Documente Academic
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Su-Yang Xu
A Dissertation
Presented to the Faculty
of Princeton University
in Candidacy for the Degree
of Doctor of Philosophy
January 2015
Abstract
The discoveries of new forms of matter have been so definitive that they are used to
name periods of the history of mankind, such as the stone age, the bronze age, and
the iron age. Although all matter is composed of component particles, particles can
organize in various ways leading to different states or phases of matter. Finding all
possible distinct states that matter can form and understanding the physics behind
each of them are fundamentally important goals in physics research. Meanwhile, the
discoveries of new phases, such as superconductivity, ferromagnetism, also usually
lead to new technologies, which benefit our society. It had been long believed in
physics that all phases of matter (solid, liquid, gas, superconductivity, etc) are due
to the breaking of certain symmetries and can be described by local order parameters. However, the discovery of the topological phase of matter provided a striking
exception that cannot be described by a local order parameter. A topological phase
fundamentally differs from a conventional material in that a topological phase of matter is described by a nontrivial topological number, which is a global quantity based
on the bulk electronic wavefunction throughout the momentum-space Brillouin zone
of a crystal. The nontrivial topological number guarantees the existence of protected
surface states, which are of interest because these surface states are insensitive to
smooth changes in material parameters and cannot be removed unless the system
passes through a topological quantum phase transition. In 2007, the 3D Z2 topological insulator (TI) state was identified in bismuth-based materials. A 3D TI is a
band insulator in the bulk but features spin-polarized Dirac electronic states on its
surfaces. This discovery has tremendously accelerated the research field of topological matter. Not only the 3D Z2 TI phase itself has attracted huge research interest,
but also, more importantly, it has inspired theoretical predictions for a range of new
topological phases of matter. The primary examples include a topological crystalline
insulator, a topological Dirac/Weyl semimetal, a topological Kondo insulator, a topo-
in a prototype Z2 TI Bi2 Se3 , which are the keys to realizing a topological superconductor or a Chern insulator. The works in this thesis constitute the realization of
a number of new topological phases of matter beyond a Z2 TI state that are being
studied by many groups worldwide. With these discoveries, the world of topological matter gradually unveil itself. And we have many reasons to believe that this is
just the tip of the iceberg and there are many more of them with yet more exciting
properties that await their discovery.
Acknowledgements
First and foremost, I would like to thank my advisor Prof. M. Zahid Hasan for
his mentorship and support. He has been a constant source of encouragement and
advice throughout my graduate studies. I always remember his words: The idea
is to keep trying. Everyone will face failure. But if we keep trying, on average we
will do fine. Every time I run into difficulties in my experiments or in fighting with
the reviewers to get a paper published, these words encouraged me. Indeed, now I
understand that there is no sure path to success, and the key is to keep trying. I
also benefited tremendously from his ability to understand and explain the essences
of physics without bringing many formations, and his insights in condensed matter
physics, especially when it came to looking out for the next exciting topics in our
field. This is one the main driving forces to maintain our group in the front line in
the fierce competition. Moreover, I am grateful for the freedom he gave me and also
every other member in our group to pursue our individual interests in our research
work. He allowed us to come up with our own research projects, design our own
experiments and consult experts in relevant areas such as ARPES technique, material
growth and condensed matter theory. I sincerely thank Zahid for every single aspect
of my graduate research.
I am also indebted to my colleagues and friends in my group. I wish to thank David
Hsieh, Dong Qian, and Matthew Xia for introducing me into the group and helping
me settle down. Andrew Wray taught me how to use ARPES and was extremely
generous as a teacher when I started to work on ARPES on topological insulators.
Madhab Neupane, Chang Liu and Nasser Alidoust have been wonderful teammates
in experiments, and Madhab and Chang have also been great friends in my personal
life. I thank Ilya Belopolski for his infinite curiosity when it came to new physics and
for always being unsatisfied with the answers that I provided to his questions. This
drove me crazy but lead to many new and exciting ideas. I thank Guang for being
not only a wonderful labmate, but also such a reliable friend. I thank his generous
help when I got into trouble.
During my Ph.D. studies, I was very lucky to have the unique opportunity to
work at ARPES beamlines at synchrotron radiation laboratories all over the world.
As these facilities, I learned a lot from many wonderful local scientists and staff.
I thank Alexei Fedorov, Sung-kwan Mo, Jonathan Denlinger and Zahid Hussain at
the ALS in Berkeley. I thank Makoto Hashimoto and Donghui Lu at the SSRL in
Stanford. I thank Hugo Dil, Fabian Meier, Bartosz Slomski, Gabriel Landolt and
Vladimir Strocov at the SLS in Switzerland. I thank Mats Leandersson, Thiagarajan
Balasubramanian, Johan Adell and Craig Polley at MAX-lab in Sweden. I thank
Jaime Sanchez-Barriga and Oliver Rader at Bessy II in Germany. I thank Yushiyuki
Ohtsubo, BERTRAN Francois and Amina Taleb-Ibrahimi at Soleil in France. I thank
Koji Miyamoto and Prof. Taichi Okuda-sensei at the Hisor in Hiroshima University
in Japan. I thank Ishida Yukiyaki, Takeshi Kondo and Prof. Shik Shin-sensei at the
ISSP at the University of Tokyo in Japan.
None of the work would be possible without our sample growth and first-principles
band structure calculation collaborators. I was truly lucky to work with a number of
sample growth groups, and their hard work produced so many high quality samples.
These samples were breakthroughs in solid state chemistry and physics. I thank Prof.
Bob Cava and his world-renowned team in Princeton Chemistry for single crystal
samples. I thank Anthony Richardella and Prof. Nitin Samarth in Penn state for
the MBE film samples. I also thank Raman Sankar and Prof. Fangcheng Chou in
National Taiwan University and Prof. Shuang Jias group in Peking University for
single crystal samples. I thank Hsin Lin at National University of Singapore, TayRong Chang and Horng-Tay Jeng at National Tsing Hua University, Cheng-Yi Huang
and Wei-Feng Tsai at National Sun Yat-Sen University, and Prof. Arun Bansil at
Northeastern University for their collaboration on first-principle calculations. They
viii
were always ready to help and sent the calculation results on short notices. The
timely response from our sample growth and theoretical calculation collaborators
was crucially important in the competitive research.
I have also been very fortunate to be able to learn from world-renowned scientists
at Princeton Physics. I thank Chen Fang for all the discussions we had in his office, at
lunch or dinner, while we were walking from the parking lot to the department or at
so many random places and random times where we suddenly had some inspiration.
Chen almost single-handedly taught me the physics of topological phases beyond Z2
topological insulators. The discussions with him led to many fruitful ideas and new
results. I thank Prof. Phuan Ong for agreeing to be second reader on my thesis and
for his kind advice. And I thank Prof. Jason Petta and members of his group from
whom I learned a great deal during my experimental project.
Only people who have experienced the synchrotron life would understand the
meaning of constant night shifts. I cannot imagine myself going through all the
physical and mental hard times without my friends. I thank my Princeton friends
Jingke Xu, Bo Yang, Jun Xiong, Ke Wang, Zhizhen Zhao, and many others. I also
thank my friends back in China. Especially I want to thank Hei (Liang Zhang) for
being an honest, generous, reliable friend, for bearing my complaints, for comforting
my pains, and for sharing my happiness.
I thank my dear sister Chujun for being connected heart to heart. Wherever she
is and however the world changes, I wish her happiness in her life. I thank Cindy
for her wonderful cooking during the SF time. I thank Jingjing and Tian for their
accompany and education. I thank my angel girl momo for her warm care, for her
positive thinking and encouragement, and for always sticking with me to share my
thoughts and feelings.
Finally but most importantly, I am extremely grateful to my family, my grandparents Ruizhi and Ruilan, my mom Xiaobei, my dad Yuping, my aunt Hong, and
all family members for all their selfless love and care. Family is my forever source of
happiness.
Contents
Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
iii
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
vii
1 Introduction
1.2.1
The integer quantum Hall state and the Chern insulator state
1.2.2
1.2.3
11
21
1.3.1
22
1.3.2
. . . . . . . .
22
1.3.3
23
24
1.4.1
24
1.4.2
27
2 Experimental techniques
31
31
34
2.2.1
Mott polarimetry . . . . . . . . . . . . . . . . . . . . . . . . .
xi
36
CONTENTS
2.2.2
VLEED . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
39
42
2.3.1
42
2.3.2
43
45
2.4.1
2.4.2
45
47
52
53
56
3.2.1
56
3.2.2
58
3.2.3
64
3.2.4
66
68
3.4 Topological phase transition and preformed critical behavior in (Bi1 In )2 Se3 82
4 Topological Crystalline Insulator Phase in Pb1 Sn Te(Se)
84
85
89
4.2.1
89
4.2.2
91
4.2.3
98
CONTENTS
4.3.1
4.3.2
4.3.3
114
5.3.2
5.3.3
156
. . . . . . . . . . . . . . . . . . . 166
174
. . . . . . 175
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
231
Chapter 1
Introduction
In this chapter, we give an introduction about how a topological phase can arise from
a conventional material via the band inversion process. We then briefly review the
research works that discovered the first topological phases (the quantum Hall states,
and the 2D and 3D Z2 topological insulator states). We try to avoid bringing in many
theoretical formulations or experimental details but explain in an intuitive way. After
all, there have already been a number of reviews and books that systematically describe the detailed theoretical formations or the experimental details. The spirit here
is to highlight the physical picture. In the third section, we provide the theoretical
formulations for various topological phases. In the last section of this chapter, we
elaborate how these previous works inspire us to search and discover new topological
phases of matter.
1.1
The insulating state is one of the elemental groundstates for solids [118]. According
to band theory, an insulator is described by a set of completely filled electronic bands
1
Figure 1.1: The band insulator state and the band inversion . (a) The crystal
structure of a solid argon lattice. (b) The energy levels of a solid argon in the atomic
limit where the lattice constant goes to infinity resulting in a number of unbound argon
atoms. (c) As the lattice constant goes to the experimental value, the Ar3p and Ar4s
orbitals bceome Bloch bands where they gain energy dispersion as a function of the Bloch
momentum k. (d) First-principles calculation of the electronic band structure of a solid
argon, where the Ar3p valence band, Ar4s conduction band, and the normal band-gap are
seen. (e-h) The same as Panels (a-d) but for a topologically nontrivial band insulator
Bi2 Se3 . In this case, the relative energy positions of the conduction and valence bands are
reversed with respect to their atomic limit (indicated by the blue and red color code in
Panels (f,g). This results in a topologically nontrivial state in Bi2 Se3 . In Panel (h), a
within the bulk energy gap is seen.
single Dirac cone surface state (red line) enclosing the
new topological states and understanding the topological nature in various topological
materials, which are the main goals of the experiments in this thesis. For example in
numerical band structure calculations, which serves as a useful guide for experiments,
it is usually much easier to identify the band inversion in a material (by computing
the bulk band structure at different lattice constant) than calculating the actual
topological number (e.g. the Chern number involves an integral of the bulk electronic
wavefunction throughout the BZ, which is usually impractical to compute). Similarly,
experimentally driving a band inversion (by applying pressure, varying temperature
or chemical substitution) can drive a conventional material into a topological state
or transform an understood topological phase to an unknown and more exotic one by
going through a topological quantum phase transition. Therefore, it is in this context
that we highlight the importance of band inversion here.
1.2
1.2.1
The experimental discovery of the 2D integer quantum Hall (IQH) state [19] in 1980
marks the first realization of a topological phase of matter. The IQH effect is a
quantum version of the Hall effect, which is achieved by applying strong magnetic
field in two-dimensional electron systems at low temperatures. In band theory, the
quantization of the electrons circular orbits leads to quantized Landau levels. The
IQH state is an insulator in the bulk because the Fermi level is located in the middle
of two Landau levels. On the other hand, the edges of the IQH state feature chiral
1D metallic states, leading to remarkable quantized charge transport phenomena
(xy = ne2 /h) [Fig. 1.2(a)]. It turns out that the key difference between an IQH state
and a 2D conventional band insulator is a matter of topology [2022]. The quantized
Figure 1.2: The interface between a quantum Hall state and an insulator has
chiral edge mode. (a) The skipping cyclotron orbits. (b) The electronic structure of a
semi-infinite edge described in a Chern insulator with a Chern number of n = +1. A single
edge state connects the valence band to the conduction band.
1.2.2
Although a Chern insulator does not require external magnetic field, its internal
magnetization still breaks time-reversal symmetry. Can we construct a topological
phase that respects time-reversal symmetry? This is particularly motivated by the
fact that there are many more time-reversal invariant materials than the time-reversal
breaking ones in nature. Such motivation leads to the theoretical prediction of the
third type of topological insulator - the quantum spin Hall (QSH) insulator [26, 27].
In a QSH insulator, the bulk is insulating and features a pair of counter-propagating
edgestates, which are related by time-reversal symmetry. And the whole system,
unlike a Chern insulator, respects time-reversal symmetry. We provide a physical
picture to build a quantum spin Hall insulator from two Chern insulators: Let us take
a Chern insulator with a Chern number of n = +1, which is achieved by an out-ofplane magnetization +M [Fig. 1.3(a,b)]. Under time-reversal operation T , quantities
Figure 1.3: A quantum spin Hall insulator can be constructed by two Chern
insulators that are related by the time-reversal symmetry. (a) A Chern insulator
with a Chern number of n = +1 has a chiral edge mode as a result of an out-of-plane
magnetization. (b) The bottom edge projection of the electronic structure the n = +1
Chern insulator. (c,d,) Same as Panels (a,b) but with a time-reversal operation onto the
system. (e,f,) A quantum spin Hall state can be obtained by combining the above-two
Chern insulator states. The resulting electronic structure on the edges is described by two
couterpropagating edge modes that cross each other at k = 0 (or k = ). The crossing is
protected by the time-reversal symmetry as a result of the Kramers theorem.
In 2005, theoretical advances realized that the quantum spin Hall phase is indeed
topologically nontrivial [26]. In fact, it is characterized by a new topological number,
the Z2 invariant () [14, 26, 29]. The Z2 invariant can only take two values, 0 or
1, where = 0 (1) is topologically trivial (nontrivial). In 2007, the QSH phase was
experimentally demonstrated in the (Hg,Cd)Te quantum wells using charge transport
by measuring a longitudinal conductance of about 2e2 /h (two copies of quantum Hall
currents) at mK temperatures [28]. However, no spin polarization was measured in
this experiment thus spin momentum locking, which is essential for the Z2 topological
physics, was not experimentally observed [28].
