fit08
OD fit02

t (eV)
0.27860
0.293280.27551t’ (eV)
0.07535
0.073758
0.06905t’/t0.270460.251500.25062u (eV)-0.25528-0.32714-0.29590

t’’ (eV)
t’/2
t’/2
t’/2

t ┴ (meV)n.a.
n.a.
88.773

Table 5.1 Summary of all the resulting fit parameters for all the Bi2212 samples. t’’ is fixed to behalf of t’. The bilayer splitting term was applied only to the overdoped sample, where the band
splitting is observed.
69

a

b

c

Fig.5.7 Tight binding fit results along the ARPES cuts for a the optimally doped, b the underdoped cthe overdoped samples. The kF displayed are determined experimentally until cut 5, 6 and 9 for
the AB and 10 for the BB in the 3 samples. After these cuts the kF displayed are determined fromthe tight binding function in the antinodal region.

70

as it can be seen in Fig.5.7 and Fig.5.8. In Fig.5.7 both the experimental kF position, in the nodal
and intermediate region, and the kF position determined from the tight binding, in the antinodal
region, are shown. The kF determined experimentally are from the first cut to cut 5, 6 and 9 for the
AB and 10 for the BB in the optimally underdoped and overdoped samples, respectively. From thisfigure it can be seen how the tight binding fails to model the anomalies of the band. In particular,
the kink in the band around -0.05 eV and the flat dispersionless band in the antinode cannot bemodelled. However this is sufficient for the present calculation.
In Fig.5.8 we can see how the Fermi surface shifts towards the origin of the Brillouin zone withincreasing doping, even if there is only a small shift going from the optimally doped to theoverdoped sample. In doing this consideration, for the overdoped sample the band with no bilayer
splitting term can be considered, since this term shifts the AB band towards Γ and the BB band
away from it. This shift of the Fermi surface towards the origin of the BZ with increasing doping is
the expected trend and shows that the mapping and the tight binding have a consistent doping
behaviour. If we recall the Kubo formula:
′′
𝜒𝛾Γ
=

∞
2
Δ2𝒌
′′
′′
∑ 𝛾𝒌 𝛤𝒌 ∙ ∫ (𝑓𝜔 − 𝑓𝜔+𝛺 ) 𝐺𝒌,𝜔𝐺𝒌,𝜔+𝛺
(1 −)(𝜔 + 𝜉𝒌 )(𝜔 + 𝛺 + 𝜉𝒌 )
𝜋𝑉
−∞

(5.3)

𝒌

we see how the tight binding has multiple uses in this calculation. Not only the calculated function
enters directly as the bare band function 𝜉𝒌 , but it is also used to obtain the kF positions in theantinodal region. Additionally the tight binding function is also used to determine thesuperconducting gap value along the cut ∆𝒌 . This is done by obtaining the position of the band at
low temperature and calculating ∆𝒌 as the quadratic difference between the tight binding and the
low temperature band. This is seen in Fig.5.9 where the calculated ∆𝒌 is shown along the ARPES
cut by the green curve, together with the tight binding function and the experimental lowtemperature band. Here it is again evident how the tight binding fails to model the flat dispersion
towards the antinode. However this is not problematic for the calculation, since the tight binding
enters in the Kubo formula (5.3) only when ∆𝒌 ≠ 0 as the bare band 𝜉𝒌 . Therefore by using a ∆𝒌function as the one shown in Fig.5.9, which is non-zero only between kF and the point where thesuperconducting experimental band and the tight binding band have the same value, thelimitations of the tight binding will not influence the calculation. The tight binding function entersin the equation only in a limited region of the momentum space, where the superconducting gap
opens, therefore even if the tight binding is not a good model the real band, we can expect it to bea valid first approximation of the bare band in this limited momentum region.
The calculation is done for each ARPES cut between the Fermi vector and the point where the cut
reaches the (0,0)-(π,π) line in the momentum space. This calculation interval is shown in Fig.5.9 by
the two vertical white lines. The weight of the band quickly becomes zero after kF, therefore as afirst approximation it was not considered. The background was subtracted from these EDCs inside
the calculation interval, using the Shirley background shown in the equation (3.12) in an iterative
matter, as seen in Fig.3.7, and assuming that the intensity at the highest binding energy iscompletely composed by background. As mentioned early, a difficulty comes from the fact that71Fig.5.8 Resulting tight binding fit Fermi surface together with the experimentally obtained Fermi
vectors for all the samples. For the overdoped sample the AB and BB bands are shown together
with the band with no bilayer splitting term (red dotted line)

Fig.5.9 Example of superconducting gap ∆𝒌 calculation along the cut (green line), and other inputs
for the calculation. The tight binding function is shown by the red curve, the low temperatureexperimental band by the green cross marks and their interpolating function. The calculationinterval is between the two vertical white lines.
72

the high energy anomalies in the antinodal region introduce some uncertainty. For example, howmuch the high energy intensity is composed by background, and how much by the anomalies thatshould contribute to the Raman signal. This could cause some uncertainty on the intensity of thehigh energy side of the calculated Raman spectra, with respect to the intensity of the peaks that′′are given by the band at the lower energy. The Green function 𝐺𝒌,𝜔is obtained from the ARPES
intensity with the equation (3.10) and (3.11), assuming the matrix element to be constant. Since
the Green function of the unoccupied states is needed for the calculation, a symmetric behavior of
the band with respect to the Fermi level was assumed. This should be valid in the case of aparticle-hole symmetric superconducting band. Therefore the EDCs were symmetrized withrespect to the zero energy. The intensities of the all ARPES cuts were normalized by the maximum
intensity value of the EDC at the Fermi vector kF. This together with the assumed constant matrix
element, means we are assuming initially a constant intensity profile along the Fermi surface.
The intensities of the two bands of the overdoped sample were separated to calculate theircontribution to the Raman spectra separately. This was done by fitting the EDCs with 3 Gaussian
peaks. Two peaks were used to fit one band each, while the remaining peak was used to fit thehigh energy features. An example of a similar EDC fit is shown in Fig.5.19 in the similar case of theinner plane and outer plane bands of Bi2223. The fit was done initially with completely freeparameters; however this leads to good results only for the EDCs where both bands are clearlyobserved. For the EDCs where one of the two bands intensities is weak a different approach isneeded. In this case the band position was fixed by examining the ARPES cuts and the peak
position extracted by the fit in the EDCs where the intensity was strong enough. The width of the
bands was also fixed by assuming a linear relationship between the width and the binding energy,
and the slope of this relationship was assumed by observing the results of the fit where both band
were intense enough. At low binding energy this linear relationship is not valid, therefore an
appropriate width had to be assumed for the more nodal cuts at low binding energy, and this wasagain done by observing the results of the fit where the intensity was appropriately high. The
results of these EDC fits are shown in Fig.5.10. As it can be seen from these obtained intensity
images, the bonding and anti-bonding bands have been successfully separated in the region where
they overlap. The abrupt change of intensity where the fit ends could not be avoided
unfortunately. This is due to the intensity of one of the bands becoming too small to be fitted atthat point. This residual may introduce some unwanted intensity in the calculation, but the effectshould be small compared to the intensity given by the rest of the band. The high energy
incoherent contribution was also fitted, and was inserted either in the BB or in the AB intensity,with attention not to double count this contribution in the momentum position where both bands
contribution to the Raman spectra was calculated.
The ratio of the intensity of the two bands is an additional parameter in the case of multiple bands.
The ARPES intensity can change heavily between two different bands because of the matrix
element and the previously discussed orbital selectivity. Therefore this ratio is heavily influenced
by experimental conditions such as photon energy and photon polarization. In this calculation, inorder not to add too many different free parameters, we normalized the ARPES intensity of the73

Fig.5.10 ARPES cuts after the subtraction of the fitted BB intensity (first row) and after thesubtraction of the fitted AB band intensity. These intensities were used for the AB and BB
calculations respectively.
two bands and sumed them up, therefore we performed the calculation assuming a band ratio
equal to 1 for simplicity.