It is important to note that the 2D topological (IQH, FQH, and QSH) insulators
have only been realized at buried interfaces of ultraclean semiconductor heterostructures at very low temperatures to date. Furthermore, their metallic edge states can
only be probed by the charge transport method. These facts hinder the systematic
studies of many of their important properties, such as their electronic structure, spin
polarization texture, tunneling properties, optical properties, as well as their responses
under heterostructuring or interfacing with broken symmetry states. For example,
the two counter-propagating edge modes in a QSH insulator are predicted to feature
a 1D (usually Dirac) band crossing in energy and momentum space. And edge mode
moving along the +k direction is expected to carry the opposite spin polarization
as compared to that of one moving in the k direction. However, neither the Dirac
band crossing nor the spin-momentum locking of the edge modes in a QSH insulator
are experimentally observed, due to the lack of experimental probe that can measure
these key properties for a 1D edge mode at a buried interface at mK temperatures.
10
1.2.3
In 2007, it was theoretically realized that the Z2 topological number in a QSH insulator can be generalized to three-dimensions, thus realizing the first three-dimensional
topological phase of matter [1418]. This is again a critical breakthrough in experimental and material physics because there are more 3D bulk materials than 2D films
in nature and the preparation of bulk materials is usually easier. How do we construct a 3D Z2 TI? The most straightforward approach is to simply stack a number
of uncoupled 2D quantum spin Hall states to form a 3D bulk. It turns out that such
simple stacking of the 2D QSH states does lead to a type of 3D Z2 TI, which is the so
called 3D weak TI. A weak TI is not the most topologically protected Z2 nontrivial
states in bulk materials. But let us start from a weak TI.
As shown in Fig. 1.4, let us assume that we start from a 2D QSH state that has an
inverted band-gap at the point. The blue and green colors in Fig. 1.4(a) show the
orbital nature of the bulk bands near the point, where a band inversion is evident.
Now let us have N copies of such QSH state and stack them along the out-of-plane
z direction. This will form a bulk material. And in momentum space, it means that
the 2D BZ will gain periodicity in the kz direction and becomes a cube representing
the 3D BZ [Fig. 1.4(b)]. In the 3D BZ, the Kramers points can be sorted by their
origins from the 2D BZ before stacking. For example, both the and the Z points
in the 3D BZ results from the point in the 2D BZ. We assume that the physical
coupling between these 2D QSH slices are extremely weak (e.g. in real materials,
imagine they are coupled by a very weak van der Waals interaction). This means
that the energy dispersion along the kz direction is sufficiently weak, so that it does
not change the orbital nature of the conduction and valence bands by going from the
(3D) point to the Z point. Therefore, the one band inversion in the 2D point in
the QSH slice becomes two band inversions at both the and the Z points in the 3D
BZ after stacking (here only the band inversions at the Kramers points are counted).
12
Figure 1.5: The surface of a weak TI shows even number of protected surface
states or no surface states depending on the surface termination. (a) A bulk BZ
of the weak TI. The green slices are chosen for detailed studies. (b) The edge projected
electronic structure for the green slices shown in Panel (a). Without any inter-slice coupling, these slices are identical and independent. The surface states for the kx kz surface
projection is a straight line. (c) A bulk BZ showing the two band inversions at the and
the Z points. (d) After turning on the inter-slice coupling, the edge states can hybridize and
open out gaps, except at the and the Z points due to the protection of the time-reversal
symmetry. Therefore, the surface state Fermi surface is described by two dots at the and
the Z points.
16
Figure 1.7: The surface of a strong TI features an odd number of protected surface
states at all surfaces irrespective of the surface termination. (a) A bulk BZ of the
strong TI. The green slices are chosen for detailed studies. (b) The edge projected electronic
structure for the green slices shown in Panel (a). Without any inter-slice coupling, these
slices are identical and independent. The surface states for the kx kz surface projection
is a straight line. (c) A bulk BZ showing the one band inversion at the point. (d) After
turning on the inter-slice coupling, in the case of a strong TI, only the band inversion at
the point remains whereas the band inversion at the Z point is removed. Furthermore,
for kspace region near the point where the conduction and valence bands are inverted,
the edge states can hybridize and open out gaps, except at the point itself due to the
protection of the time-reversal symmetry. Therefore, the surface state Fermi surface is
described by one dots at the point.
18
etc., remain elusive due to the difficulty of identifying a real system that has the
necessary material parameters. Moreover, the experimental study of a topological
phase relies on measuring its gapless boundary states. In a topologically ordered state,
the boundary modes are fractionalized non-electron like quasi-particles. Although in
the case of FQH, their existence can be demonstrated by charge transport. But it is in
general extremely challenging to systematically study the energy dispersion, angular
momentum (spin polarization), and other key properties of fractionalized non-eletronlike quasiparticles. On the other hand, these difficulties do not exist in a SPT state
such as a Z2 TI state in Bi2 Se3 . Furthermore, the requirement of a symmetry in
a SPT state is usually a given in a solid state system. For example, in a solidstate crystal, the translational symmetry or sometimes also space group symmetries
(mirror, Cn ) is a given. Furthermore, time-reversal symmetry is also a very common
property that exists in most non-magnetic materials. In fact, in experiments, it is
quite often that one has to make considerable effort to break a certain symmetry (e.g.
to apply strong magnetic field to break time-reversal symmetry for a FQH state)
in order to realize certain topological order. Therefore, by these (experimental or
material) considerations, the realization, the systematic study and the utilization of
SPT states are of importance and interest. In this thesis, we focus on the experimental
discoveries of new symmetry-protected topological states (mostly weakly interacting
systems within the band theory) beyond a Z2 TI.
1.3
Theoretical formulations
In this section, we provide the theoretical formulations for the Chern number and the
Z2 invariants.
1.3.1
In the IQH effect, the quantized Hall conductivity can be written as xy = ne2 /h,
where n is an integer. Thouless, Kohmoto, Nightingale and den Niks (TKNN) found
that the integer n in the transverse magneto- conductance xy is precisely the Chern
number - a topological number calculated using the electronic wavefunction over the
entire Brillouin zone. Specifically, the Chern number in the IQH state in a periodic
potential is written as [21]:
1
n=
2
BZ
[k A(kx , ky )]z d2 k
(1.1)
with
A = i < u(k)||u(k) >
(1.2)
1.3.2
There are several mathematical formulations of the Z2 invariant , including a Pfaffian construction, as a topological obstruction, as a type of pumping, or in terms of
homotopy of Hamiltonian spaces [7]. We take the Pfaffian approach developed by Fu,
Kane and Mele [14]. We define a unitary matrix:
(1.3)
where |um > is the occupied wavefunction, is the time-reversal operator. Since
is anti-unitary and 2 = 1, thus T (k) = (k). There are four special points
22
(1.4)
(1) =
4
Y
(1.5)
a=1
If the crystal has inversion symmetry, there exists a shortcut to obtain [29]. At
the Kramers points a the Bloch states um (a ) are also the eigenstates of the parity
operator with the eigenvalue m (a ) = 1. The Z2 invariant then simply follows
from with
a =
m (a )
(1.6)
where the product is over the Kramers pairs of occupied bands. This has proven
quite useful for identifying Z2 topological insulators from numerical band structure
calculations.
1.3.3
In three dimensions there are eight Kramers points, which are expressed in terms of
primitive reciprocal lattice vectors as a = (n1 b1 + n2 b2 + n3 b3 )/2, with n = 0, 1.
This leads to four independent Z2 topological invariants to define the Z2 topological
(1)0 =
8
Y
(1.7)
a=1
Det[(a)] = 1.
Besides the strong invariant, it has been shown in theory that one can define
another 3 independent weak invariants (1 , 2 , 3 ) as
(1)
i =1,2,3
8
Y
a .
(1.8)
ni =1;nj 6=i=0,1
Again, the conclusion from the above topological theory is that if all four invariants
are zero (0 = 1 = 2 = 3 = 0), then the system is a conventional band insulator; if
0 = 1, then the system is a strong (Z2 ) topological insulator; if 0 = 1 but at least
one of the weak invariants is nonzero, then the system is a weak (Z2 ) topological
insulator.
1.4
Now that we have gone through all previous topological phases, we discuss the inspirations that are brought by these previous works for discovering new topological
matter.
1.4.1
First of all, it is evident that the band inversion is a key (a critical necessary condition)
that gives rise to the topological insulator state. More specifically, by band inversion,
we mean two phenomena in the bulk electronic structure: (1) At certain k points, the
24
Figure 1.8: Band Inversions and the spin-orbit interaction. (a-c) In the case of
sodium chloride Na+ Cl , the system does not have any band inversion. The fact that there
is a large band-gap between the Cl 3p and the Na+ 3s bands is consistent with that it is
energetically costly to give the electron that is taken by the Cl back to the Na+ . (d-f )
In a material A+ B , the valence and conduction bands gain energy dispersion in a way
so that these two bands actually cross at certain Kramers point. Further consideration of
the spin-orbit interaction opens a full insulating gap. SnTe is a real material example for
this case. (g-i) In this case, without spin-orbit coupling, there is no band crossing, and the
spin-orbit interaction is responsible for both inverting the conduction and valence bands
and for opening up the full insulating gap. We note that Bi2 Se3 belongs to this case.
26
1.4.2
How do we construct new topological phases? From the discussions in the previous
sections, we know that the band inversion is a necessary but not a sufficient condition
30
Chapter 2
Experimental techniques
In this chapter, we introduce the basic principles of the experimental technique used
in this thesis (the spin-resolved angle-resolved photoemission spectroscopy) and the
review how such technique is used to reveal the 3D Z2 topological insulator state in
Bi1x Sbx and Bi2 Se3 bulk materials.
2.1
Angle-resolved photoemission spectroscopy (ARPES) is a direct experimental technique to observe the distribution of the electrons (more precisely, the density of singleparticle electronic excitations) in the reciprocal space of solids [132, 133]. ARPES is
one of the most direct methods of studying the electronic structure of the surface of
solids. The photoelectric effect was first observed by Hertz. When photons of energy
h, strike a sample surface, electrons absorb the energy and escape into the vacuum
with certain kinetic energies. A good approximation of the photoemission process
can be described by the three-step model, as shown in Fig. 2.1:
An electron is first excited by the photon inside the bulk.
31
Figure 2.1:
sample.
The three-step model used to describe the photoemission process inside the
kx =
(2.1)
(2.2)
(2.3)
Ekin = h |EB |
(2.4)
32
Figure 2.2: (a) The Scienta analyzer setup used to measure emitted photoelectrons from
the sample surface. The two hemispheres probe the electrons to produce a 2D image of
energy (E) vs. momentum (k) in one measurements. (b) The geometry of the detector
relative to the sample surface. The momentum of the electron inside the sample can be
extracted from the measured values of Ekin , , .
Ef = Ekin + V0
(2.5)
~2 k k 2
2m
~2 k 2
2m
2mEkin sin .
get:
k =
1p
2m(Ekin cos2 + V0 )
~
(2.6)
2.2
The traditional one is the Mott polarimetry. Such a technique arises from spinorbit interaction of heavy elements (such as gold) that are used as the detector target
where a spin polarized electron beam is injected, causing spin-dependent scattering.
However, since the spin-orbit interaction is usually a small effect compared to the
Coulomb interaction between electrons, the spin dependence for most scattering targets and a wide range of parameters is small. The relative influence of the electron
spin on the scattering cross section only becomes significant under conditions, where
the mean scattering cross section is small. Thus in general, the efficiency of the Mott
polarimetry method is not so high. For example, measuring the spin polarization of
the surface state of TI Bi2 Se3 at a fixed energy E along a fixed momentum space direction cut takes about 6 - 8 hours to gain good statistics using the Mott polarimetry
with synchrotron radiation light source.
A newer technology, the very low energy electron diffraction (VLEED) spin detector was recently applied. A VLEED uses a magnetic scattering target. In electron
diffraction on ferromagnets, the intensities of diffracted beams in general depend on
the spin polarization of the primary electron beam relative to the sample magnetization. If the incident electron beam has a very low energy (usually < 10 eV), then the
efficiency of measuring spin polarization is dramatically improved as compared to a
Mott polarimetry.
2.2.1
Mott polarimetry
1
2
Hint =
1
e~
e~ 2
~ + ie~ E
~ p~ e~ ~ (E
~ p~) (2.7)
+ e
(~p A)
~ ( A)
2
2
2m
c
2mc
4m c
4m2 c2
(2.8)
(2.9)
() = R ()[1 + S()P~ n
]
(2.10)
where S() is the asymmetry or Sherman function, P~ is the polarization ~2 (< Sx >
, < Sy >, < Sz >), and n
is the unit normal to the scattering plane defined by
n
=
~ki ~kf
|~ki ~kf |
(2.11)
Where ~ki and ~kf are the initial and final wave vectors of the electron respectively.
The direction n
depends on whether scattering to the left or right is being considered.
This spin-orbit scattering relation allows for the measurement of the component of
spin polarization perpendicular to the scattering plane in the following way. Consider
a beam of N incident electrons with N of them polarized along +z and N of them
along -z, which leads to a net polarization Pz = (N N )/(N + N ). When the
scattering of this beam from a nucleus takes place in the xy plane, there results a
left-right scattering asymmetry Az () defined as:
Az () =
NL NR
NL + NR
(2.12)
where NL and NR are the number of electrons scattered to the left and right
respectively through an angle . Substituting the relations NL N [1+S()]+N ][1
S()] and NR N [1 S()] + N ][1 + S()] derived from Equation 5 to Equation 7
38
2.2.2 VLEED
yields:
Pz =
Az ()
S()
(2.13)
2.2.2
VLEED
The concept of VLEED spin detector is based on a simple and intuitive phenomenon,
which is that as electrons are injected to a ferromagnetically ordered material, the intensities of diffracted beams in general depend on the spin polarization of the primary
electron beam relative to the sample magnetization.
Obviously, the efficiency of such detector depends on the ratio of electrons that
are being reflected with respect to other processes. In a simplified kinematic picture,
the intensity modulation can be described in terms of constructive or destructive
interference of reflections from different lattice planes. As the energy of the primary
beam is lowered, the radius of the Ewald sphere decreases until it is smaller than the
smallest reciprocal lattice vector. In this situation there are no higher-order diffracted
beams, and only the specularly reflected beam can be observed. This leads to an
increase of the intensity of the specular beam in LEED at very low energies VLEED,
which sets one of the foundation for using VLEED as an efficient spin detector.