5.1.2: Calculation Results and Discussion

The results of the Bi2212 calculations assuming constant intensity profile along the Fermi surface,
for all the samples, both in B1g and B2g configuration, are show in Fig.5.11 together with theexperimental Raman spectra for these same samples.
Starting from the optimally doped sample, it can be seen in Fig.5.11 (c,d) that we obtain a good
reproduction of the experimental Raman spectra. For the B1g configuration in Fig.5.11 (c) we
obtain a good reproduction of the peak position, which is only slightly overestimated. Regarding
the shape of the calculated spectra we have only a small underestimation of the intensity at low
frequency (below 350 cm-1) and a small overestimation at higher frequency than the peak (at 650cm-1), therefore we have an overall really good reproduction of the shape of the experimental
peak. The same can be said for the B2g configuration spectra shown in Fig.5.11 (b). The overall
shape is well reproduced, with only a small underestimation at low frequency (below 250 cm-1)
and a small overestimation at higher frequency (above 650 cm-1). The peak position seems to bewell reproduced, even though the peaks, both the experimental one and the calculated one, arereally broad, and therefore there is a big error margin.
74

For the overdoped sample, the calculated and experimental Raman spectra are shown in Fig.5.11(a) and (b) for the B1g and B2g configuration, respectively. Here both the AB and BB contribution isshown, with magenta and green dashed lines, respectively. Their contribution summed up withband ratio equal to 1, as discussed earlier, is shown by the red curve. In B1g configuration in
Fig.5.11 (a) the calculated AB and BB contribution are not so different between each other andFig.5.11 Experimental Bi2212 spectra together with the calculated spectra using the Kubo formulaand assuming constant profile along the Fermi surface, for the overdoped sample in a B1g and b B2g
configuration the optimally doped sample in c B1g and d B2g configuration and for the underdoped
sample in e B1g and f B2g configuration. In the overdoped sample panels a and b both the AB andBB bands calculated contributions are shown by magenta and green dashed lines respectively.
Here the red solid line represents the total contribution of both bands summed up withnormalized intensity and band ratio equal to one.
75

quite similar to the experimental spectra. In both cases the peak position is slightly overestimated;
therefore the summed calculated spectrum also overestimates the peak position. The intensity athigh frequency is slightly overestimated in the AB band calculated spectra, and underestimated in
the BB calculated spectra, but the total calculated spectra estimates quite well the ratio between
intensity of the peak and high energy intensity. In B2g configuration in Fig. 5.11 (b) the AB and BB
bands show quite different calculated spectra. The BB peak position is quite good, with only asmall overestimation of the peak position, while the AB calculated spectra shows a broad feature
at high frequency in place of the peak. As in B1g the high energy intensity is overestimated for the
AB band but underestimated by the BB band. The total spectrum on the other hand, reproduces
quite well the experimental B2g spectra, overestimating only slightly the peak position andreproducing well the shape of the experimental spectra. Overall we can conclude that theexperimental spectra of the overdoped sample are quite well reproduced, with only a small
overestimation of the peak position, in both B1g and B2g configurations.
In Fig.5.11 (e,f) the underdoped calculated spectra are shown, and as it can be seen, we cannot
reproduce well the shape of this sample spectra. For the B1g spectrum in Fig.5.11 (e) we can see
how the peak position is significantly overestimated, and this leads to a strong underestimation of
the intensity at frequency lower than the peak frequency. It follows that the overall shape is notwell reproduced. A similar situation presents itself in the B2g configuration in Fig.5.11 (f). Again thepeak position is overestimated and this lead to an underestimation of the intensity at frequency
lower than the calculated peak. Also in this case the overall shape is not well reproduced.
Altogether we can conclude that a good reproduction of the experimental Raman peak was
obtained, with the exception of the underdoped sample. The advantage of using the Kubo formula
to calculate the Raman spectra starting from experimental ARPES data can be clearly seen whencomparing these spectra to Kinetic theory calculation that use as input some assumed band profile.
[38], [39] The overall shape is more realistic and the peaks are naturally broad as compared to the
sharp peaks of the previous calculations. [47], [49], [142], [143] In the present work there is noneed to introduce a scattering rate, which comes naturally from the experimental ARPES data.
Another clear advantage of this approach is that here the anomalies of the band, such as the flatband dispersion in the antinodal region, are accounted for, unlike in the case of a calculation
starting from an assumed tight binding dispersion.
Our calculation fails to correctly describe the underdoped sample and the doping dependence ofthe peak position, since the energy of the peak is constantly increasing with decreasing doping forboth B1g and B2g configurations. However this is likely to be an effect of the pseudogap. As
previously discussed in section 2.7 to correctly describe the underdoped sample peak position, a
special profile of the quasiparticle spectral weight ZΛ must be assumed.[47], [49], [142], [143]Here a decreasing weight is given to the antinodal region with decreasing doping, and this can givethe correct B2g peak positions and therefore the correct doping dependence. This decreasing
quasiparticle spectral weight in the antinodal region with lower doping is justified by the effect ofthe pseudogap, which suppresses superconductivity and confines the Cooper pairs in the nodal
region with decreasing doping.[50]–[55] In our calculation the ARPES cuts were normalized.
76

Fig.5.12 Experimental and calculated Raman spectra with different linear intensity profiles for the
overdoped sample in a B1g configuration and b B2g configuration. These spectra are given by thesums of the AB and BB contributions, which are summed up with a band ratio equal to one as in
the previous calculation.
Therefore, we considered a constant intensity profile along the Fermi surface. Additionally thematrix element was considered to be constant in the momentum, which is likely to be a roughapproximation.
To try to model these two effects we change the intensity along the Fermi surface and repeat thecalculation. For simplicity, linear intensity profiles are assumed, where the kF positions are plottedagainst their d-wave positions |cos 𝑘𝐹,𝑥 𝑎 − cos 𝑘𝐹,𝑦 𝑎| and the intensity profile is assumed to belinear along this coordinate. In Fig.5.12 the calculation with different linear profiles for the
overdoped sample, together with the experimental spectra are shown. These spectra are again
obtained as a summation of the AB and BB bands contributions with a band ratio equal to one, as
in the previous calculation for the overdoped sample. Here the nomenclature adopted for theintensity profile is N1ANx which means that the nodal value of the intensity profile is 1 while theantinodal value is x. x can be greater or smaller than one, enhancing or suppressing the antinodal
77

Fig.5.13 Experimental and calculated Raman spectra with different linear intensity profiles for the
optimally doped sample in a B1g configuration and b B2g configuration.
region. In the case x<1 the notation 0px is used which indicates an antinodal intensity of 0.x. In
Fig.5.12 (a) the B1g calculated spectra for different linear profiles is shown. Here it can be seen thatneither enhancing (magenta curve) nor suppressing (yellow curve) the antinodal region produces
significant changes in the calculated spectra, with the only significant difference being the slightly
enhanced high frequency intensity when the antinodal region is suppressed. The peak position isrobust against modification of the intensity profile and there is no significant improvement inchanging it. In Fig.5.12 (b) the B2g calculated spectra for the same linear profiles is shown. Here themodifications are more substantial when the profile is changed. The peak position does not seemto change, while the width of the peak increases when the antinodal region is suppressed (or viceversa decreases when it is enhanced). However this does not seem to produce significant
improvement of the calculated spectrum, since, when suppressing the antinode, the low
frequency intensity increases, improving the calculated spectra, but so does the high frequency
intensity, decreasing the quality of the calculated spectra. Therefore also in B2g configuration there
is no significant improvement in changing the profile. Considering that there is no improvement
neither in B1g configuration nor in B2g configuration, and that the calculated spectra with linear78