So far in the above-paragraph, the discussion only contains the issue how to enhance the the simple reflection of an electron beam, but it has not covered the spin
sensitivity. Let us consider a VLEED process on a ferromagnet, such as an iron
(Fe) crystal. In a ferromagnetic material the spin degeneracy of the electronic states
is lifted by the exchange interaction, such that, e.g., a critical point in the band
Fig. 2.5 (left panel) shows schematically the layout of the Fe VLEED spin detector.
The spectrometer is a commercial hemispherical analyser (HA 50, 50 mm mean radius,
with power supply HAC 300 by VSW). Behind the exit slit of the analyzer, the
40
2.2.2 VLEED
channeltron was replaced by a three-element electron lens, which transfers the energyanalyzed electrons to a drift chamber. The scattering target is located on the optical
axis in the drift chamber. The drift chamber is equipped with coils for magnetizing
the Fe target. The coils are made of self-supporting 1 mm Cu wire with four turns of
20 25 mm diameter. During data acquisition they are kept at the same potential
as the scattering chamber and the target.
The right panels of Fig. 2.5 demonstrate the ability of such Fe VLEED detector
for measuring spin polarization. Polarized electrons were excited from a magnetized
Fe sample by 90 eV photons. Such polarized electrons are injected to the VLEED
detector with the magnetization of the Fe target set for one direction. The counts
for the scattering at different binding energies are recorded by the empty triangles
in the top right panel of Fig. 2.5. Now we flip the magnetization of the Fe target
in the VLEED detector, and perform the same measurements, where the counts are
recorded by the solid triangles in the top right panel of Fig. 2.5. It can be seen
that a clear asymmetry between these two scattering geometries is observed, which
demonstrates that the scattering of a polarized electron beam is quite sensitive to
the magnetization direction of the VLEED target. Thus the spin polarization of the
incidnet electrons can be measured based on this principle.
In reality, although Fe (001)/Ag(100) surface has a very high spin dectection
efficiency as a VLEED detector, one complication is that the efficiency is strongly
dependent on the quality of the Fe (001) surface [136]. And furthermore, the Fe
(001)/Ag(100) surface quality is found to degrade quite fast even within a day [136].
Thus one has to re-prepare the surface once per 12 hours which is inconvenient. In
reality, the preoxidized Fe(001)-p(1 1)-O targets are often used because they are
found to be stable for a much longer time than a clean Fe surface, presumably for
weeks. For example, the VLEED spin-resolved ARPES endstation at the Hiroshima
Synchrotron Radiation Center (Hisor) in Hiroshima University in Japan uses the
2.3
2.3.1
Figure 2.6: A schematic of the single crystal bulk sample geometry mounted inside the
ARPES measurement chamber. The ceramic top post was used to cleave the sample surface
in situ, to ensure a clean surface for measurements.
For single crystal bulk samples, they are grown by our collaborators including
Prof. R. J. Cavas group in the Department of Chemistry in Princeton University,
Prof. F. C. Chous group in the Center for Condensed Matter Sciences in National
Taiwan University, Prof. Y. Chens group in the Physics Department in Purdue
University, Prof. S. Jias group in the International Center for Quantum Materials,
Peking University, Beijing 100871, China.
In order to measure them in ARPES, one needs a very clean and flat surface
because ARPES is a very surface-sensitive probe. To do so, the sample is then
42
2.3.2
For MBE film samples, they are grown by our collaborators such as Prof. N. Sarmarths group in the Department of Physics in The Pennsylvania State University,
and Prof. S. Ohs group in the Department of Physics & Astronomy, The State
University of New Jersey.
For MBE samples, they are usually too thin ( 40 nm) to be cleaved. Let us
take the example of thin Bi2 Se3 films grown on some substrates [e.g. GaAs(111)]. In
order to protect the surface from oxidation, a thick Se capping layer is deposited on
the Bi2 Se3 thin film immediately before taken out of the MBE growth chamber [see
Fig. 2.7(a)]. Such a Se capped sample is then loaded into the ARPES chamber and
pumped down to high vacuum. In order to reveal the clean Bi2 Se3 surface needed
for photoemission measurements, the MBE-grown thin films are heated up inside
the ARPES chamber to 250 C to blow off the Se capping layer on top of the
Bi2 Se3 film. During the annealing, the pressure goes up and typically remains better
than 1 109 torr. Fig. 2.7(b) demonstrates the decapping process by ARPES core
level spectroscopies measurement. Only selenium core level is observed before the
decapping process (blue curve), whereas both selenium and bismuth peaks are shown
after the decapping (red curve). ARPES measurements are then performed on the
clean thin film surface. Fig. 2.7(c) shows a typical ARPES measured dispersion
mappings after decapping of a Bi2 Se3 thin film, where the sharp ARPES spectrum
demonstrates our surface preparation procedure.
44
2.4
Since the topological number is defined by calculating a global quantity (an integral,
a Pfaffian) of the bulk electronic wavefunction over the entire BZ, it is not feasible
to measure its value in experiments based on this definition. Rather, the topological
number and topological properties are usually probed by studying the boundary of a
topological system. Such an approach takes advantage of a fundamental consequence
of the topological classification of gapped band structures, which is the existence
of gapless conducting states at interfaces where the topological invariant changes.
For example, in the case of 2D IQH effect, the quantized transverse conductance
provides a measure of the systems topological number - the Chern number n. How
do we probe the topological number in a 3D bulk material? This is particularly an
important question to ask in three-dimensions since a 3D bulk topological material
is believed to exhibit no quantized transport response. In this section, we use the
example of the discovery of the 3D Z2 TI phase in Bi1x Sbx and Bi2 Se3 classes of
materials, to elaborate the way of measuring a 3D topological number by the spinand angle-resolved photoemission spectroscopy (spin-ARPES). For the sake of the
simplicity of the presentation, we put the Bi2 Se3 class before Bi1x Sbx although it
was discovered later, because Bi2 Se3 has a simpler surface state that is more suitable
for elaborating the methodology.
2.4.1
In order to probe its topological number states in a 3D Z2 TI via studying its surface
states using spin-ARPES, the first thing is to separate the surface states from the
bulk bands, which both exist in the electronic structure near the Fermi level. This
kz =
1p
2m(h + V0 )
~
(2.14)
From the equation above, it can be immediately seen that the kz value of the electronic
state at the Fermi level and the normal emission is a function of the incident photon
energy value h. Effectively, by varying the incident photon energy value, one can
effectively probe the electronic states at different kz values.
The topological surface state in 3D TIs is a type of 2D state that are localized
on the surface. Therefore, it is expected to be strictly non-dispersive along the kz
direction that is perpendicular to the sample surface normal. On the other hand,
the bulk conduction/valence bands are (3D) bulk bands. Thus they are expected to
show dispersion along all three momentum space directions including kz . Therefore,
by measuring the dispersion along the kz direction, one can effectively isolate the
topological surface states from the bulk bands.
Fig. 2.8 shows an ARPES study on Bi2 Se3 as a function of the incident photon
energy. As shown in Fig. 2.8(a). there are three major features in the measured
electronic structure: (1) a parabolic intensity continuum at 0EB 0.15 eV; (2) an
X shaped band that runs from 0 eV to -0.35 eV; (3) an M shaped band at higher
binding energies (EB 0.4 eV). As photon energy value is changed, It can be seen
that the X shaped band shows no change in its dispersion, whereas the a parabolic
intensity continuum at the Fermi level and the an M shaped band are dispersive.
The strong kz dispersion of the bulk valence band at binding energies higher than
46
Figure 2.8: Topological Surface States and electronic band dispersion along the
kz -direction in momentum space. (a) A schematic diagram of the full bulk threedimensional BZ of Bi2 Se3 and the two-dimensional BZ of the projected (111) surface. (b)
Electronic dispersion (EB vs kk ) of Bi2 Se3 at different incident photon energies. (c) The
(kk = 0) at different photon energies, showing the strong
energy distribution curves at the
kz dispersion of the bulk valence band at binding energies higher than 0.4 eV. The figure
is adapted from Ref. [32].
0.4 eV is better visualized in Fig. 2.8(c). Therefore, these incident photon energy
measurements demonstrate that the X shaped Dirac band is a 2D surface state,
whereas the other two features originate from the bulk (the bulk conduction and the
valence bands).
2.4.2
Now that we have identified the surface states in Bi2 Se3 , we experimentally show
the following properties of the surface states to demonstrate the strong topological
insulator state with 0 = 1 in Bi2 Se3 :
The two branches (left-moving and right moving) of the surface states cross
each other, forming a surface Dirac point [Figs. 2.9(c,d)].
The Dirac surface states span across the bulk energy gap, and connect the bulk
conduction and the bulk valence bands [Figs. 2.9(c,d)].
48
Figure 2.10: Spin texture of the topological surface states in Bi0.91 Sb0.09 encodes
its Z2 topological number of the bulk (2008). (a) Schematic sketches of the bulk
Brillouin zone (BZ) and (111) surface BZ of the Bi1x Sbx crystal series. (b) Schematic
of Fermi surface pockets formed by the surface states (SS) of a topological insulator that
carries a Berrys phase. (c) Partner switching band structure topology. (d) Spin-integrated
ARPES intensity map of the SS of Bi0.91 Sb0.09 at EF . Arrows point in the measured
direction of the spin. (e) High-resolution ARPES intensity map of the SS at EF that
1 and M
2 points. Corresponding band dispersion (second derivative images)
enclose the M
are shown below. The left right asymmetry of the band dispersions are due to the slight
M
1 (M
2 ) direction. (f ) Surface band dispersion image
offset of the alignment from the M
direction showing five Fermi level crossings. (g) Spin-resolved momentum
along the distribution curves presented at EB = 25 meV showing single spin degeneracy of bands
at 1, 2 and 3. Spin up and down correspond to spin pointing along the +
y and -
y direction
respectively. (h) Schematic of the spin-polarized surface FS observed in our experiments.
This figure is adapted from Ref. [31].
50
Chapter 3
Topological Quantum Phase
Transition in BiTl(S1 Se )2
A topological material is a distinct phase of matter since it features a nonzero topological number in the bulk electronic structure groundstate that can only be removed by
a topological quantum phase transition into a trivial phase. The topological number
guarantees the existence of protected surface states, which serve as the experimental
signature for the nontrivial topology. In this chapter, we present our experimental realization of a topological quantum phase transition (TQPT) from a conventional band
insulator to a 3D Z2 topological insulator in the BiTl(S1 Se )2 system. We systematically study the evolution of surface and bulk electronic and spin groundstate across
the topological phase transition. This study provides a general paradigm for understanding how various topological phases and their protected surface states arise from
a conventional material in experiments, and is of value for searching for new and engineered topological states in real materials. Our study is further suggestive for realizing
many fascinating physics such as higher dimensional Dirac fermions [119, 138], Weyl
fermions under magnetization [118, 119, 138140], supersymmetry SUSY state [127]
and interacting topological states [141] predicted in the vicinity of the critical point
52
3.1
As we have discussed above, if the system changes from a conventional band insulator
to a 3D Z2 topological insulator, it must go through a band inversion process. The
basic evolution of the bulk electronic structure across a topological quantum phase
transition from a conventional band insulator to a 3D Z2 TI have been theoretically
discussed in Ref. [119]. Here we state the conclusions in Ref. [119] without going into
the details of the formulations.
Figure 3.1: Phase transition in 3D between the conventional band insulator to the 3D Z2 TI
phases for inversion-symmetric and inversion-asymmetric cases. In the inversion symmetric
case, all bands are doubly degenerate.
Since time-reversal symmetry is indispensable for a Z2 TI phase, thus here we restrict ourselves on time-reversal-symmetric systems. Besides time-reversal symmetry,
another symmetry that plays an essential role is the space inversion symmetry. This
Figure 3.2: Bulk band-gap across the topological phase transition in 3D between the
conventional band insulator to the 3D Z2 TI phases for inversion-symmetric and inversionasymmetric cases.
is because inversion symmetry can force the bulk bands to be doubly degenerate at all
k-points throughout the BZ, whereas for systems without inversion symmetry, their
bulk bands can be singly degenerate at all k-points except the Kramers point (doubly degeneracy forced by the Kramers theorem). We will discuss the band inversion
process for inversion symmetric and asymmetric cases separately. Finally, we note
that we do not consider any additional space group symmetries (such as mirror symmetries or rotational Cn symmetries). In the case of the presence of these additional
symmetries, then the conclusion can be different again. For example, please refer to
the topological Dirac semimetal phase discussed in Chapter 5.
Suppose we start from a conventional band insulator in 3D, and there exists some
tuning parameter (e.g. spin-orbit coupling, lattice constant, chemical composition,
temperature, etc.) that can effectively change the bulk band-gap.
For an inversion symmetric case, the conclusion is shown in Figs. 3.1, 3.2: (0) In an
inversion symmetric crystal, all bulk bands must remain doubly degenerate at all kpoints. (1) As the system goes through the band inversion, its band-gap decreases to
zero and then increases again. (2) There exists only a single value for the , where the
band-gap is zero. This is the critical point of the band inversion and the topological
phase transition. At this critical point, the bulk conduction and valence bands cross,
and the bulk band structure can be described by a 3D massless Dirac cone. (3) The
54
bulk band crossing (the 3D Dirac point) must occur at a Kramers point.
For an inversion asymmetric case, the conclusion is shown in Figs. 3.1, 3.2: (0)
In an inversion asymmetric crystal, bulk bands (with consideration of the spin-orbit
coupling) are usually singly degnerate except at the Kramers points. (1) As the
system goes through the band inversion, its band-gap decreases to zero and then
increases again. (2) There exists a range of values for the where the band-gap is
zero. Thus the gapless phase is not a single point by a region along the axis. The
gapless region is called the Weyl semimetal phase, because the low energy excitation
from the bulk bands are described by the Weyl equation. This is called a Weyl
semietal phase because one can actually identify a distinct topological number to it,
and therefore it is a new topological phase of matter. (3) The bulk band crossings
(the 3D Weyl points) will not occur at any Kramers points.
The Weyl semimetal phase in inversion asymmetric systems are of great current
interest, which remains experimentally elusive, and many groups are trying to realize
it. On the other hand, in the following sections in this chapter, we only consider
systems with inversion symmetry because it is directly relevant to our experiments
(BiTl(S1 Se )2 has inversion symmetry). In the next section, we present the experimental work that demonstrates the general frame of the band inversion and the
topological phase transition in BiTl(S1 Se )2 . Then in the following section, we focus on the vicinity of the critical point of the topological phase transition, and try
to reveal the formation mechanism of the topological surface states (how protected
surface states arise from a conventional material) by going through a topologicalcritical-point.
3.2
3.2.1
Figure 3.3: (a) Bulk 3D Brillouin zone of Bi1 Sb showing the eight bulk Kramers points
(T , , 3 L, 3 X). (b) Schematic evolution of the near EF band structure from Bi to Sb.