Fig.5.14 Experimental and calculated Raman spectra with different linear intensity profiles for theunderdoped sample in a B1g configuration and b B2g configuration.
profile already reproduces well the experimental one , we can simply consider the constant profile
calculated spectra as the best one and as our final pick.
In Fig.5.13 for the optimally doped sample the experimental and calculated with different linear
profile spectra are shown. As it can be seen from Fig.5.13 (a) for the B1g configuration, the peak
position is again robust against changes of the profile, with only a modification of the broadness ofthe peak. The suppression of the antinodal region causes the peak to become much broader, andthis is accompanied by an overall worsening of the calculated spectra with respect to theexperimental one. In B2g configuration in Fig.5.13 (b), the situation is similar to the overdoped B2g
configuration case. Again the peak position does not seem to shift and we have a small broadeningof the peak with decreasing antinodal spectral weight, accompanied by a small enhancement at
lower and higher frequencies. As in the case of the overdoped sample, this is a small improvement
for the lower frequencies but a worsening for the higher frequencies, and in total there is no
significant improvement by changing the profile in the B2g configuration. Considering bothconfigurations there is no improvement of the calculated spectra by changing the profile we can79pick the constant profile calculated spectra as our best fit also in the case of the optimally doped
sample.
For the underdoped sample the calculated spectra with different linear profiles are shown Fig.5.14
together with the experimental Raman peak. In Fig.5.14 (a) the B1g configuration spectra areshown, and here a significant improvement can be seen. By suppressing the antinodal spectral
weight the calculated peak position shifts to lower energy, getting closer to the experimental peak
position. Additionally the intensity at lower frequency increases, and this is also an improvementof the calculated spectra, since the calculated spectra with constant profile underestimates theintensity at lower frequency. For the B2g configuration in Fig.5.14 (b) the improvement is minute.
As in the cases of the other samples the B2g peak broadens, even if only slightly. This is again an
improvement in the lower frequencies region and a worsening in the higher frequency region.
However in this case of the underdoped sample this is a small improvement since the low
frequency region, below the peak, is much larger and more significant than the one at highfrequency above the peak. Therefore suppressing the antinodal region constitutes a minor
improvement in the calculated B2g configuration spectrum. Altogether we obtain a major
improvement in the B1g configuration spectrum and a minor improvement in the B2g configuration
spectrum, therefore the antinodal suppressed profile N1AN0p1 can be taken as our pick of the
profile that gives the best reproduction of the experimental spectra so far. The N1AN0p1 profile
suppresses heavily the antinodal region, giving it an intensity of 0.1 as compared to the nodal
region whose intensity is 1.
This profile however, does not decrease the peak energy of the B2g configuration enough toFig.5.15 Intensity profiles for all of the calculated spectra for the underdoped sample, the cyan andyellow profiles are the ones where the nodal intensity was suppressed.
80Fig.5.16 Experimental and calculated Raman spectra with different intensity profiles for theunderdoped sample in a B1g configuration and b B2g configuration. Nod. Sup. Stands for nodal
suppressed, and these are the profiles shown in Fig.5.15 where the intensity of the most nodal cut
was suppressed.
reproduce the experimental observation, since the peak energy of this configuration
monotonically increase with lower doping in the three samples. One possibility to try to improve
the B2g configuration calculated spectra is, to suppress only the most nodal cut. The reason for thisis that the most nodal cut gives a broad spectra which sometimes shows no peak, depending on
the intensity profile of the band in the cut, and if the contribution of this cut is overestimated it
could hide the peak feature of the B2g configuration in the calculated spectra and prevent us from
improving the spectra with a change of the profile. Therefore we calculated the spectra with the
suppression of the most nodal cut and with different linear intensity profile for the other cuts. The
intensity profiles for all of the calculated spectra for the underdoped sample can be seen in
Fig.5.15. The result of the calculation with these nodal suppressed profiles can be seen in Fig.5.16.
From this figure we can see that the suppression of the nodal cut does not change neither the B1g
nor the B2g calculated spectra drastically if we compare the normal constant profile in the red
curve, with the constant profile where only the most nodal cut was suppressed in the cyan curve.
81

The B1g configuration is not affected since the Raman vertex makes this probe insensible to thenodal cuts. The B2g calculated spectra peak positon does not shift, but the peak becomes sharper,
which is a small improvement. If we now apply a decreasing linear profile to the remaining cuts,
therefore we use the N1AN0p1 profile, which improved the spectra, for all of the cuts, except forthe most nodal one (which we keep suppressed) a great improvement of the spectra can be seen,
and this is shown in Fig.5.16 by the yellow curve. The B1g configuration peak shift as the case of the
N1AN0p1 profile, since this configuration is not affected by the nodal cut. However, in this case,also the B2g spectra is shifted to lower frequency, and this is a clear improvement, even if the peak
position is still overestimated, and the low frequency intensity is still underestimated. The
improvement is particularly significant because now the calculated B2g peak energy is lower thanthe optimally doped one, and therefore we are reproducing the correct doping dependence thatwas discussed in the previous chapters, and that is shown in Fig5.18. Comparing the nodal
suppressed constant profile and the nodal suppressed N1AN0p1 profile (cyan and yellow curve in
Fig5.16 and Fig5.15) we can see that the shift to lower frequency of both of the B1g and of the B2g
calculated spectra peak is not due to the nodal cut suppression, but to the gradual decrease of theantinodal spectral weight with the N1AN0p1 profile. It is likely that in this dataset an excessive
intensity of the nodal cut was hiding the shift of the B2g calculated spectra peak caused by themodification of the profile. Therefore the improvement of the peak and the reproduction of thecorrect doping dependence are due to the antinodal intensity decreasing profile.
This result is analogous to the previous calculation results that use the kinetic theory[47], [49],[142], [143] in which the antinodal intensity must be suppressed in the underdoped sample toobtain a good reproduction of the B2g peak position and of the B1g peak intensity. Our result isslightly different in the sense that also the B1g peak position is particularly improved by thissuppression, but this is most likely due to the different nature of our calculation, that takes as
input experimental ARPES data. In these previous works this improvement with decreasing
antinodal spectral weight was justified by the competition with the pseudogap, that suppresses
superconductivity in the antinode with decreasing doping.[50]–[55] We believe that the present
result can be explained in the same manner. In particular if the large antinodal gap in the ARPES
data in the underdoped sample is to be attributed mostly to the pseudogap, it makes sense thatthe calculated Raman spectra using these ARPES data, will have a peak at a higher energy
determined by the pseudogap, which will be much larger than the real superconducting energy.
Therefore by suppressing the intensity at the antinodal region we are suppressing the contribution
from pseudogap dominated states, and enhancing the contribution from lower energy
intermediate momentum region states, which have a stronger superconducting character, and weare therefore decreasing the energy of the peak, taking it closer to the experimental value.
Considering that in the overdoped and optimally doped samples the effect of the pseudogap ismuch less than in the underdoped sample, it is reasonable that we can reach a good reproductionof these two higher doping samples Raman spectra with a simple constant profile along the Fermi
surface, unlike the pseudogap dominated underdoped sample, where the antinodal spectral
weight must be suppressed.

82

The calculated spectra who give the best reproduction of the experimental Raman spectra aresummarized in Fig.5.17, here the constant profile spectra are used for the optimally doped andoverdoped samples while the nodal suppressed N1AN0p1 profile is used for the underdoped

Fig.5.17 Experimental Bi2212 spectra together with the calculated spectra using the Kubo formulaand assuming constant profile along the Fermi surface, for the overdoped sample in a B1g and b B2g
configuration and for the optimally doped sample in c B1g and d B2g configuration. Experimental
Bi2212 spectra together with the calculated spectra assuming decreasing intensity profile towards
the antinode but with the nodal cut supressed (nodal suppressed N1AN0p1) for the underdoped
sample in e B1g and f B2g configuration. In the overdoped sample panels a and b both the AB andBB bands calculated contributions are shown by magenta and green dashed lines respectively.
Here the red solid line represents the total contribution of both bands summed up withnormalized intensity and band ratio equal to one.
83

Fig.5.18 Experimental Bi2212 peak positions together with the calculated spectra preak positions
using the Kubo formula
sample. Here it can be seen how we were able to reach a good reproduction of all theexperimental Raman spectra, with the exception of the underdoped sample, which is not
optimally reproduced, but has been improved by our choice of intensity profile suppressing theantinodal region.
In Fig5.18 the calculated and experimental Bi2212 preak positions are summarized. As it can beseen here, the calculated peak positions in all samples and in all of the configurations are higher
than the experimental ones. One possible reason for this overestimation is that the effect of thepseudogap is different in ARPES and Raman. The pseudogap dominates the antinodal region in
ARPES, but is only weekely observed in Raman as a small suppression of spectral weight. If Raman
is not so sensitive to the pseudogap but ARPES is, it is reasonable that the calculated spectra
starting from ARPES data overestimates the gap size and therefore the peak position. The different
doping dependence in the underdoped side of the B1g and the B2g peak position, namely the twoenergy scale, was correctly reproduce by our calculation, even if it is not as evident as theexperimental one. In particular the B2g doping dependence was reproduced starting from ARPES
data where the nodal gap slope is constant, using an appropriate intensity profile that suppressed
the antinodal region. This shows how the decreasing B2g peak energy in the underdoped side canbe explained, without considering a decreasing gap value, but considering a decreasing antinodal
spectral weight caused by the competition of the pseudogap with superconductivity.
845.2: Bi2223 Analysis
5.2.1: Calculation Input preparation

The Bi2223 Kubo calculation has been performed in a similar manner to the Bi2212 Kubo
calculation. The ARPES experiment was performed by S.Ideta (National Institute for Molecular
Science) on a slightly underdoped, but almost optimally doped sample (TC=108K) grown by UchidaGroup in Tokyo University. The details of the experiment were reported in section 3.4, and will not
be repeated here. The only parameter that will be repeated is the photon energy hν=8eV. Thisparameter is of high interest here, since, as discussed previously, the ARPES sensitivity to a certain
band can change dramatically when the photon energy is changed, due to the modification of thematrix element. It was shown in Ref.[123] that the relative intensity of the IP and OP strongly
varies with the incident photon energy.With the photon energy used here, the IP band issuppressed with respect to the OP band. This can be seen clearly in Fig.5.19, where all of the
ARPES cuts are shown, zooming on the two bands. The IP band is extremely weak in the nodal
region in the present dataset. By moving away from the node the band becomes gradually more
intense in the intermediate momentum region, but it starts disappearing again towards theantinode and is observed only until cut 13 in which it is extremely weak (panel C13 in Fig 5.19).
After the cut 13 the IP band is undistinguishable from the high energy incoherent intensity. On theother hand the OP band remains intense in all the present ARPES cuts. The fact that the IP band is
extremely weak in the nodal and antinodal region in the present dataset poses a challenge to thecalculation, since these 2 momentum regions are the most important for calculating the B2g and
B1g configuration respectively due to the momentum dependence of the Raman vertex of these 2
configurations shown in equations (3.16) and (3.15). However, since in this dataset both the IP and
OP bands are observed, we attempt to use it to calculate the contribution to the Raman spectra ofeach of these 2 bands, as it was done for the overdoped sample.
There is a certain amount of interaction between the 2 bands in the intermediate and antinodal
region as it can be seen in Fig 5.19. It is not clear if this intensity should contribute to the Raman
spectra, therefore we tried to avoid this contribution in the calculation for the IP band by
removing it through the EDC fit.
As in the case of Bi2212 calculation the kF positions have been extracted by inspection of the
MDCs. Unlike in the case of Bi2212, this operation could be done also in the most antinodal cuts,since also in these cuts the band is dispersive enough, and not completely flat. This may be due tothe fact that these cuts are in fact not so close to the border of the Brillouin zone as the ones ofBi2212, and this can be seen in Fig.5.20. The mapping was done by ensuring that the position of
the band along the nodal line was consistent with the previous reports,[123] and the result of thismapping can be seen in Fig.5.20. The fact that the measured ARPES cuts do not reach the antinode
may also be a limitation when using these data for the calculation, since this region may be quite
necessary for a better reproduction of the B1g configuration. However the underdoped IP band
peak disappears even more far from the antinode, so the IP calculated contribution should be85

Fig.5.19 ARPES cuts for the slightly underdoped (but almost optimally doped) Bi2223 sample,
going from the node in C2 to the most antinodal cut in C16

Fig.5.20 ARPES data mapping for the slightly underdoped (but almost optimally doped) Bi2223
sample The extracted Fermi vectors are represented by the purple crosses for the inner planeband, and by red crosses for the outer plane band. A ghost image of one of the bands is also
observed closer to the (π,π) point of the momentum space.

86unaffected by this limitation. The same is not true unfortunately for the OP band, therefore thepeak position in the B1g configuration may be slightly changed.
The tight binding fit was performed in this case using two separate tight binding equations, one foreach band, unlike the Bi2212 overdoped sample case where a bilayer splitting term was used. The
doping imbalance between the IP and OP layer gives a large band splitting, therefore in the Bi2223
case we can simply fit the two bands separately using the equation (5.1). The tight binding
parameters are summarized in Table 5.2, and are found to be roughly consistent with the previous
reports.[123] The ratio of the nearest and the next nearest neighbour hopping parameter t’/t isfound to be increasing from the OP to the IP band which is the expected behaviour. From Fig.5.21
and Fig.5.22 the good quality of the fit can be assessed. In Fig.5.21 the experimental kF together
with the Fermi surface calculated from the tight binding fitting are shown for both the OP and IP
bands. Here it can be seen how the calculated Fermi surface follows well the experimental kF for
both bands. In Fig.5.22 the fitted tight binding function along the ARPES cuts, together with theexperimental kF are shown. Also from this figure we can see how the fitted function follows well
the kF positions, but we can also see how the tight binding fails to describe well the experimental
bands. This is analogous to the Bi2212 case, where again the tight binding fails to describe theanomalies of the bands, such as the kinks and the flat band dispersion. However, as we previously
discussed for the Bi2212 case, since we have only a limited use for the tight binding function in our
calculation, that is to give a first approximation of the gap opening along the ARPES cuts, we
proceed with the calculation with confidence that the tight binding result is sufficient as a first
approximation, despite its limitations.
Since, as said previously, all of the Fermi vector positions could be experimentally determinedfrom the MDCs, also the most antinodal ones, in the Bi2223 case there was no need to use thetight binding fit to determine these antinodal kF. The tight binding is only used to determine thesize of the superconducting gap along the ARPES cuts, and is inserted in the Kubo equation (5.3),
and plays a role in the calculation only for the small interval of momenta where ∆𝒌 ≠ 0.
The raw ARPES intensity was treated in a similar manner to the Bi2212 case. Firstly we removed
the Shirley background in the iterative manner previously described, and assuming that theintensity at the highest binding energy was composed only by background. An example of Shirley
background subtraction for an EDC of Bi2223 can be seen in Fig.5.23. After the backgroundOPIPt (eV)t’/tt’’

μ (eV)

0.734
0.633

0.251
0.275

t'/2
t'/2

-0.773-0.386

Table 5.2 Summary of all the resulting fit parameters for the 2 bands of the Bi2223 sample. t’’ isfixed to be half of t’.

87Fig.5.21 Resulting tight binding fit Fermi surface together with the experimentally obtained Fermi
vectors for both the inner and outer plane bands.