This figure is adapted from Ref. [135]
insulator, pure Sb is a metal. (2) By going from Bi0.91 Sb0.09 to pure Bi (0.09 0),
the topological nature is indeed changed, because it induces another three band inversions at the three L points of the bulk BZ [see Fig. 3.3(a)]. Thus Bi0.91 Sb0.09 is
Z2 topologically nontrivial 0 = 1, whereas pure Bi is Z2 topologically trivial 0 = 0.
However, the reality is much more complex. Since there do exist four band inversions
at the 1T and 3L points in pure Bi, and furthermore these band inversions coincide
with the mirror planes of the Bi crystal, therefore pure Bi does have surface states
within its partial energy gap (energy gap at each k point) and these surface states
can be protected by the mirror symmetries [116] (although pure Bi is Z2 topologically
trivial). Moreover, pure Bi is also a metal lacking a global energy gap. Furthermore,
the Bi0.91 Sb0.09 (0 = 1) is known to have multiple pieces of surface state Fermi sur and the M
points), but so is pure Bi (0 = 0). These facts
faces (both at the
suggest that the Bi1 Sb is quite complicated both in terms of its evolution of the
topology and in terms of its surface state electronic structure as a function of . Thus
it is difficult to demonstrate a prototypic topological phase transition in the Bi1 Sb
system.
Another important topological insulator material is Bi2 Se3 discovered in 2009 [32,
33]. It has a layered rhombohedral structure with the space group of R 3m. In Ref.
[33], Zhang et al. further predicted that Sb2 Se3 is topologically trivial. Thus it seems
3.2.2
Figure 3.4: (a) Bulk 3D Brillouin zone of BiTl(S1 Se )2 showing the eight bulk Kramers
points (T , , 3 L, 3 X), and their (111) surface projections. (b) Fermi surface map over
the entire first surface BZ of the (111) surface of BiTlSe2 ( = 1). Only a single surface
point is observed. (c) ARPES dispersion maps of the single
state Fermi surface at the
point at three different incident photon energies.
Dirac cone surface state at the
Our interest on the BiTl(S1 Se )2 system starts from its selenium end compound.
BiTlSe2 ( = 1) was identified as a 3D Z2 TI with a single Dirac cone surface state
point [143147], which is very similar to Bi2 Se3 . However,
at the surface BZ center
interestingly, we found that unlike in Bi2 Se3 where the crystal structure changes by going from Bi2 Se3 to Bi2 S3 or Sb2 Se3 , the BiTl(S1 Se )2 system remains the same crystal structure (Fig. 3.5) throughout the compositional range going from BiTl(S1 Se0 )2
to BiTl(S0 Se1 )2 . Thus by going from the sulfur end to the selenium end, the two
major changes are the change of the lattice constant [Fig. 3.5(b)] and the strength of
spin-orbit coupling (since Se is heavier than S). Both changes are adiabatic, leading
58
Figure 3.5: (a) The crystal structure of the BiTl(S1 Se )2 system. (b) In-plane lattice
constant a and out-of-plane lattice constant c determined by x-ray diffraction measurements.
The crystal structure remains the same, only the lattice constant value is found to change
as a function of the composition .
sualized. Using linear interpolation, we estimate the critical point of this topological
phase transition to be at composition value c = 0.5 0.05. In the next section, we
will systematically study the surface electronic and spin groundstate near the critical
point with finer compositional steps. Nevertheless, the work presented in Figs. 3.6, 3.7
sets the foundation for the realization of the topological quantum phase transition in
60
62
Figure 3.7: Bulk band inversion process in BiTl(S1 Se )2 . A band inversion is revealed by tracking the ARPES measured energy positions of the conduction band minimum
and valence band maximum at various composition values. The figure is adapted from
Ref. [37].
3.2.3
Figure 3.8: Comparing the role of spin-orbit coupling and lattice constant in the
topological phase transition in BiTl(S1 Se )2 . (a) Bulk band structure calculation of
BiTl(S0 Se1 )2 and BiTl(S1 Se0 )2 . Top row: Calculated Band structure will full SOC. Bottom
row: Calculated Band structure with S or Se SOC setting to zero. Black (parity ) and red
(parity +) represent orbital symmetries associated with the parity eigenvalue at the high
symmetry points. (b) Lattice constant change as a function of composition.
We try to determine what is the pivotal tuning parameter that drives the topological phase transition in BiTl(S1 Se )2 . As we have discussed above, as the composition is varied, the two major changes in the system are the spin-orbit coupling
strength (since Se is heavier than S) and the lattice constant. Here we evaluate which
one plays the decisive role in this topological transition. Fig. 3.8(a) shows the bulk
band structure calculation with the parity eigenvalues of the lowest conduction and
valence bands. Let us first focus on the top row of Fig. 3.8(a), which are calculations
with full spin-orbit coupling strength. It can be seen from Fig. 3.8(a) that the Se
end compound BiTl(S0 Se1 )2 ( = 1) shows a parity inversion, consistent with a nontrivial TI phase, whereas the S end compound BiTl(S1 Se0 )2 ( = 0) does not show
parity inversion, consistent with a topologically trivial phase. Now, in the bottom
64
3.2.4
Figure 3.9: 3D Dirac semimetal state at the critical point of the topological
phase transition in BiTl(S1 Se )2 . (a) Theoretically calculated band inversion and
topological phase transition in the BiTl(S1 Se )2 system. Inset: a 3D Dirac semimetal
state at the critical point of this phase transition is seen in calculated bulk band structure
(b) ARPES results at the composition = 0.5, which corresponds to the critical point.
We also note that a 3D Dirac semimetal state is realized at the critical point of
the topological phase transition in BiTl(S1 Se )2 . This has been discussed in the
first section of this chapter (see section 3.1). Since BiTl(S1 Se )2 has inversion symmetric, according to the discussion in section 3.1, the bulk band-gap goes to 0 at
only one value of the tuning parameter , which corresponds to the critical point
of this topological phase transition. At the critical point, the bulk band structure
is exptected to be described by a 3D Dirac fermion state, where the band disperses
66
3.3
After establishing the topological phase transition and band inversion in the BiTl(S1 Se )2 ,
in this section we systematically study the electronic and spin groundstate of the
BiTl(S1 Se )2 near the critical point of the topological transition. Studying the
topological-critical-point of a topological phase transition is of fundamental importance for the following reasons:
Understanding the physics of distinct phases of matter is one of the most important
goals in physics in general. For a new phase of matter, a powerful route toward such
understanding is to study the way it arises from an understood state by investigating
the nature of a phase transition. Studying the phase transition critical point not
only deepens our understanding of the new phase, but also sometimes even produces
surprising new phenomena. A well-known example is the study of the superconducting
phase transition between the high-Tc dwave cuprate superconductor and the normal
state, which leads to the surprise of the pseudo-gap state with the concept of the
preformed Cooper pairing. In our context, a topological insulator is a distinct phase
of matter that cannot be adiabatically connected to a conventional material without
going through a topological quantum (T 0 K) phase transition (TQPT), which
involves a change of the bulk topological invariant. Inspired by the discovery of 3D Z2
topological insulator state [29,1113], many new topological phases of matter, such as
a topological crystalline insulator [3941], a topological Kondo insulator [4851, 117],
a topological Dirac/Weyl semimetal [4345,118,119,138], etc, have just been predicted
or realized. All these phases are predicted to feature protected surface states, which
serve as the experimental signature for their nontrivial topology in the bulk, and they
are in fact formed via TQPTs and need to be understood in real materials. Therefore,
it is of general importance to study how protected surface state emerge from a trivial
68
and valence bands are separated by an observable bulk gap, which is traversed by the
gapless topological surface states. Thus, our data show that the system belongs to
the topological insulator regime for compositions of 0.60. As for the system lying
very close to the bulk inversion at = 0.50 or 0.525, based on the in-plane dispersion
data in Fig. 3.10(b) alone, the nature of the observed Dirac-like band cannot be conclusively determined, because it can be interpreted as two-dimensional topological
surface states or three-dimensional bulk Dirac states [138] expected near the bulk
band inversion. However, one of the two possibilities can be identified by measuring
the dispersion along the out-of-plane kz direction, since the three-dimensional bulk
Dirac states are expected to be highly dispersive [37, 43, 45] (the velocity along kz
1
[37]),
whereas the 2D surface states are not expected to show observable dispersion along
the kz direction.
Thus, in order to better understand the nature of the bands at compositions near
the TCP, we perform ARPES measurements as a function of incident photon energy
values [Fig. 3.10(e),(f) to probe their out-of-plane kz dispersion. Upon varying the
photon energy, one can effectively probe the electronic structure at different outof-plane momentum kz values in a three-dimensional Brillouin zone. Left panel of
Fig. 3.10(f) shows the incident photon energy (kz ) measurements at = 0.525 by the
Fermi surface mapping in kk vs kz momentum space. The straight Fermi lines that
run parallel to the kz axis show nearly absence of observable kz dispersion. Similarly,
incident photon energy measurements are also performed at compositions = 0.40
and 0.45, where a clear bulk band-gap is observed (0 = 0). Surprisingly, even for
the gapped electronic structure at = 0.40, 0.45, our data show clear absence of kz
dispersion. Therefore the observed bands cannot be interpreted as three-dimensional
bulk Dirac bands expected near the bulk band inversion. In fact, Our systematic kz
measurements [(Figs. 3.10(g),(h)]reveal that the electronic structure at = 0.40, 0.45
of the sample. These experimental facts guarantee that the observed quasi-2D states
at . 0.5 are consistent with the conventional semiconductor phase of the system
(0 = 0, trivial Z2 index).
In order to better understand the spin texture of the quasi-2D states, we propose a phenomenological picture consistent with the basic topological physics for our
observation (Fig. 3.14): The quasi-2D states can be viewed as a Rashba-like state,
whose inner band is not observable because it is severely damped due to its strong
overlap with the bulk bands in E k. As the system is tuned approaching the TCP
from the trivial side, the inner band completely loses its surface character, whereas
the outer band is systematically enhanced in terms of its surface spectral weight and
spin polarization, and evolve into the topological surface states (as clearly observed
in our data). We emphasize that we use the term Rashba-like for the observed perform surface states because there are two singly degenerate bands as in a real Rashba
2DEG. However, the Rashba surface states are due to a combined effect of atomic
spin-orbit coupling and the electrical field perpendicular to the surface, and follows
the Rashba Hamiltonian, whereas it is not fully applicable for the observed preformed
surface states. This issue needs further theoretical studies to illuminate the microscopic origin of the preformed surface states in theory. Regardless of this issue, our
systematic data, which is the main theme of this experimental paper, show: (1) these
preformed surface states show spin polarization texture that resembles a topological
insulator; (2) their surface spectral weight and magnitude of spin polarization are enhanced as we approach the TCP; (3) they evolve into the topological surface states.
These measurements with spin and mometum resolution clearly show that these preformed surface states are critically relevant to the bulk band inversion and TQPT in
the bulk. In the Supplementary Figure 8, we show our observation of preformed surface states near the TCP of another prototypical TQPT system (Bi1 In )2 Se3 [74].
Therefore, these systematic and careful measurements on multiple systems suggest
76
Figure 3.10: textbf(g),(h) ARPES dispersion maps at various incident photon energy values
for the compositions of = 0.4 < c and = 0.525 c . Some panels of this figure can also
be found in Ref. [68].
cut. (e) same as panel (d) but for the out-of-plane component of the spin
the -M /-K
polarization. Some panels of this figure can also be found in Ref. [68].
78
Figure 3.12
Figure 3.12: Evolution of the quasi-2D states spin polarization with binding energy and composition. (a),(e),(i), ARPES kk -EB maps with dotted lines indicating the
energy levels of spin-resolved measurements. Compositions of the samples are marked on the
top of each map. (b),(f ),(j), MDCs with highlighted curves chosen for spin-resolved measurements. (c),(g),(k), Spin-resolved momentum distribution spectra, and (d),(h),(l),
the corresponding net spin polarization measurements. Some panels of this figure can also
be found in Ref. [68].
80
Figure 3.14: A band-like schematic showing the phenomenological picture we proposed in the main text. The blue and green shaded areas represent the bulk conduction
bands (BCB) and the bulk valence bands (BVB), which go through a band inversion at
the critical point. The red lines represent electronic states that are strongly localized on
the surface due to their minimal overlap with the bulk band continuum. The inner band
(dotted lines) become bulk-like. One might worry about their singly degenerate nature,
which is inconsistent with the doubly degenerate nature of the bulk bands. However, it is
important to consider that there is another copy of these bands that has the opposite spin
texture one the opposite surface of the sample.
3.4
We note that the topological phase transition from a conventional band insulator to a 3D Z2 TI can be realized in another material, namely (Bi1 In )2 Se3 [74].
Here, again, the crystal structure remains the same throughout the whole range of
the chemical composition . Fig. 3.15(a) shows the ARPES dispersion maps of the
(Bi1 In )2 Se3 system at various In composition values, where a topological phase
82
transition is clearly seen. The critical composition for this system is found to be
about = 0.04 [74]. In Figs. 3.15(b),(c), we show a composition ( = 0.06) that
is in the trivial regime, where a small band-gap is found. Fig. 3.15(c) shows the
spin-resolved ARPES data near the Fermi level of the = 0.06 sample. Clear spin
polarization is observed. Furthermore, the spin polarization is found to reverse as
one goes from one side of the Fermi surface (cut1) to the other (cut2). These data
show the observation of preformed surface states in the (Bi1 In )2 Se3 system. This
finding strongly suggests that the preformed surface state is not a special case in the
BiTl(S1 Se )2 system but an important proximity phenomenon that describes the
TCP in the electronic and spin groundstates in many TQPT systems.
In the following chapters, we will also discuss the topological phase transition in
a topological crystalline insulator (TCI) phase in the Pb1 Sn Te(Se) system and
the associated phenomena in a topological Kondo insulator (TKI) candidate SmB6 .
This Chapter gives a general experimental guideline for how topological state and its
protected surface states can emerge from a conventional material by going through a
topological quantum phase transition.
Chapter 4
Topological Crystalline Insulator
Phase in Pb1 Sn Te(Se)
A topological crystalline insulator is a new topological phase where space group symmetries replace the role of time-reversal symmetry in a Z2 (Kane-Mele) topological
insulator. In this chapter, we present our experimental identification of a topological crystalline insulator state (TCI) in the Pb1 Sn Te(Se) systems, marking the
first realization of the topological crystalline insulator phase in real materials. In the
first section, we briefly review the key theoretical concepts for a TCI state. Then
we present the realization of a TCI state protected by the mirror symmetries in
Pb1 Sn Te. Particularly, our surface state spin texture data provide a direct experimental measurements of its topological number (the mirror Chern number nM ).