Fig.5.22 Tight binding fit results along the ARPES cuts for both the inner and outer plane band
(green and red dashed lines respectively) going from the node in C3 to the most antinodal cut inC12, together with the experimental kF (green and red stars for the IP and OP respectively)88subtraction, the inner and outer plane bands must be separated. This was done in a similarmanner to the overdoped Bi2212 sample, by fitting the EDCs with 3 different Gaussian peaks after
the background subtraction. This procedure is clearly shown in Fig.5.23. Also in this case 2
Gaussian peaks are used to fit the IP and OP bands (one for each), and an additional peak is used
for the high energy incoherent intensity.
The EDC fit had to be done in multiple steps. Firstly the fit was done with fully free parameter,
which gives good results only in the momenta where both bands are strong. This is not the casefor the nodal and antinodal regions where the IP band is extremely weak, and for case of theantinodal region is also mixed with other strong contribution, such as the high energy incoherent
intensity and the back-bending of the OP band. Since the IP band was so weak in the nodal region(see cut C3 and C4 in Fig.5.19) it had to be fitted on its whole length, also for the momenta where
the OP band was not observed, otherwise the calculated Raman spectra would have been
submerged by noise. In this step the peak position was fixed and the width was calculated with anappropriate relationship with the binding energy (peak position), therefore the only freeparameter was the intensity. This fit with less free parameters was also done for the intermediate
and antinodal cuts at the momenta where the free parameter fit was not successful. For the last 3
antinodal cuts before the IP band disappears, where the band was extremely weak, and mixed
with other contribution, this had to be taken a step further, by assuming also an appropriate
intensity profile along the band, and leaving therefore only a multiplication constant for the wholeband as free parameter. Since the IP band was so weak on the whole Fermi surface, we opted to
calculate the Raman contribution only from the fitted IP band function for the whole Fermi surface.
This had to be done to avoid the strong contribution that noise has on a low intensity band in theFig.5.23 Example of treatment of the raw ARPES EDCs, the Shirley background is subtracted fromthe raw spectra, which is subsequently fitted with 3 Gaussian peaks, one for each band and one
for the high energy incoherent intensity.
89Raman calculation with the Kubo formula.
The result of our EDC fitting and the input of our calculation can be seen in Fig.5.24. In the upper
row, the intensity used as an input for the outer plane calculation is shown. Since this calculation isdone until the OP kF and not past this momentum point, it is not necessary to subtract properly
the IP intensity past this point and an intermediate fit result, which subtracts appropriately the IP
intensity before the OP kF could be used. For this reason the residual IP intensity seen in the figure
is not a reason of concern. In the lower row of Fig.5.24 the input intensity for the IP can be seen.
Here, as said before, we take as input only the fitted IP intensity to avoid contributions from thebackground intensity. From this figure we can see that, even if the fit result is kind of crude, wewere able to successfully separate the OP and IP intensity, and we could therefore proceed to
calculate their contribution to the Raman spectra separately.
The ARPES cuts intensity was again normalized by the maximum intensity value at the Fermi
momentum kF for each cut, and both the inner and outer plane cuts where normalized to thesame value. Therefore this calculation will consider constant intensity profile along the Fermi
surface, as the initial Bi2212 calculation, and considering the same intensity for the inner andouter plane bands. Since there is a strong dependence of the relative intensity of the two bands on
the ARPES photon energy, it is difficult to predict what should be the real relative intensity of the
bands (of the spectral function) after the elimination of the matrix element effect. Therefore
considering it equal may be a rough approximation. One quick consideration is that there is a

Fig.5.24 Results of the EDC fitting and input intensity for the Kubo calculation for the outer plane(upper row) and for the inner plane (lower row). For the outer plane the total cut intensity after
the subtraction of the fitted IP intensity was used as an input for the calculation. For the IP
calculation only the IP fitted intensity was used.
90

double number of OP than the number of IP in a unit cell, therefore the OP intensity might belarger.
The calculated intensity of Fig.5.24 was symmetrized and the calculation was performed on an
appropriate momentum range. For the OP band this range is constituted by the momentum
interval between the point of the cut on the (0,0)-(π, π) line and the OP Fermi vector. For the IP
this was done from the momentum where the fit of Fig.5.24 begins to the IP kF.

5.2.2: Calculation Results and Discussion

The result of the Bi2223 Kubo calculation using this separated IP and OP intensity is shown in
Fig.5.25. In Fig.5.25 (a) the calculated B1g contribution can be seen. The first observation from thispanel is that the OP and IP calculated Raman spectra shown with red and green lines respectively,
give a peak at a significantly different energy position. Additionally the energy positions of thesecalculated IP and OP Raman peaks are close to those of the two experimental pair breaking peaks
that were found in this study and discussed in section 4.2. The calculated peak positions together
with the experimental peak positions are summarized in Table 5.3. As it can be seen, these values
are close, with a difference of only 65 cm-1 for the OP and 23 cm-1 for the IP. In both cases thecalculated peak position is slightly lower than the experimental one. This result is a strong
evidence that our peak assignment was correct and more importantly it constitutes a strong proof
that the origin of the experimental double pair breaking peak is indeed the double
superconducting gap of Bi2223 which originates from the two chemically inequivalent inner andouter Cu-O2 layers.
By summing up the calculated B1g IP and OP contribution with a band ratio of 1.7 (enhancing the IP
contribution) we can obtain the magenta line in Fig.5.25 (a) which is a good fit of the lowtemperature experimental B1g Raman spectrum. Unlike the case of the overdoped Bi2212 sample,
here we had to use a band ratio greater than one, enhancing the IP band contribution, to obtain agood fit. This will be discussed more in detail later on. This obtained total calculated spectrum
reproduces well the shape of the experimental B1g Raman spectrum, with only a small
overestimation of the intensity between 250 cm-1 and 500 cm-1 which originates from the small
underestimation of the OP peak positon. One possible reason for this underestimation is that theB1g peak Exp cm-1 Calc cm-1
OP
565
500
IP
805
782
Table 5.3 comparison between the calculated and experimental peak energies in cm-1. A goodcorrespondence between the two is found.
91Fig.5.25 Experimental and calculated Raman spectra for the optimally doped Bi2223 sample in a
B1g configuration and b B2g configuration. The red and green curves are respectively the OP and IP
calculated contribution to the Raman spectra. The magenta curve is the summation of the OP and
IP peak contribution with a band ratio of 1.7 enhancing the inner plane band intensity.
starting ARPES data does not reach the antinodal region as discussed before and as shown in the
mapping in Fig.5.20. The fact that we are missing out the contribution from these most antinodal
cuts may reduce the total calculated peak position with respect to the experimental one andgenerate this discrepancy. On the other hand the IP peak is well reproduced by the calculated
contribution, in both of the peak position and the overall shape. This may signify that even if someresidual of the IP band remains, at more antinodal cuts than the one where the ARPES intensity of
the IP band disappears in our dataset, this does not contribute significantly to the Raman
spectrum.
92

In Fig.5.25 (b) the B2g calculated contribution for the two bands is shown together with theexperimental B2g low temperature Raman spectrum. Here we can see that even if the IP calculated
spectrum is quite strange, the IP and OP calculated peaks have an overall similar shape, which issimilar in both cases to the experimental spectrum. Both of these two bands calculated spectra
seem to reproduce quite well the broad peak and the shape of the experimental spectrum. Herethe IP calculated contribution shows a peculiar shape with three humps. This behaviour is most
likely not intrinsic, and it is probably due to limitations of the ARPES data and of our fit. As
discussed earlier the nodal IP band is extremely weak, and in the most nodal cut the band intensity
is just above the noise intensity. It follows that even a good fit of such a low intensity band cannot
be of high quality, and modifications in the band profile may occur. Unfortunately the mostantinodal cut is the one that, due to the Raman vertex, contribute the most to the B 2g calculated
contribution. For these reasons the quality of the fit is not so high, and this is reflected in the
unrealistic humps of the IP B2g calculated contribution. Nevertheless this calculated spectra overall
shape is not so far from the experimental B2g Raman spectrum, and not so different from the OP
calculated spectrum, which does not share the IP problem of low intensity. Therefore we believethat even with these limitations the IP B2g calculated contribution is not completely unrealistic.
The OP B2g peak overall shape is quite good, with a peak that only slightly underestimates theexperimental peak positons, and is only slightly too sharp. Summing up the calculated contribution
from the two bands, with the same band ratio that was used for the B1g calculated spectrum (bandratio of 1.7), we obtain the total B2g calculated spectrum, shown with the magenta line in Fig.5.25(b). This total calculated spectrum also reproduces quite well the shape of the experimental peak,with a good reproduction of the peak position and of the peak broadness.
Altogether we were able to reach a good reproduction of the experimental Raman spectra both in
B1g and B2g configurations, using the Kubo formula with ARPES data as input, and calculating theseparated contribution of the two bands. We believe that the fact that we were able to reproduce
the double peak structure separately with the OP and IP ARPES intensities constitutes a strong
proof that the origin of this double peak structure is to be attributed to the double
superconducting gap of Bi2223 and to the two inequivalent kind of copper oxygen layers.
As stated before the present result was obtained with an enhancement of the IP band intensitywith respect to the OP one, more specifically a band ratio of 1.7. The IP and OP ARPES cuts havebeen normalized, in the manner described previously, and following this normalization the IP band
had to be enhanced by a factor of 1.7. The reason we had to give this enhancement to the IP
intensity can be seen in Fig.5.26 (a). Here the summated Raman contribution with many different
band ratios is shown for B1g in Fig.5.26 (a) and for B2g in Fig.5.26 (b). It is evident that thesummation with band ratio equal to one, which is same intensity along the Fermi surface for bothbands, shown in Fig.5.26 (a) by the yellow curve, is dominated by the OP contribution and the IP
peak is only slightly visible. To obtain the correct relative intensity of the B1g peaks the IP ARPES
intensity must be enhanced up to a band ratio of 1.75, which is shown by the green dashed curve,
and which gives the best fit of the experimental spectra. For the B2g configuration in Fig.5.26 (b)we see how the band ratio does not play a big role in the overall shape of the calculated peak. Thisis due to the fact that the OP and IP calculated contributions are not so different between each93

Fig.5.26 Experimental and calculated Raman spectra with different band ratios for the optimally
doped Bi2223 sample in a B1g configuration and b B2g configuration. The green dashed curve is thesummation of the OP and IP peak contribution with a band ratio of 1.7, enhancing the inner planeband intensity, which gives the best fit reproducing correctly the relative intensity of the Ramanpeaks.
other, and therefore the band ratio does not change much the total spectra. Since this parameter
does not influence so much the B2g configuration spectrum but gives a clear improvement of theB1g configuration spectrum for a band ratio of 1.75, this value was taken as the final one for thebest fit.
We have to note however that it is unlikely that this value of the band ratio represent the real
relative intensity of the band, but that it is probably better to view this parameter as mere fitting
parameter with little physical meaning. There are multiple reasons for this. Firstly there is theconsideration that the double number of OP layer per unit cell may signify that the OP intensity
94

should be intrinsically stronger. Then, the ARPES photon energy must be considered and in thiscase it is supposed to furtherly enhance the OP band intensity. However in this calculation the
ARPES intensity of the two bands was normalized to the same value, therefore it seems strange,
given the previous considerations that we need to furtherly enhance the IP band with a band ratioof 1.75, and this value may be unrealistic. One possible source of this anomaly may be that since
the IP band was so weak in the nodal and antinodal region we had to assume several parameters
including the width and, in the antinodal region, the intensity profile. Since the Kubo calculation isa convolution of the peaks of the symmetrized EDCs with themselves, not only the intensity profileof the band, but also the width of the EDC may strongly influence the intensity. Overall too manyfactors may influence this parameter, and therefore it is better to view it as a mere fit parameterwith little physical meaning. An additional reason that may cause us to have given an excessive
weight to the IP may in fact come from the OP calculated spectrum. The B1g calculated spectrum
shows a dip structure above its peak at approximately the same frequency of the IP peak. If thisdip structure was overestimated in the OP spectrum, this may happen for example with anexcessive background subtraction, the needed IP peak intensity to correctly reproduce theexperimental B1g spectrum would increase.
In this calculation we were able to obtain a good fit of the experimental Raman spectra using alinear intensity profile along the Fermi surface, but there are multiple reasons to consider adifferent profile. Firstly the real intensity profile (or quasiparticle spectral weight) may change withthe momentum, or the ARPES intensity may be influenced by the matrix element. Additionally if
we consider the result on Bi2212 discussed in the previous section, in which we were able toimprove on the spectrum calculated for the underdoped sample by using a profile suppressing theantinodal region, it is certainly better to try different profiles also in the Bi2223 case forcompleteness. This has been done in Fig.5.27 and Fig.5.28 for the outer and inner plane calculated
contribution respectively. Here the same notation used in the previous section is adopted, where
the name of the profile indicates the intensity value in the node and in the antinode.
In Fig.5.27 (a) the OP calculated contribution with different linear profiles for the B 1g configurationis shown. Here it is obvious that the spectrum is extremely robust against modifications of theintensity profile, since the spectrum is almost unchanged. The only modification may be a minuteshift of the peak at higher energy, accompanied by a minute sharpening of the peak, withincreasing antinodal weight. However these modifications are so small that they can beconsidered irrelevant. This may be due to the strong similarities between the cuts in the antinodal
region for the OP band, that collectively give extremely similar contributions, and make thisspectral shape robust. In Fig.5.27 (b) the OP calculated contribution with different linear profiles
for the B2g configuration is shown is also shown. Here the effect of enhancing the antinodal regionis to make the peak shaper, while suppressing it has the opposite effect, and the peak position
does not seem to shift by a significant amount. However since the constant profile calculated OP
contribution has an appropriately broad peak, that reproduces quite well the experimental shape,
it seems that there is no improvement in the fit by neither suppressing nor enhancing theantinodal spectral weight. The N1AN2 spectra (that doubles the antinodal weight) gives a small
improvement in the lower frequencies, however the sharpening of the peak is not an
95

Fig.5.27 Experimental Raman spectra and calculated OP contribution to the Raman spectra withdifferent linear profiles for the optimally doped Bi2223 sample in a B1g configuration and b B2g
configuration.
improvement since the experimental spectra is broader, and also causes an underestimation of
the intensity at the higher frequencies. Overall it seems that no improvement is obtained bychanging the intensity profile and a since the result seems to be worsening in the B 2g configuration,
we believe that the best reproduction of the peak was already reached with the constant profile
calculated spectra and we therefore pick it as our best result for the OP contribution calculation.
The same procedure of calculating the Raman spectra with different linear profiles is repeated forthe IP in Fig.5.28. The calculations with different profiles for the B1g configuration are shown in
Fig.5.28 (a), and as in the case of the OP calculation the peak positon is found to be very robust
against changes of the intensity profile. The tail of the peak at high frequency is suppressed96Fig.5.28 Experimental Raman spectra and calculated IP contribution to the Raman spectra withdifferent linear profiles for the optimally doped Bi2223 sample in a B1g configuration and b B2g
configuration.
together with suppression of the antinodal region, however the peak is almost unchanged. The
only minute changes that are visible are a tiny shift at a higher frequency and a minute sharpeningof the peak when the antinodal intensity is suppressed. The shift at higher frequency would be an
improvement, since as discussed earlier, the peak position is slightly underestimated. However,the shift is so tiny that it can hardly be considered a significant improvement. In Fig.5.28 (b) the B2g
calculated intensity for the IP with different linear profiles is also shown. These calculated spectra
suffer greatly from the previously discussed limitations of the nodal IP band fit, and the threeartefact humps are visible. Apart from those, no significant improvement is observed when the
profile is changed. Suppressing the antinodal region makes the peak shift at lower frequency,97

while enhancing it shifts the peak at higher frequency, additionally the overall shape seems to bemodified in both cases. However since the starting peak position and the overall shape of thecalculated spectrum with constant profile are already quite good, these modifications of thespectral profile seem to lead only to a worsening of the calculated spectrum. Therefore,
considering both configurations, also in the case of the inner plane our choice of profile that gives
the calculated spectrum better representing the experimental one is again the constant profile.
However, we do feel that these data do not exclude the possibility of an improvement withdifferent profiles if a different ARPES dataset was to be used, especially for the underdoped inner
plane, since this failure of the different profiles to give a better reproduction of the Raman spectra
may be simply due to the previously discussed limitations of this ARPES data. More specifically the
IP band is extremely weak in the nodal and antinodal region, and while this may be sufficient toroughly reproduce the peak position under the right assumptions, it may not be sufficient toreproduce a consistent evolution of the contribution along the Fermi surface, preventing therefore
relevant observations when the profile is changed. Since the IP is underdoped, it is especially on
this layer contribution that we expected a decreasing antinodal weight to be beneficial, since thishas been shown in the previous kinetic calculation for single and double layer components, [47],[49], [142], [143] and we also were able to show it in this work in the case of underdoped Bi2212.
In conclusion, even if the IP intensity is extremely weak, we were able to separate the IP and OP
band intensity in the ARPES input data and reproduce well the experimental Raman spectra of
Bi2223. The fact that we can reproduce the energies of the two experimental peaks observed inthis work in the B1g spectra, using the separated OP and IP intensities, constitutes a strong
evidence that our assignment of the peaks is correct, and that the double peak structure truly
originates from the two superconducting gaps on the OP and IP bands. Unfortunately thelimitations of the ARPES data forced us to perform some assumptions on the IP band in the nodal
and antinodal region. These assumptions, while being sufficient to reproduce the B 1g peaks energy,
are likely to prevent us from drawing further conclusions on the bands ratio and on the intensity
profile along the Fermi surface. For this reason, the enhancement of the IP intensity, andtherefore the obtained band ratio of 1.7, that was used to reproduce the Raman spectra, is likely
to carry little physical meaning, and should be viewed as a mere fitting parameter. Since
suppressing the antinodal region gave an improvement of the calculated spectra in the case ofunderdoped Bi2212 samples, both in the present work and in previous calculation, we expected
the same improvement in the underdoped IP contribution to the Raman spectra, however this was
not observed. The reason for this is again likely to be the weakness of the IP band in the input
ARPES data, which forced some assumptions on the IP band.