Finally in the last section, we show systematic ARPES studies on the surface state
electronic structure of a similar TCI compound Pb1 Sn Se, where a saddle point
surface electronic structure singularity is directly resolved.
Our ARPES and spin-resolved ARPES measurements identified the topological crystalline insulator (TCI) phase protected by the mirror symmetries in the
Pb1 Sn Te, and further experimentally revealed its topological number, the mir84
4.1
Figure 4.1: (a) A bulk BZ with a mirror (yellow) plane. (b) The surface (blue and red
solid lines) and bulk (grey shaded area) electronic structure alone the mirror plane.
in which a crystal has a bulk BZ as shown in Fig. 4.1(a), where the ky = 0 plane (the
yellow plane) is a mirror plane for the system. The fact that the kx kz plane is a
mirror plane means the system is invariant under the mirror reflection with respect to
ky = 0, where M(
y ) = P C2 (
y ). This immediately implies that all the bulk electronic
states in the plane ky = 0 can be labeled with a mirror eigenvalue i [169]. Now
suppose that the bulk electronic structure within this 2D plane has a full energy gap,
then it is possible to assign a Chern number for the occupied energy bands for each
mirror eigenvalue:
ni
i
=
2
ky =0
(4.1)
where the bulk electronic wavefunction |ui (k) > is labeled by its mirror eigenvalue. The total Chern number of the occupied bands is n = n+i + ni . In a
time-reversal symmetric system, one has n = 0. However, one can define a mirror
nM = (n+i ni )/2
(4.2)
Further theoretical analysis has shown that the mirror Chern number nM is a
topological invariant under the condition that the mirror symmetry is preserved in
the system [116, 169]. With these theoretical foundations, one could consider the
band structure at ky = 0 as two sets of band structures labeled by their different
mirror eigen values i. These two sets are related by the mirror symmetry operation
M(
y ). For each set, lets say mirror eigenvalue of +i, the band structure has a well
defined Chern number n+i . Thus we can conceptually view it has a Chern insulator,
where at the 1D boundary there are |n+i | altogether chiral edge states. Since we
assume time-reversal symmetry, we have ni = n+i . Therefore, for the sets of
bands with mirror eigenvalue i, there will be the same number (|n+i | = |ni |) of
chiral edge states but moving to the opposite direction since ni = n+i . These edge
states should have the same mirror eigen value (+i or i) as their corresponding bulk
bands, which means the counterpropagating edge states must have the opposite mirror
eigen values. Therefore, the edge band-crossing between two counterpropagating edge
states at the mirror plane ky = 0 must be protected by the mirror symmetry. Because
if one can add a term that will gap out the band-crossing (degeneracy) between these
two counterpropagating edge states, that term must break the mirror symmetry. Any
term that respects the mirror symmetry only shifts the crossing in energy within the
mirror plane. Fig. 4.1(b) presents a case of n+i = 1 and ni = 1. Thus one has one
right-going (red) edge state derived from the mirror eigenvalue +i bulk bands and
one left-going (blue) edge state derived from the mirror eigenvalue i bulk bands.
Their edge band-crossing is protected by the mirror symmetry with a mirror Chern
number nm = +1. A similar argument applies to Fig. 4.1(c). We note that the mirror
symmetry at ky = 0 only requires the edge band-crossing to be within the ky = 0
88
plane. In principle, perturbations that respect the mirror symmetry can shift the
band-crossing along the energy axis and also only the momentum kx , as long as the
band-crossing stays within the ky = 0 mirror symmetry plane and the bulk bandgap along the energy-axis. Thus the schematics in Figs. 4.1(b),(c), where the edge
point kx = 0 is just a special case.
band-crossing is at the
4.2
In this section, we present the realization of a TCI state protected by the mirror
symmetries in Pb1 Sn Te. Particularly, our surface state spin texture measurements
provide a direct experimental measure for its topological number (the mirror Chern
number nM ).
4.2.1
The Pb1 Sn Te pseudo-binary alloy system crystallizes in the sodium chloride crystal
structure, (space group Fm3m (225)). In this structure, each of the two atom types
(Pb/Sn, or Te) forms a separate face-centered cubic lattice, with the two lattices
interpenetrating so as to form a three-dimensional checkerboard pattern. The first
Brillouin zone (BZ) of the crystal structure is a truncated octahedron with six square
faces and eight hexagonal faces. The band-gap of Pb1 Sn Te is found to be a direct
gap located at the L points in the BZ [171]. The L points are the centers of the eight
hexagonal faces of the BZ. Due to the inversion symmetry of the crystal, each L point
and its diametrically opposite partner on the BZ are completely equivalent. Thus
there are four distinct L point momenta. It is well established that the band inversion
transitions in the Pb1 Sn Te take place at the four L points of the BZ [172174].
As a result, an even number (four) of inversions exclude the system from being a
Figure 4.2: Band inversion transitions and mirror symmetries in Pb1 Sn Te.
(a) The lattice of the Pb1 Sn Te system is based on the sodium chloride crystal structure.
(b) The first Brillouin zone (BZ). The mirror planes are shown using green and light-brown
X
mirror
colors. These mirror planes project onto the (001) crystal surface as the X
lines (shown by red solid lines). (c) ARPES measured core level spectra (incident photon
energy 75 eV) of two representative compositions, namely Pb0.8 Sn0.2 Te and Pb0.6 Sn0.4 Te.
(d) The bulk band-gap of Pb1 Sn Te alloy system undergoes a band inversion upon changing the Pb/Sn ratio at each L point in the bulk BZ [171174]. (e), (f ) First-principles based
calculation of band dispersion (e) and iso-energetic contour with energy set 0.02eV below
the Dirac node energy (f ) of the inverted end compound SnTe. This figure is adapted from
Ref. [40].
4.2.2
94
96
Figure 4.5: Mirror protected surface states in Pb0.6 Sn0.4 Te. (a) First-principle
calculated surface states of SnTe with energy set 0.02eV below the Dirac node energy are
shown in red. (b) Left panel: ARPES iso-energetic contour mapping (EB = 0.02 eV) of
Pb0.6 Sn0.4 Te covering the first surface Brillouin zone (BZ) using incident photon energy
of 24 eV. Right panel: Spectral intensity distribution as a function of momentum along
the horizontal mirror line (defined by ky = 0). (c) High resolution Fermi surface mapping
points. (d)-(f ) Dispersion maps (EB vs k)
(EB = 0.0 eV) in the vicinity of one of the X
and corresponding energy (momentum) distribution curves of the momentum space cuts 1,
2, and 3. The momentum space cut-directions of cuts 1, 2, and 3 are defined by the blue
dotted lines in panel (c). The second derivative image (SDI) of the measured dispersion is
additionally shown for (d). This figure is adapted from Ref. [40].
4.2.3
100
Figure 4.6: Experimental measurement of the mirror Chern number. (a) ARPES
dispersion map along the mirror line direction. The white dotted lines show the binding
energies chosen for spin-resolved measurements SR-Cut 1 at EB = 0.06 eV and SR-Cut
2 EB = 0.70 eV respectively. Inset: Measured spin polarization are shown by the green
and blue arrows on top of the ARPES iso-energetic contour at binding energy EB = 0.06
eV for SR-Cut1. (b),(c) Measured in-plane spin-resolved intensity (b) and in-plane spin
polarization (c) of the surface states (SR-Cut 1) near the Fermi level at EB = 0.06 eV.
(d),(e) Measured in-plane spin-resolved intensity (d) and in-plane spin polarization (e)
of the bulk valence bands (SR-Cut 2) at high binding energy at EB = 0.70 eV. f, Surface
spin texture configurations corresponding to mirror Chern number of nM = 2 and nM =
2. g, Theoretically expected spin polarization configuration of the surface states which
corresponds to a mirror Chern number) nM = 2.
102
4.3
4.3.1
Saddle point singularities in two-dimensional Dirac electron gas often results in electronic instabilities leading to exotic correlated quantum phenomena. A notable example is the extensive research efforts on the van Hove singularity in graphene, where
d-wave superconductivity and unusual magnetism or Kondo effect have been predicted to take place [175178]. Very recently, striking Hofstadter butterfly spectrum
and fractional quantum Hall effect have been experimentally observed in twisted
graphene system due to the saddle point singularity in its Dirac band structure,
which further adds to the interest [179, 180]. Like graphene, the surface states of
topological insulators (TIs) also possess the light-like Dirac dispersion. What is more
interesting is that the Dirac surface states of TIs are spin-momentum locked, since
they are a consequence of the bulk band inversions and the nontrivial topology of the
bulk electronic band structure. As a result, saddle point singularities in topological
surface states (a spin-helical two-dimensional Dirac electron gas) are even more exotic
because they not only host correlated physics, but also allow one to explore the coexistence and the interplay between topological order and strong correlation. While none
of the surface states in any known Z2 TI materials satisfy the conditions to realize
a Lifshitz transition, the newly identified TCI surface states in the Pb Sn1 Se(Te)
system in fact provide an ideal platform.
As we have shown in the previous section, the (001) surface states in Pb Sn1 Se(Te)
momentum-space band structure, we focus on the upper blue square in Fig. 4.9(a)
and study the energy-momentum dispersion cuts along three important momentum
space cut-directions, namely cuts 1,2, and 3. Cuts 1 and 2 [Figs. 4.9(c),(d)] are along
the horizontal (kx ) and verticle (ky ) directions across the blue square. Interestingly,
the blue square is found to be a local band structure minimum along cut1 shown in
Fig. 4.9(c), whereas it is a local maximum along cut2 [Fig. 4.9(d)]. Observation of
104
106
X
and M
X
M.
(f )
Figure 4.8: (e) ARPES measured dispersion plots along
Momentum (kx and ky ) integrated ARPES intensity as a function of binding energy (left).
2nd derivative of the ARPES intensity with respect to binding energy is presented to further
highlight the features. The upper Dirac point (UDP), upper van Hove singularity (VH1),
Dirac point (DP), lower van Hove singularity (VH2) and lower Dirac point (LDP) are
marked. This figure is adapted from Ref. [80].
Figure 4.9: Observation of the saddle point singularity. (a) ARPES constant energy
point in the surface (001) BZ at binding energy 40 meV,
contour map in the vicinity of an X
which corresponds to the surface Lifshitz transition and saddle point energy of the upper
part of the Dirac cones. The blue and green squares denote the momentum space locations
of the two surface saddle points. The blue dotted lines indicates the momentum space
cut-directions for cuts1, 2, and 3, which are centered at the blue square. (b) Calculated
surface state constant energy contour at the saddle point singularity energy (top) and a
three-dimensional schematic of a saddle point (bottom). (c)-(e) ARPES dispersion maps
(left) and their second derivative images along cuts 1, 2, and 3. The white and green arrow
point the saddle points [blue and green squares in Panel (a)]. This figure is adapted from
Ref. [80].
4.3.2
110
4.3.3
112
Figure 4.11: Topological phase diagram Pb1 Sn Se. (a) ARPES dispersion map for
PbSe (trivial insulator), Pb0.7 Sn0.3 Se (TCI) and SnSe (trivial insulator). (b) Topological
phase diagram of the Pb1 Sn Se system. For composition range of 0 < x < 0.45, the
system is in the single crystalline FCC phase. The bulk band of Pb1 Sn Se undergoes a
band inversion with Pb/Sn substitution. Topological crystalline insulator (TCI) phase is
observed in the band inverted region toward the Sn-rich side. The critical composition c1
is 0.20 0.23 depending on the temperature. The conduction and valence band states
+
representing odd and even parity eigenvalues are marked as L
6 and L6 , respectively. For
composition range of 0.45 < < 0.75, the system shows multi-structural-phase (cubic and
orthorhombic phases coexist. See the XRD data in the inset for = 0.5 and 0.6.). The
point. The inset in the bottom
upper insets are schematic Fermi surface plots around the X
right conner shows the resistivity measurements on SnSe, which proves its insulator nature.
BS FS and SS FS denote the bulk state Fermi surface and surface state Fermi surface,
respectively. The arrows at bottom notes the compositions where our ARPES studies have
been performed. For composition range of 0.75 < < 1, the system is in a single crystalline
orthorhombic phase. This figure is adapted from Ref. [80].
Chapter 5
Topological Dirac semimetal state
in Cd3As2 and Na3Bi
Unlike insulators, semimetals are materials, whose bulk conduction and valence bands
have small but finite overlap. Thus there does not exist a full band-gap irrespective
of the choice of the chemical potential. This is in contrast to all topological phases
discussed before this chapter (quantum Hall states, Chern insulators, quantum spin
Hall insulators, 3D Z2 topological insulators, and topological crystalline insulators),
where a band-gap is important both for the definition of a topological number and
for the existence of surface states. We ask the following questions: Can we construct
a topological state in a semimetal - a topological semimetal? What kind of surface
states it will have and how these surface states reflect the nontrivial topology in the
bulk of a semimetal?
In this chapter, we present our experimental realization of a topological Dirac
semimetal phase in Cd3 As2 and Na3 Bi. We show that the bulk has linearly dispersive
nodal crossings, realizing a 3D analog of graphene, whereas the surface features Fermi
arc surface states (FASS) that connect across the bulk Dirac nodes. Previously, Fermi
arc states were only found in the bulk bands of high Tc cuprate superconductors in
114
a strongly interacting condition. Our observation of novel surface states here thus
realizes disjoint Fermi arc states on the surface of a weakly interacting topological
system. The observed FASS serve as a new type of 2D electronic gas, which are distinct from both a regular 2DEG in semiconductor heterostructures and the surface
states in a topological insulator. The observed exotic surface and bulk electronic and
spin groundstate in topological Dirac semimetals Cd3 As2 and Na3 Bi here suggests
many interesting transport and tunneling phenomena, and is multiply-connected to
other novel groundstates under additional superconducting or ferromagnetic symmetry breakings [10, 118123, 138140, 148, 184191].
In the first section, we discuss the theoretical works that are directly relevant
to the prediction the topological Dirac semimetal state. In the second section, we
present our ARPES observation of the 3D Dirac cone state in the bulk electronic
structure in Cd3 As2 . In the third section, we present our ARPES and spin-ARPES
data on Na3 Bi, not only showing the existence of 3D Dirac nodes in the bulk, but
also showing a spin-polarized double Fermi arc surface state (FASS) that connect
the bulk Dirac nodes. We further demonstrate how the observed FASS and its spin
texture provide an experimental measurement of the nontrivial topological number
in semimetal Na3 Bi. Finally in the last section, we go back to theory. We discuss the
general classification of topologically nontrivial semimetals, including the topological
Weyl semimetal [118, 187], the topological Dirac semimetal [121123] and the topological nodal-line semimetal [192], and how they can transform into each other via
breaking or restoring certain symmetries.
5.1
In this section, we introduce the basic theoretical concepts relevant to the topological Dirac semimetal phase. We constrain ourselves within bulk materials that have
time-reversal T and space inversion symmetries I, and possess non-negligible spinorbit coupling. These conditions are needed for a topological Dirac semimetal. For
systems breaking T or I, and for spinless fermion systems (no spin-orbit coupling),
there are also theoretically predicted distinct topological semimetal phases, such as
a topological Weyl semimetal and a topological nodal-line semimetal. These phases
have not been experimentally realized to date. In the last section of this chapter, we
will briefly discuss them and their connection to a topological Dirac semimetal.
In a time-reversal and space inversion symmetric system, if the energy of the
top of a valence band goes above that of the bottom of a conduction band, without
considering spin-orbit interaction, these two bulk band will become degenerate (bandcrossing) at a finite number of momentum space locations. However, a finite spinorbit interaction is expected to lift the degeneracy at these band-crossing momenta.
Without considering any additional symmetry, there is no reason one would expect
certain band-crossing momenta are more special than others. Therefore, if spinorbit coupling open an energy gap, it should opens an full energy gap, meaning
the degeneracy at all band-crossing momenta are lifted. This is the case of the
BiTl(S1 Se )2 and the Pb1 Sn Te(Se) systems [37, 40] that we present in Chapters
3,4.
However, the situation can become very different if additional symmetries are
considered, in particular if we consider a time-reversal and space inversion symmetric
system with an additional uniaxial rotational symmetry. Let us take the example of
Na3 Bi, where a band inversion occurs between the Na3s and the Bi6p bands in the
116
vicinity of the point. Due to an additional C3 rotational symmetry along the kz axis
[Fig. 5.1(c)], the bulk electronic bands along the C3 (kz ) axis must be the eigenstates of
the C3 operation. In particular for the Na3s and the Bi6p bands in Na3 Bi, theory [122]
shows that these two bands have different C3 eigenvalues and therefore the bulk band
degeneracy is protected by C3 crystalline rotational symmetry even with a finite
spin-orbit coupling. Therefore, spin-orbit coupling opens an energy gap at all bandcrossing k-points except at two special momenta along the C3 (kz ) axis on opposite
sides of the point. Similarly, in another tetragonal structured material Cd3 As2 ,
it has been theoretically shown that the band-crossing between inverted conduction
and valence bands is protected by an additional C4 rotational symmetry of the same
reason [121]. A systematic theoretical classification for all the possible topological
Dirac semimetal states with different rotational symmetries have been proposed in
Ref. [123] [also see Fig. 5.2].
Another important theoretical question is to define a topological number to characterize a Dirac semimetal state. Let us again take the example of Na3 Bi, in absence
of a full energy gap in the bulk BZ, one cannot define the Z2 invariants (0 ; 1 2 3 )
as in a 3D Z2 topological insulator, even though there is a band inversion at the
point in Na3 Bi. However, as pointed out in Ref. [123], since the bulk band-gap only
vanishes at two momenta along the C3 (kz ) axis on the opposite sides of the point,
there exist many 2D k planes in the 3D BZ, where a full energy gap is present. In
particular, for Na3 Bi, the kz = 0 plane is invariant under time-reversal operation, and
also contains the point where the band inversion happens. Therefore, Ref. [123]
shows that the kz = 0 plane can be viewed as a 2D quantum spin Hall system with
a distinct 2D topological number 2D (kz = 0) = 1. The approach of assigning topological numbers to certain 2D k slices in a 3D BZ can be further generalized to other
Dirac semimetals (see Fig. 5.2 and Ref. [123]) and even Weyl semimetals [10,118,187].
Furthermore, the distinct 2D topological number (e.g. 2D (kz = 0) = 1 in Na3 Bi) in a
118
Figure 5.2: Classification table for 3D topological Dirac semimetals. This table is
adapted from Ref. [123].
120
5.2
In this section, we present our ARPES results on the Dirac semimetal candidate
Cd3 As2 . We observe a highly linear bulk band crossing to form a three-dimensional
dispersive Dirac cone projected at the (001) surface BZ center by studying the (001)cleaved surface. These results demonstrate the existence of the 3D Dirac nodes (bandcrossing) in the bulk electronic structure of Cd3 As2 . Remarkably, an unusually inplane high Fermi velocity up to 1.5 106 ms1 is observed in our samples, where the
transport mobility is known up to 40,000 cm2 V1 s1 [193,194] suggesting that Cd3 As2
can be a promising candidate as an anisotropic-hypercone (3D) high spin-orbit analog
of graphene. Our observation of the 3D Dirac semimetal state in the stoichiometric,
stable and high mobility material Cd3 As2 opens the door for exploring the exotic
transport and tunneling phenomena based on 3D Dirac fermions [139, 140, 148, 185].
The crystal structure of Cd3 As2 has a tetragonal unit cell with a = 12.67
A and
c = 25.48
A for Z = 32 with symmetry of space group I41 cd [see Figs. 5.3(a),(b)].
In this structure, arsenic ions are approximately cubic close-packed and Cd ions are
tetrahedrally coordinated, which can be described in parallel to a fluorite structure
of systematic Cd/As vacancies. There are four layers per unit and the missing CdAs4 tetrahedra are arranged without the central symmetry as shown with the (001)
projection view in Fig. 5.3(b), with the two vacant sites being at diagonally opposite
corners of a cube face [195]. The corresponding Brillouin zone (BZ) is shown in
Fig. 5.3(d), where the center of the BZ is the point, the centers of the top and bottom
square surfaces are the Z points, and other high symmetry points are also noted.
Cd3 As2 has attracted attention in electrical transport due to its high mobility of 105
cm2 V1 s1 reported in previous studies [193,194]. The carrier density and mobility of
our Cd3 As2 samples are characterized to be of 5.2 1018 cm3 and 42850 cm2 V1 s1 ,
respectively, at temperature of 130 K, consistent with previous reports [193, 194],
which provide evidence for the high quality of our single crystalline samples. In band
the Fermi level, only the upper Dirac band, but no other electronic state, is are observed. On the other hand, the linearly dispersive lower Dirac cone is found to coexist
with another parabolic bulk valence band, which can be seen from Fig. 5.3(e). From
122
the observed steep Dirac dispersion [Fig. 5.3(f)], we obtain a surprisingly high Fermi
velocity of about 9.8 eV
A ( 1.5 106 ms1 ). Compared to the much-studied 2D
Dirac systems, the Fermi velocity of the 3D Dirac fermions in Cd3 As2 is thus about
3 times higher than that of in the topological surface states (TSS) of Bi2 Se3 [32], 1.5
times higher than in graphene [197] and 30 times higher than that in the topological
Kondo insulator phase in SmB6 [49]. The observed large Fermi velocity of the 3D
Dirac band provides clues to understand Cd3 As2 s unusually high mobility reported
in previous transport experiments [193,194]. Therefore one can expect to observe unusual magneto-electrical and quantum Hall transport properties under high magnetic
field [139, 140, 148, 185]. It is well-known that in graphene the capability to prepare
high quality and high mobility samples has enabled the experimental observations of
many interesting phenomena that arises from its 2D Dirac fermions. The large Fermi
velocity and high mobility in Cd3 As2 are among the important experimental criteria
to explore the 3D relativistic physics in various Hall phenomena in tailored Cd3 As2 .
We compare ARPES observations with our theoretical calculations, which is qualitatively consistent with previous calculations [122]. The reason for the use of our
calculations is two fold: first, our calculations are fine tuned based on the characterization of samples used in the present ARPES study, second, sufficiently detailed cuts
are not readily available from Ref. [122] which is necessary for a detailed comparison
of ARPES data with theory. In theory, there are two 3D Dirac nodes that are expected at two special k points along the Z (kz ) momentum space cut-direction,
as shown by the red crossings in Fig. 5.3(d). At the (001) surface, these two k points
point of the (001) surface BZ [Fig. 5.3(d)].
along the Z axis project on to the
Therefore, at the (001) surface, theory predicts one 3D Dirac cone at the BZ center
point, as shown in [Fig. 5.4(a)]. These results are in qualitative agreement with
our data, which supports our experimental observation of the 3D 3D Dirac semimetal
state in Cd3 As2 . We also study the ARPES measured constant energy contour maps
out-of-plane momentum value of the 3D Dirac point. Thus at a fixed kz value (which
is determined by the incident photon energy value), do we have an in-plane electronic
2
(kz k0 )2 . It can be seen that only
dispersion takes the form: vk2 (kx2 + ky2 ) = E 2 v
at kz = k0 the in-plane dispersion that is a gapless Dirac cone, whereas in the case
for kz 6= k0 the nonzero kz k0 term acts as an effective mass term and opens up
a gap in the in-plane dispersion relation. Fig. 5.5(a) shows the ARPES measured
in-plane electronic dispersion at various photon energies. At a photon energy of 102
eV, a gapless Dirac-like cone is observed, which shows that photon energy h = 102
eV corresponds to a kz value that is close to the out-of-plane momentum value of the
3D Dirac node k0 . As photon energy is changed away from 102 eV in either direction,
the bulk conduction and valence bands are observed within experimental resolution
to be separated along the energy axis and a gap opens in the in-plane dispersion. At
photon energies sufficiently away from 102 eV, such as 90 eV or 114 eV in Fig. 5.5(a),
the in-plane gap is large enough that the bottom of the upper Dirac cone (bulk con124
duction band) is moved above the Fermi level, and therefore only the lower Dirac
cone is observed. We now fix the in-plane momenta at 0 and plot the ARPES data
at kx = ky = 0 as a function of incident photon energy. As shown in Fig. 5.5(b), a
Ekz dispersion is observed in the out-of-plane momentum space cut direction, which
is in qualitative agreement with the theoretical calculations [Fig. 5.5(c)]. The Fermi
velocity in the z-direction can be estimated (only at the order of magnitude level)
to be about 105 m/s. These systematic incident photon energy dependent measurements show that the observed Dirac-like band disperses along both the in-plane and
the out-of-plane directions suggesting its three-dimensional or bulk nature consistent
with theory.
In order to further understand the nature of the observed Dirac band, we study the
spin polarization or spin texture properties of Cd3 As2 . As shown in Fig. 5.5(f), spinresolved ARPES measurements are performed on a relatively ptype sample. Two
spin-resolved energy-dispersive curve (EDC) cuts are shown at momenta of 0.1
A1 on the opposite sides of the Fermi surface. The obtained spin data shown in
Figs. 5.5(g),(h) show no observable net spin polarization or texture behavior within
our experimental resolution, which is in remarkable contrast with the clear spin texture in 2D Dirac fermions on the surfaces of topological insulators. The absence of
spin texture in our observed Dirac fermion in Cd3 As2 bands is consistent with their
bulk origin, which agrees with the theoretical prediction. It also provides a strong
evidence that our ARPES signal is mainly due to the bulk Dirac bands on the surface
of Cd3 As2 , whereas the predicted surface (resonance) states [122] that lie along the
boundary of the bulk Dirac cone projection has a small spectral weight (intensity) contribution to the photoemission signal. In other words, according to our experimental
data, the surface electronic structure of Cd3 As2 is dominated by the spin-degenerate
bulk bands, which is very different from that of the 3D topological insulators.
The distinct semimetal nature of Cd3 As2 is better understood from ARPES data
the disorder due to strong chemical alloying. More importantly, the fine control
of doping/alloying value and keeping the composition exactly at the bulk critical
composition is difficult to achieve [37]. For example, although similarly high electron
mobility on the order of 105 cm2 V1 s1 has been reported in the bulk states of
Pb1 Sn Se ( = 0.23) [157], the bulk Dirac fermions there are in fact massive due
to the difficulty of controlling the composition exactly at the critical point. These
issues do not arise in the stoichiometric Cd3 As2 system since its 3D Dirac semimetal
state is protected by the crystal symmetry, which does not require chemical doping
and therefore the natural high electron mobility is retained (not diminished). We
further note that Cd3 As2 is stable in ambient environment, whereas the other Dirac
semimetal candidate Na3 Bi reacts in seconds in air. These advantages are vital in
further studying the 3D Dirac electronic structure in transport.
Figure 5.3: Sample characterization on Cd3 As2 . (a) Cd3 As2 crystalizes in a tetragonal
body center structure with space group of I41 cd, which has 32 number of formula units in the
unit cell. The tetragonal structure has lattice constant of a = 12.670
A, b = 12.670
A, and
c = 25.480
A. (b) The basic structure unit is a 4 corner-sharing CdAs3 -trigonal pyramid.
(c) Core-level spectroscopic measurement where Cd 4d and As 3d peaks are clearly observed.
Inset shows a picture of the Cd3 As2 samples used for ARPES measurements. The flat and
mirror-like surface indicates the high quality of our samples. (d) The bulk Brillouin zone
(BZ) and the projected surface BZ along the (001) direction. The red crossings locate at
(kx , ky , kz ) = (0, 0, 0.15 2
c ) (c = c/a). They denote the two special k points along the
Z momentum space cut-direction, where 3D Dirac band-touchings are protected by
the crystalline C4 symmetry along the kz axis. (e) Second derivative image of ARPES
dispersion map of Cd3 As2 over the wider binding energy range. Various bands are wellresolved up to 3 eV binding energy range. (f ) ARPES EB kx cut of Cd3 As2 near the
point. This figure is adapted from Ref. [43].
Fermi level at around surface BZ center
128
Figure 5.4: Observation of in-plane dispersion in Cd3 As2 . (a) Left: First principles
2
calculation of the bulk electronic structure along the (, , 0.15 2
c ) (0, 0, 0.15 c ) direction
(c = c/a). Right: Projected bulk band structure on to the (001) surface, where the
shaded area shows the projection of the bulk bands. (b) ARPES measured dispersion
map of Cd3 As2 , measured with photon energy of 22 eV and temperature of 15 K along
the (, ) (0, 0) (, ) momentum space cut direction. (c) ARPES constant energy
contour maps using photon energy of 22 eV on Cd3 As2 growth batch I. (d) ARPES constant
energy contour maps using photon energy of 102 eV on Cd3 As2 batch II. In order to achieve
chemical potential (carrier concentration) control, we have prepared different batches of
samples under slightly different growth conditions (temperature and growth time). For the
two batches studied here, batch I is found to be slightly more ntype than batch II (e.g.
compare batch I in Fig. 5.3(f) with batch II in Fig. 5.5(a) rightmost panel). This figure is
adapted from Ref. [43].