98

6: Conclusions
6.1: Bi2223 experimental Raman results
In this work we obtained Bi2223 samples of four different doping levels, spanning from a slightly
overdoped sample to a strongly underdoped one, through annealing in oxygen atmosphere. The
samples were characterized by SQUID magnetometry and by X-ray diffraction to evaluate thecritical temperature and the average sample doping level.
Raman scattering measurement revealed a double pair-breaking peak structure in the lowtemperature B1g spectra, which was never observed before in the Raman spectra of Cuprates. We
interpret this double peak structure as a Raman direct signature of the double superconducting
gap of the triple layer cuprate Bi2223, originating from the two inequivalent Cu-O2 layers, theinner and the outer plane. The two peaks energies values for the optimally doped sample were
found to be consisted with the gap energies values found by ARPES in the literature.
Within our experimental resolution the two peaks were found to be appearing at the same
temperature. The different hole concentration in these two layers could lead to two different
critical temperatures for the two kinds of layers, however since the two peaks were found to
appear simultaneously at the same temperature, this points to an interaction between the twolayers. In this picture, through tunneling of Cooper pairs between the layers, the layer with thehighest critical temperature drives the layer with lower critical temperature to superconduct at
higher temperatures.
Under the assumption that the doping imbalance between the two different Cu-O2 layers of
Bi2223 does not change when the average doping of the sample is changed, we were able toestimate the layer doping level, starting from the layer doping level found by NMR for the
optimally doped sample, also for the remaining samples.
Going from the optimally doped sample to the lower doping sample, the energy of the B1g peaks
increased, both for the inner and outer plane peak, while that of the B2g peak decreases, meaningthat the two energy scale that was observed in the other single and double layer cuprates, hasbeen found also in the triple layer Bi2223. The present result constitutes, to our knowledge, thefirst doping dependent spectroscopic study on the triple layer cuprates where the OP and the IP
signals were resolved.
Considering that the superconducting gap was found to be constant in a broad range of doping by
ARPES, the increase in the B1g pair breaking peaks energy with lower doping is strange. Since theantinodal gap, which is associated with the pseudogap is increasing with lower doping, one
possible explanation is to assume that, despite the competition between the pseudogap state andsuperconductivity, some positive interaction also exists between the two and that this enhances
the pair-breaking energy in the antinodal region with lower doping. However even if the antinodal
superconducting energy is enhanced, the two state still competes, and superconductivity gets99

gradually expelled from the antinode when the hole content decreases. This could explain why theB1g pair breaking peaks energy increases with lower doping but the same time it loses intensity
and TC is suppressed.
Additionally, when the layer doping estimated was used to plot the B1g peaks energy, we foundthat the inner and outer plane energies seem to align on a single line, and this unifying picture issurprising. This seems to imply that despite the chemical and structural differences between the
two layers, the peak energy is not different, and is only influenced by the layer doping. This is likely
to be due to proximity effects, where the interaction between the two layers averages out thevalue of the two gaps.
Finally after the division of the peak energy, by the maximum sample critical temperature, we
found that this ratio PE/kBTC,MAX is much higher in Bi2223 than in the other single and double layer
cuprates, meaning that Bi2223 has a low TC relative to its large gap value. This is likely to be amultilayer effect. There are several possible explanations for the increased IP gap, that could
include: protection from the blocking layer disorders[8], high next-nearest neighbor hoping valuet’,[7] or the strong pseudogap in this underdoped layer if we assume some degree of positive
interaction with superconductivity as discussed above. The tunneling of Cooper pairs could
average the IP and OP gaps out, giving large values for both of the two, and increasing thesuperfluid density of the underdoped IP.[158] All of these effects could contribute to increase thepeak energy PE value, while the TC could be reduced by the competition of the strong pseudogap
state, originating from the underdoped IP, with superconductivity, confining the Cooper pairs
towards the antinode. The combination of these effect could explain the large ratio PE/kBTC,MAX
found here.
All of these considerations point to a complex situation in the triple layer components, where the
combination of multilayer effects, and the non-trivial relationship between superconductivity andthe pseudogap, could give the right condition for the high TC of these materials.

6.2: Bi2212 Raman results analysis based on ARPES
In this work we were able to reproduce the Bi2212 Raman spectra starting from the ARPES
experimental data for samples of three different dopings using the Kubo formalism.
The more realistic Raman spectra obtained, with respect to the previous calculations using the
kinetic theory, show the advantage of this method. Using the experimental ARPES data as an input
we can introduce naturally the scattering rates in the calculation, and correctly account for theexperimental band anomalies, which are ignored in calculations using assumed tight binding-likebands as input.
Assuming constant intensity profiles along the Fermi surface we could reproduce correctly the
overdoped and optimally doped Raman spectra, with good reproduction of the overall shape and100

only a small overestimation of the peak positions. However we could not reproduce correctly theunderdoped sample spectra. To improve the fit of this sample we had to assume a particularintensity profile along the band, suppressing the antinodal intensity (and also the most nodal cut).
With this suppression of the antinodal weight, both the B1g and B2g configuration spectra were
improved, and we were able to obtain the correct doping dependence, namely the two energy
scale. This result is analogous to the result of previous kinetic theory calculations, [47], [49], [142],[143] where the antinodal intensity is suppressed to improve the calculation results. This can be
explained by the competition between superconductivity and the pseudogap state, where in theunderdoped samples the Cooper pairs are confined in the nodal region, and therefore it isnecessary to suppress the contribution of the pseudogap dominated antinodal states for thecorrect calculation of the pair breaking Raman peak behavior. The fact that we can reproduce thedoping dependence of the nodal B2g Raman peak in the underdoped side, starting from the doping
independent ARPES nodal gap, shows that there is no inconsistency between the two techniques,but that this is an effect of the different way the two techniques pick up the confinement of the
Cooper pairs in the nodal region caused by the competition of the pseudogap withsuperconductivity.
In all of our calculation both the B1g and B2g configuration peak positions are overestimated. This
could be also caused by a difference in the effect of the pseudogap in the two techniques ARPES
and Raman. The pseudogap state is only weakly visible in Raman as a suppression of spectral
weight, but it has a strong effect in ARPES dominating the antinodal spectra. This could mean that
ARPES is more sensible to the pseudogap. Therefore it is plausible that in the calculation of theRaman spectra starting from the ARPES data, the pseudogap dominated spectra increase thecalculated Raman peak energy, leading to an overestimation of the peak position.
In conclusion these calculations proved the viability of the Kubo calculation of the Raman spectra
starting from the experimental ARPES data and show that the apparent inconsistency between the
two techniques may be due only to a difference in how the two pick up the pseudogap effect.