Figure 5.5: Observation of out-of-plane dispersion in Cd3 As2 . (a) ARPES dispersion
maps at various incident photon energies are shown in the first and third rows. First
principle calculated in-plane electronic dispersion at different kz values near the 3D Dirac
node k0 is plotted in the second and forth rows. (b) ARPES measured out-of-plane linear
E kz dispersion. (c) ARPES measured in-plane E kx dispersion. The white dotted
lines are guides to the eye tracking the out-of-plane dispersion. (d) Theoretically calculated
out-of-plane E kz dispersion near the 3D Dirac node shown over a wider energy window.
(e) Schematic (cartoon) of the 3D (anisotropic) Dirac semimetal band structure in Cd3 As2 .
(f ) Spin-integrated ARPES dispersion cut measured on the sample used for spin-resolved
measurements. The dotted lines indicate the momentum locations for the spin-resolved
EDC cuts. (g),(h) Spin-resolved ARPES intensity (black and red circles) and measured
net spin polarization (blue dots) for Cuts 1 and 2. This figure is adapted from Ref. [43].
130
5.3
5.3.1
Figure 5.7: Characterization of Na3 Bi system. (a) Crystal structure of Na3 Bi. The
two Na sites and Bi atoms are marked with different colors. (b) Projected crystal structure
at the (100) surface. (c) Structure of bulk and surface Brillouin zone at (001) and (100)
surfaces. Bulk Dirac nodes are marked by blue crosses. Note that the two bulk Dirac cones
point on the (001) surface, while they are separated in momentum
project to the same
when studied at the (100) surface. (d), (e), First principles calculation of the (001) (d)
and (100) surface (e) electronic structure. Theoretical nontrivial surface state (green lines)
appears along the edge of the bulk 3D Dirac cone in the (001) surface, while it becomes
separated from the bulk continuum when seen from the (100) surface (e). (f ) First principles
bulk band calculation for Na3 Bi. It is clear from the calculation that the band touching
happens along the A--A direction close to the zone center.
134
5.3.2
In order to observe the FASS and to illuminate the topological nature of the Dirac
semimetal state in Na3 Bi, we systematically study the electronic and spin groundstate
of its (100) surface-surface. Fig. 5.8(a) shows the ARPES measured Fermi surface of
our Na3 Bi sample at its native Fermi level. Remarkably, the measured Fermi surface
is found to consist of two Fermi points along the ky (100) direction and two arcs
that connect the two Fermi points. The measured Fermi surface topology [Fig. 5.8(a)]
is in agreement with the theoretical prediction [122], where two surface Fermi arcs
connect the two bulk nodal touchings. In order to confirm that the observed Fermi
surface is indeed the double Fermi arcs connecting two bulk nodal points, we study the
evolution of constant energy contour as a function of binding energy EB . As shown in
Fig. 5.8(b), the energy contour area of the two bulk nodal touching points is found to
enlarge into contours as EB is increased (hole-like behavior), whereas the two surface
Fermi arcs shrink while increasing EB (electron-like behavior). The evolution of the
constant energy contour as a function of binding energy EB (electron or hole behavior
for different bands) is also consistent with the theoretical expectation [see Fig. 5.8(d)].
To further confirm, we study the energy dispersion for important momentum space
cut directions [Fig. 5.8(b)]. As shown in Fig. 5.8(c), surface states with a surface
Dirac crossing are clearly observed near the Fermi level in Cut , consistent with the
theoretical calculation. The bulk valence band for Cut is found to be away from
the Fermi level. On the other hand, for Cuts and , no surface states are observed
but the bulk linear band is seen to cross the Fermi level, also consistent with the
calculation [see Fig. 5.8(e)]. The contrasting behavior that for Cut only surface
states cross the Fermi level whereas for Cuts and only the bulk linear bands cross
the Fermi level serves as a piece of critical evidence for the existence of double Fermi
arc surface states. We note that the two bulk nodal touchings observed in Fig. 5.8(a)
still expand in a finite area in momentum space, rather than being ideal points.
I(B)
I(S)
upon varying photon energy shows that the bulk Dirac band becomes much weaker
relative to the surface states as h is changed from 58 eV to 40 eV, due to the reason
that the kz value is moved away from the bulk nodal (Dirac) point. Furthermore,
Fig. 5.9(d) shows the dispersion along Cut , where the surface states with a clear
Dirac crossing are observed at different photon energies. This confirms the 2D nature
of the Fermi arc surface states along Cut . In Fig. 5.9(e), we present photon energy
dependent dispersion of the bulk nodal band [cut indicated by the white dotted line
136
Figure 5.8: Observation of Fermi arc surface states. (a) A Fermi surface map of the
Na3 Bi sample at photon energy of 55 eV. The BDP1 and BDP2 denote the two bulk Dirac
points momentum space locations. Two surface Fermi arcs are observed to connect these
two BDPs. (b) APRES constant energy contours as a function of binding energy at photon
energy of 55 eV. The dotted lines note the momentum space cuts for Panel (c). (c) ARPES
dispersion cuts , , as defined in Panel (b) at photon energy of 55 eV. Surface states for
the Fermi arcs are observed in cut , whereas the two bulk Dirac bands are seen in cuts
, . (d) Schematics of the constant energy contours drawn according to the theoretically
calculated band structure. The red shaded areas and the orange lines represent the bulk
and surface states, respectively. (e) Calculated band structure along Cut and Cut ().
138
Figure 5.8: (f ) Structure of bulk and surface Brillouin zone at (001) and (100) surfaces.
Bulk Dirac nodes are marked by blue crosses. Note that the two bulk Dirac cones project to
point on the (001) surface, while they are separated in momentum space when
the same
studied at the (100) surface. The (100) surface was not studied in previous works due to the
challenge of such cleavage in ARPES experiments (g) First principles bulk band calculation
for Na3 Bi. (h) First principles calculation of the (100) surface electronic structure.
Figure 5.9: Systematic studies on the double Fermi arc surface states.
Figure 5.9: Systematic studies on the double Fermi arc surface states. (a) ARPES
Fermi surface maps at different photon energies. The double Fermi arcs are observed independent of the photon energy value, whereas the two bulk Dirac band points along ky
become much weaker in intensity as the h is changed from 58 eV to 40 eV, revealing their
surface state and bulk band nature, respectively. (b),(c) In order to quantitatively evaluate
how much the bulk band intensity gets weaker as h is changed from 58 eV to 40 eV (its kz
dependence), we denote the middle point of the left Fermi arc as S and the bottom bulk
Dirac point as B. Panel (c) show the relative ARPES intensity between S and B.
The strong dependence of I(B)
I(S) upon varying photon energy shows the strong kz dependent
nature the bulk band Dirac points. (d) ARPES dispersion maps of the surface states at
two different photon energies. The surface states with a Dirac crossing are observed at
both photon energies, which further supports its 2D nature. (e) ARPES dispersion maps
of the bulk Dirac band at different photon energies [indicated by the white dotted lines in
Panel (a)]. The bulk Dirac band only crosses the Fermi level for excitation photon energies
around 58 eV, which demonstrates their three-dimensional dispersive (bulk) nature.
Figure 5.10: Spin-momentum locking in double Fermi arc surface states. (a) The
white dotted lines note the two momenta chosen for spin-resolved measurements. (b),(c)
Spin-resolved ARPES intensity and net spin polarization along the in-plane tangential direction for S-Cuts1 and 2 at photon energy of 55 eV. Clear spin polarization and spinmomentum locking are found in the data, which demonstrate the singly degenerate nature
of the Fermi arc surface states along the cut k-space direction.
140
5.3.3
We use the obtained electronic and spin data for the (100) Fermi arc surface states to
gain insights to the predicted 2D topological number (2D = 1) in bismuth trisodium.
In Fig. 5.11, we present a series of ARPES dispersion maps. As schematically shown
in Fig. 5.11(a), these maps, which are perpendicular to the k[001] axis, intersect with
the axis at different k[001] values. As one goes from Slice1 to Slice7 along the k[001] axis,
the ARPES measured and schematic energy dispersion for different sides are shown
in Figs. 5.11(b),(c). Due to the existence of the two bulk nodes (Slices 2 and 6),
the bulk band gap closes and reopens as one goes across each bulk node. Therefore,
it is interesting to note that the k[001] axis serves as an effective axis for a bulk
mass parameter in a 2D system. It is further interesting to note that the bulk band
gap closings at Slices 2 and 6 correlated with the absence/appearance of the surface
states at the Fermi level. As clearly seen in Figs. 5.11(b),(c), there are no surface
states for Slice1. As one moves from Slice1 to Slice3, the bulk band gap closes and
reopens, and surface states appear at the Fermi level of bismuth trisodium. Similarly,
as one further goes from Slice3 to Slice7, the bulk band gap closes and reopens,
and the surface states do not exists anymore for the data in Slice7. We note that
the gap closing and reopening property that we observed here does not exist in the
Fermi surface of any known topological insulator system such as Bi2 Se3 , which again
highlights that the observed Fermi arc surface states (FASS) are different from the
topological surface states (TSS) in a topological insulator.
We focus on Slices 3-5, which are in-between the two bulk nodes. Interestingly,
as seen in Figs. 5.11(b),(c), although surface states exist at the native Fermi level for
any Slices that are in-between the two bulk nodes, they are in general gapped [e.g.
Slice3 in Figs. 5.11(b)(c)]. The gapped nature of the surface states means that, for
these Slices (k[001] 6= 0), there does not exist a nontrivial 2D topological number that
can protect a doubly degenerate Dirac crossing for the surface states. This is intuitive
Figure 5.11: 2D topological number: Surface spin polarization and Momentumdependent band gap closing. (a) A schematic view of the band structure of the topological Dirac semimetal phase. Seven slices/cuts that are taken perpendicular to the k[001] axis
are noted. (b),(c) ARPES measured [Panel (b)] and schematic [Panel (c)] band structure
for these slices are shown.
146
Figure 5.12: Evolution through the bulk singularity. (a) ARPES constant energy
maps obtained on the (100) surface. At EB = 50 meV and higher binding energies, the
electronic states are mainly from the two bulk Dirac bands. The Constant energy contour
at EB = 150 meV, where the two bulk disconnected (bulk) Dirac band contours just merge
(the Lifshitz transition energy). (b) Dispersion of Cuts x and y, which are defined in Panel
(c). The hybridization of the two bulk Dirac cones results in a saddle point singularity at
the intersection of Cut X and Cut Y, signified by band maximum (lowest binding energy)
along cut X and band minimum (highest binding energy) along cut Y. (c) Lifshitz transition
of two bulk Dirac bands in bismuth trisodium with the Lifshitz transition of two surface
Dirac bands in a topological crystalline insulator Pb0.7 Sn0.3 Se.
148
Figure 5.13: The groundstate in the inverted regime is described by a pair of Dirac nodes
along the rotational axis in the bulk and double Fermi arc surface states connecting the two
bulk nodes on the surface. Inset: an ARPES Fermi surface map of Na3 Bi showing the double
FASS and the two bulk Dirac nodes. (e),(f ) Schematic Fermi surface topology of bismuth
trisodium and Bi2 Se3 . In bismuth trisodium, each Dirac node (the blue shaded area) can be
viewed as a composite of two degenerate Weyl nodes (yellow and green areas). The orange
arrows note the spin polarization according to our spin-resolved ARPES measurements.
The inset of Panels (c),(e) shows the ARPES measured Fermi surface.
5.4
Now that we have presented the topological Dirac semimetal state and its double
FASS using a concrete example of Na3 Bi, in this section we discuss different classes
of topological semimetals. We note that topological semimetal is an actively ongoing research area both in experiments and in theories. The three classes (Dirac,
Weyl, and nodal-line) listed here are the currently theoretically known ones (within
band theory), but there might be other types being proposed in the future. We
also note that our observation of 3D Dirac nodes and FASS in Na3 Bi is the first
concrete realization of a topological Dirac semimetal (in the sense that the topological
surface states (FASS) are observed). The other two classes, namely the topological
Weyl semimetal [118, 187] and the topological nodal-line semimetal [192], remain
completely experimentally elusive. Again, our discussion will only cover the concepts
of these phases. While the detailed formulations can be found in theory papers
[10,118,187,192], here the idea is to point out the key concepts that serve as important
guidelines for us to experimentally search these new phases in real materials.
Let us start from a Weyl semimetal. We have briefly mentioned the Weyl semimetal
state in Chapter 3.1 (see Fig. 3.1). There we said that in a time-reversal invariant
but space inversion symmetry breaking bulk material, as the system is tuned to go
through a band inversion and a topological phase transition from a conventional band
insulator to a topological insulator, there exists a range of tuning parameter values,
where the band-gap goes to zero. Within this a range of tuning parameter values,
the system is a Weyl semimetal. We note that the key is that in an inversion asymmetric system, the bulk electronic bands are singly degenerate except at the Kramers
points. Therefore, as the bulk conduction and valence bands are inverted and cross
each other, these crossings are between two singly degenerate bands. This is in sharp
150
contrast to the case in a Dirac semimetal (see the previous two sections for Cd3 As2
and Na3 Bi), where the crossings are between two doubly degenerate bands.
For a band crossing between two singly degenerate bands, we can write down an
effective Hamiltonian that describes the vicinity of the crossing point as
H = v(px x + py y + pz z ),
(5.1)
where ~p is the momentum from the crossing point, ~ is the pseudo-spin. It can be
immediately seen that this Hamiltonian satisfy the Weyl equation, and therefore the
low-energy excitation of the bulk bands near the crossing is described by the Weyl
equation. The sign here defines the handness or chirality of the (pseudo)spinmomentum locking. In theory, the chirality is also proportional to a topological
charge, as one integrates the Berrys phase around a Weyl point [10]. Now let us
consider the simplest Weyl semimetal system where there are two Weyl nodes with
the opposite chiralities, as shown in Fig. 5.14. This is a similar situation as in
Na3 Bi (see Fig. 5.11) in the sense that there are only two points in the whole bulk BZ
where the band-gap vanishes. Therefore, we consider the surface and bulk electronic
structure on different 2D k-slices, similar to what we did in Fig. 5.11. As shown in
Fig. 5.14, except at Slides 2 and 4, the bulk band structure has a full energy gap at all
other 2D k-slices. Due to the existence of the Weyl nodes, the bulk bands go through
two band inversions (gap closing and reopening) as one scans from Slide 1 to Slide 5.