6.3: Bi2223 Raman results analysis based on ARPES
In this work we were also able to reproduce the optimally doped Bi2223 Raman spectra, startingfrom the ARPES experimental data, using the Kubo formalism.
This calculation is challenged by the fact that the signal from the inner plane band is extremely
weak in the nodal and antinodal region. Despite this difficulty we were able to separate the innerand outer plane ARPES intensity by fitting the EDCs with Gaussian peaks, and fixing different fit
parameters to solve the problem of the weakness of the IP band.
This allowed us to calculate separately the IP and OP band contribution to the Raman spectra, andthe striking result was that these two gave a peak in the B1g Raman spectra at distinct energy
positions, which correspond to the energy positions of the two experimental Raman peaks found101

in this work. This finding is a strong proof supporting our assignment of the two peaks to double
superconducting gap of Bi2223 originating from the inner and outer plane gaps respectively.
Contrary to the Bi2212 case, here the peak positions in the B1g configuration were underestimatedslightly. In the case of the OP this difference may be due to the fact that the ARPES data used as an
input do not reach the end of the first Brillouin zone, but stop at a slightly less antinodal
momentum.
We were able to correctly reproduce the shape of both the B1g and the B2g configurations, eventhough the IP intensity had to be enhanced even after the two band intensity was normalizedalong the Fermi surface. The fact that the IP intensity had to be enhanced may not have any
physical meaning, but it may only be due to the limitations of the ARPES data, where the IP
intensity is extremely weak, and forces us to assume some parameters for the EDC peaks, that
may lead to the underestimation of the IP contribution to the Raman spectrum.
The dependence of the OP and IP contribution on the intensity profile of the bands along the
Fermi surface was investigated, as in the case of Bi2212. However no clear improvement of thespectra was found, even for the underdoped IP contribution which was expected to show some
improvement of the calculated spectra with a decreasing antinodal intensity, basing on theprevious Bi2212 results. This may be again due to the weakness of the IP band, which may prevent
us from seeing the dependence on the band intensity profile for the same reason that we justdiscussed.
In conclusion, even if this calculation is hindered by the weakness of the IP band in the input
ARPES data, we were able to give a solid evidence that the assignment of the experimental double
peak structure is correct. Unfortunately the limitation of the ARPES data prevents us to draw
ulterior conclusions on the intensity profile of the band along the Fermi surface or on the ratio of
the two bands intensity.

6.4: Closing remarks
The present results hint to a complex situation in the multilayer cuprates, where the combinationof multilayer effects and the non-trivial relationship between superconductivity and thepseudogap may give the high TC of these samples. Since the complex physics of these materials is
still poorly understood, these new experimental findings may help to lay the foundation of future
experimental and theoretical works.

102

Publications


G. Vincini, K. Tanaka, T. Adachi, L. Sobirey, S. Miyasaka, S. Tajima, S. Adachi, N. Sasaki, T.
Watanabe, Double pair breaking peak in Raman scattering spectra of triple layer cuprate
Bi2223. (submitted for publication to Physical Review B in May 2018)



N.T. Hieu, G. Vincini, K. Tanaka, T. Masui, S. Miyasaka, S. Tajima, T. Sasagawa, Quantitative
comparison between electronic Raman scattering and angle resolved photoemission
spectra in Bi2Sr2CaCu2O8+δ superconductors: Doping dependence if the nodal and antinodal
superconducting gap. (in preparation)



G. Vincini, K. Tanaka, T. Adachi, L. Sobirey, S. Miyasaka, S. Tajima, S. Adachi, N. Sasaki, T.
Watanabe, Quantitative comparison between electronic Raman scattering and angle
resolved photoemission spectra in the triple layer cuprate Bi2223 (in preparation)

103

Conference presentations

104



Physical Society of Japan (JPS) Autumn meeting 2016, Giulio Vincini, L. Sobirey, K. Tanaka, T.
Adachi, N. Murai, S. Miyasaka, S. Tajima, S. Adachi,T. Watanabe, Double pair breaking peakin triple layer cuprate Bi2223



29th International Superconductivity Symposium (ISS2016) Tokyo, Japan, Giulio Vincini, K.
Tanaka, T. Adachi, N. Murai, S. Miyasaka, S. Tajima, S. Adachi,T. Watanabe, Double pairbreaking peak in triple layer cuprate Bi2223 (poster presentation)

Physical Society of Japan (JPS) Autumn meeting 2017, Giulio Vincini, K. Tanaka, T. Adachi, S.
Miyasaka, S. Tajima, S. Adachi, T. Watanabe, Doping dependence of the double pairbreaking peak in triple layer cuprate Bi2223

Physical Society of Japan (JPS) Annual (73th) meeting 2018, Giulio Vincini, K. Tanaka, S.
Ideta, T. Adachi, S. Miyasaka, S. Tajima, S. Adachi, T. Watanabe, A. Fujimori, Analysis ofRaman spectra of Bi-based cuprates using ARPES results

Acknowledgements
This work was made possible thanks to all the wonderful people that assisted me greatly and to
those who made my life in Japan wonderful. Here I would like to express my sincerest gratitude to
all of these people.
Firstly I am deeply grateful to Prof. Setsuko Tajima, for accepting me in her laboratory, and guidingme through these years in an extremely professional but cheerful attitude. Her assistance wasinvaluable both for my studies and for my life in Japan.
Secondly I would like to thank Prof. Shigeki Miyasaka, whose assistance was vital to my research
and whose help with the experimental and organizational issues was irreplaceable, both for me
and for all the other member of Tajima Lab.
My deep thanks go also to Prof. Masamichi Nakajima, for his assistance with experimental an
everyday lab life issues.
I would like to thank profoundly Prof. Kiyohisa Tanaka for his invaluable guidance in the Kubo
calculations showed in this work. I also thank sincerely Prof. Shinichiro Ideta for providing anddiscussing with me his Bi2223 ARPES data. I also have to thank deeply these two professors fortheir wonderful hospitality in the National Institute for Molecular Science, in Okamachi.
I am deeply thankful to Prof. Watanabe, for his collaboration, useful comments on my work andfor providing me the Bi2223 high quality crystals that were used for my research. I am also deeply
grateful to S. Adachi, N. Sasaki, and all the other members of Prof. Watanabe group that wereinvolved in the growth of the samples.
I would also like to express my deep gratitude to the laboratory secretaries, Ms. Ayako Owaki andbefore her Ms. Yoshiko Ishimoto. They have both helped me greatly during my stay, and they havetreated me with great kindness, for which I am extremely grateful. I also want to express myappreciation to Ms. Hitomi Ami for her assistance with both private and university matters and forhelping in my Japanese studies by organizing the Japanese Half-Hour in the Science Buddy
program at the Graduate School of Science.
I would also like to express my most sincere gratitude to all the other members of Tajima Lab. who
helped me greatly with my experiments, everyday life, and who made my life in Japan much morecheerful with their friendship. I thank Dr. Tatsuya Kobayashi for his guidance and Dr. Naoki Murai
for his precious help with the Raman instrumentation. I am profoundly grateful to Dr. Toru Adachi
for his invaluable assistance with research and everyday matters, and most of all for his sincere
friendship. I thank deeply Mr. Zi How Tin, for his precious help with my research and for his
wonderful friendship. I would also like to extend my most sincere gratitude to all the members ofTajima Lab, both older and younger than me, who I am not explicitly mentioning here. It is also
thanks to all of these people efforts that the group is a good environment to carry out our
research in a cheerful and positive manner.
105

I would like to thank the people that helped me with my Japanese studies, by giving their time forfree. I am sincerely thankful to Mrs. Mihoko Inoue for helping me with my studies for more than a
year, and later for organizing the lessons. I am deeply grateful to Mrs. Chie Sekiguchi for her longassistance with my Japanese studies and for her friendship.
I am extremely grateful to my family, for their unconditional love, for always pushing me tobecome a better person and accomplish good results in my life. Needless to say I would havenever reached this point in my life without their loving guidance.
I am also profoundly grateful to my best friend Matteo for always being close to me and my family,
even while being almost on the other side of the globe.
Finally, I am incredibly thankful to Andrea, my future wife, for all the joy that she brought to mylife, and for her invaluable support that allowed me to complete my studies. She has also
contributed actively in this thesis by editing some of the figures here presented.

Giulio Vincini
Osaka, 07/15/2018

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