It is theoretically shown [10] that the 2D k-slides Chern number n changes by ()1
as one crosses a Weyl point with the chirality. Therefore, in a Weyl semimetal, each
k-slice (except the slices that contain the Weyl points where the system is gapless)
can be treated as a 2D Chern insulator. This is shown in Fig. 5.14. Therefore, similar
to a topological Dirac semimetal, a Weyl semimetal is described by a number of Weyl
nodes in the bulk and Fermi arc surface states (FASS) connecting the Weyl nodes
other at discrete (0D) points in a bulk BZ. In a topological nodal-line semimetal, the
band-crossing between the conduction and valence bands forms a 1D-closed-loop in a
bulk BZ. And the surface states can be described as a drum surface whose boundary
is the closed-loop of the bulk band crossing (see Fig. 5.16). Theoretically, such type
of novel topological semimetal can be realized in a time-reversal and space-inversion
symmetric spinless fermion bulk material, or a time-reversal or space-inversion breaking system with additional mirror symmetries.
Since the experimental progress on these semimetals are preliminary, we do not go
into further details. Nevertheless, it can be seen that topological semimetal is a truly
exciting field. Realization of these new nontrivial semimetals can open a new era in
topological insulator research. And breaking symmetries in the known topological
Dirac semimetals Na3 Bi and Cd3 As2 is a promising route toward these new phases.
Figure 5.14: Electronic groundstate of a Weyl semimetal. Top: The Fermi surface
of a Weyl semimetal is described by two Weyl nodes with opposite chiralities in the bulk and
a FASS that connects the Weyl nodes on the surface. It has been theoretically shown that
each k-slice (except the slices that contain the Weyl points where the system is gapless)
can be viewed as a 2D Chern insulator. And as one scans across a Weyl point, the
systems Chern number changes by 1. Bottom: Bulk and surface electronic dispersions
on different 2D k-slices.
154
Figure 5.15: Tuning the Dirac semimetal Na3 Bi into a Weyl semimetal via space
inversion symmetry breaking. Each Dirac node in Na3 Bi is a composite of two degenerate Weyl nodes with the opposite chiralities. Under inversion symmetry breaking, the
Weyl nodes are separated in momentum space, realizing a Weyl semimetal.
Chapter 6
Topological states in 4f Kondo
systems SmB6 and YbB6
Understanding the physics of strongly correlated systems is one of the most challenging tasks in physics. In solid states, strong electron-electron interaction is known to
lead to many exotic groundstates ranging from Mott insulation, unconventional superconductivity, heavy fermion behavior, to a fractional quantum Hall state. Studying
the interplay between nontrivial topology and strong correlation is of fundamental
importance. In fact, the definition of a topological order (not a symmetry-protected
topological state) intrinsically requires strong electron-electron interaction [24], and
the only topological order realized in experiments to date is that of in a fractional
quantum Hall state. Moreover, even within the framework of symmetry-protected
topological states, introducing strong electronic correlation is also believed to dramatically enrich the possible topological classification as proposed recently [141, 201].
On the other hand, studying topological physics in a strongly correlated system is
very challenging. Since the surface states in a strongly correlated system becomes
non-electron-like quasi-particle excitations, currently there is no direct probe to systematically study the metallic surface modes including their energy-momentum dis156
persion and spin polarization, as what has been achieved via spin-ARPES in weakly
interacting electronic systems.
In this chapter, we present our ARPES studies on the surface and bulk electronic
groundstate of certain Kondo systems with 4f electrons, in order to search for possible
topologically nontrivial states in these correlated materials. The fact that we can still
use ARPES to measure their surface states means that the correlation effects are
not extremely strong so that band theory completely breaks down in all aspects
in these systems. However, we show that electron interaction plays a vital role in
the formation of the topological states and properties of the resulting surface states
such as the surface Fermi velocity are quite different from a nearly non-interacting
topological insulator such as Bi2 Se3 . Our study servers an important initial step
toward realizing strongly correlated topological insulator states. The identification
of topological surface states in 4f Kondo materials is particularly interesting due
to a variety of symmetry breaking states such as heavy fermion superconductivity,
ferromagnetism, antiferromagnetism, hidden order state, etc., which are known to
occur in the rare-earth Kondo materials.
6.1
Materials with strong electron correlations often exhibit exotic ground states such as
the heavy fermion behavior, Mott or Kondo insulation and unconventional superconductivity. Kondo insulators are mostly realized in the rare-earth based compounds
featuring f -electron degrees of freedom, which behave like a correlated metal at high
temperatures whereas a bulk bandgap opens at low temperatures through the hybridization [202204] of nearly localized-flat f bands with the d -derived dispersive
conduction band. With the advent of topological insulators [2] the compound SmB6 ,
from transport that the bulk is insulating, ARPES shows large Fermi surface pockets
(metallicity of the surface) at this temperature. Another unusual aspect is that not
all Kramers points are enclosed by the in-gap states. Our observed Fermi surface
thus consists of 3 (or odd number Mod 2 around each Kramers point) pockets per
Brilluoin zone and each of them wind around a Kramers point only and this number
is odd (at least 3). Therefore, our measured in-(Kondo) gap states lead to a very
specific form of the Fermi surface topology [Fig. 6.1(f)] that is remarkably consistent
with the theoretically predicted topological surface state Fermi surface expected in
the TKI groundstate phase despite the broad nature of the contours.
Since for the laser-ARPES, the photon energy is fixed (7 eV) and the momentum
162
Figure 6.1: Brillouin zone symmetry, and band structure of SmB6 . (a) Crystal structure of SmB6 . Sm ions and B6 octahedron are located at the corners and the
center of the cubic lattice structure. (b) The bulk and surface Brillouin zones of SmB6 .
High-symmetry points are marked. (c) Resistivity-temperature profile for samples used
in ARPES measurements. (d), (e) Synchrotron-based ARPES dispersion maps along the
X
M
and the X
X
momentum-space cut-directions. Dispersive Sm 5d band and
M
non-dispersive flat Sm 4f bands are observed, confirming the key ingredient for a heavy
fermion Kondo system. (f ) A Fermi surface map of bulk insulating SmB6 using a 7 eV
laser source at a sample temperature of 6 K (Resistivity= 5 mcm), obtained within
the EF 4 meV window, which captured all the low energy states between 0 to 4 meV
binding energies, where in-gap surface states spectral weight contribute most significantly
and X
reflect low-lying
within the insulating Kondo gap. Intensity contours around
metallic states near the Fermi level, which is consistent with the theoretically predicted
Fermi surface topology [206] of the topological surface states. This figure is adapted from
Ref. [49].
Figure 6.2: Temperature dependent in-gap states and its two-dimensional nature. (a) Cartoon sketch depicting the basics of Kondo lattice hybridization at temperatures above and below the hybridization gap opening. (b) Partially momentum-integrated
1
ARPES spectral intensity in a 0.15
A window (k defined in Panel (a)] above and below the Kondo lattice hybridization temperature [TH ). (c) Momentum-integrated ARPES
point at various temperatures.
spectral intensity centered at the X
164
pocket
Figure 6.2: (d) Analogous measurements as in Panel (c) but centered at the
1
(k = 0.3
A ). ARPES data taken on the sample after thermally recycling (6 K up to
50 K then back to 6 K) is shown by Re 6K, which demonstrates that the in-gap states
are robust against thermal recycling. (e) Synchrotron based ARPES energy momentum
X
M
momentum
dispersion maps measured using different photon energies along the M
space cut-direction. Incident photon energies used are noted on the plot. (f ) Momentum
distribution curves (MDCs) of data shown in a. The peaks of the momentum distribution
curves are marked by dashed lines near the Fermi level, which track the dispersion of the
low-energy states. (g) Momentum distribution curves in the close vicinity of the Fermi level
(covering the in-gap states near the gap edge) are shown as a function of photon energy
which covers the kz range of 4 to 5 at 7 K. This figure is adapted from Ref. [49].
6.2
5d and Sm 4f bands near the Fermi level leads to a Kondo insulating gap, consistent
with previous findings [206]. Interestingly, our calculation results [Figs. 6.3(a)-(c)]
show that the groundstate is insensitive to the strength of the on-site coulomb repulsion U (qualitatively the same results for U = 0 and U = 8 eV), which demonstrates
the robustness of the Kondo insulating state in SmB6 . In sharp contrast, in YbB6 ,
a Kondo insulating state is also seen without including coulomb repulsion [U = 0,
see Fig. 6.3(d)]. However, as one increases the strength of the coulomb repulsion
U, our calculation shows that the energy position of the Yb 4f bands are pushed
to much higher energies below the chemical potential [Figs. 6.3(e),(f)], and therefore
a Kondo insulating mechanism becomes irrelevant to the low energy physics.On the
other hand, the B 2p bands become closer to the Fermi level and at certain intermediate U values [U = 5 eV, see Fig. 6.3(e)], an inversion between the Yb 5d and the
B 2p bands is observed. This calculation suggests a novel scenario that a topological
insulator state can be realized in the rare-earth hexaborides even without a Kondo
insulating mechanism.
In order to reveal the electronic state of YbB6 , we systematically study its electronic structure at the (001) natural cleavage surface. As shown in Fig. 6.4(c), the
lowest 4f flat band in YbB6 is 1 eV below the Fermi energy. This is in sharp contrast
to the ARPES data on SmB6 , where the flat 4f band is found to be only 15 meV
away from the Fermi level [49]. Therefore, our data reveal the physical origin for
the absence of the Kondo insulating state in YbB6 , which also negates the recent
theoretical work that predicts the existence of the topological Kondo insulator phase
in YbB6 [221]. Apart from the intense 4f band, our data in Fig. 6.4(c) also reveal an
point that crosses the Fermi level.
electron-like pocket centered at the X
In order to systematically resolve the Fermi level electronic structure, we present
high-resolution ARPES measurements in the close vicinity of the Fermi level. It is
important to note that at the studied (001) surface, the three X points (X1 , X2 , and
Figure 6.3: Bulk band structure (GGA+U) calculation of Sm6 and YbB6 . (a),
(b) Band structure of SmB6 from GGA calculations. Sizes of yellow, blue, and green dots
denote weights of Sm-4f , Sm-5d, and B-2p orbitals in various bands. Zoomed in view in
Pane (b). (c) Low-energy band structure around EF based on GGA and GGA+U (U = 8
eV) computations. (d)-(f ) Band structure calculation of YbB6 at various U values. Top:
large energy range. Middle: Zoomed-in view. Bottom: Scematic.
170
Figure 6.4: Topological surface states in YbB6 . (a) ARPES measured Fermi surface of
and X
points. This spectrum is measured
YbB6 . Circular shaped pockets are observed at
with photon energy of 50 eV at temperature of 15 K. (b) ARPES dispersion maps measured
X
with different photon energy. (c) ARPES measured dispersion maps along the
momentum-space cut-directions. Dispersive cone like pocket and non-dispersive flat Yb 4f
bands are observed. The measured photon energy are noted on the plots. This figure is
adapted from Ref. [85].
Figure 6.5: Photon energy and temperature dependent dispersion maps. (a)
Photon energy dependent dispersion map with wider binding energy. The measured photon
energy are noted on the plots. The 4f flat bands are about 1 eV below the Fermi level. These
X
momentum space cut direction with temperature of
spectra are measured along the
15K . (b) Temperature dependent ARPES spectra. The measured temperature are noted
on the plots. The slight variation of the pocket with temperature is likely due to the thermal
M
momentum space
expansion of the sample. These spectra are measured along the
cut direction. This figure is adapted from Ref. [85].
172
Figure 6.6: Theoretical calculation showing the topological surface states on the
(001) surface of YbB6 . First-principles slab calculation of the (001) surface with U = 4
and the X
eV. Dirac-cone surface states are clearly seen in the bulk energy-gap at the
points, both of which correspond to the projection of the X points in the bulk BZ.
Chapter 7
Superconductivity and magnetism
in topological insulators
The interplay between a topological insulator state and a symmetry-breaking (superconducting or ferromagnetic) state is of interest in both fundamental physics and
applications [2, 6, 9, 5260, 124127, 222225]. Specifically, inducing superconductivity
in the Dirac surface states of a topological insulator is believed to realize Majorana
fermion excitation [124] and supersymmetry phenomenon [127] in a condensed matter setting. A Majorana fermion is a non-Abelian quasi-particle, which is believed
to be the key building block of a topological quantum computer. Supersymmetry is
a fascinating high energy physics concept, which remains elusive in particle physics
experiment to date. On the other hand, a ferromagnetically ordered topological insulator can realize a Chern insulator in its 2D thin film geometry [126], which means that
the boundary of the 2D film will host chiral electronic edge-modes with a quantized
Hall conductance even without an external magnetic field. This is of much interest
in building low-power electronics. Furthermore, a magnetic topological insulator is
predicted to show quantized Kerr rotation [125, 222], which serves as an independent
measure of the topological number besides the spin-ARPES measurements on the
174
topological surface states. The same effect is also theoretically known to simulate the
electrodynamics of the Axion [223], a particle candidate for the dark matter. Despite
the interest, none of the major TI materials (such as Bi2 Se3 ) are natural superconductors or ferromagnets. Therefore, one has to dope a TI material or interface with
a superconductor or ferromagnet, in order to induce these symmetry breaking-states.
In this chapter, we present our systematic ARPES and spin-ARPES measurements
on magnetically doped TIs and heteostructure samples between a TI thin film and an
s-wave superconductor. Since ARPES is a probe that measures the electronic quasiparticle spectrum without nanometer spatial resolution, thus it is not practically
possible to directly measure the Majorana exciations (non-electron quasi-pariticles)
in a superconducting TI or the chiral edge states (a 1D state) in a magnetically
doped TI thin film. The goal of our experiments is to experimentally demonstrate
the electronic and spin groundstates that are required for these theoretically proposed
phenomena.
7.1
doped Bi2 Se3 films [Figs. 7.1(c)]. In Mn-doped Bi2 Se3 , a hysteretic behavior in the
out-of-plane magnetic response is observed consistently which suggests a ferromagnetically ordered groundstate. The observation of ferromagnetic character and its absence in Zn-Bi2 Se3 motivate us to systematically compare and contrast the electronic
density of state behavior in the vicinity of the surface Dirac node of these samples.
Fig. 7.1(d) shows the measured electronic states of Mn(Zn)-doped Bi2 Se3 using highresolution (spin-integrated) angle-resolved photoemission spectroscopy (ARPES). In
the undoped Bi2 Se3 film [leftmost panel of Fig. 7.1(d)], a map of spectral density of
states reveals a bright and intact Dirac node (signaled by the red spot located at
the Dirac crossing in the panel), which indicates that in undoped Bi2 Se3 the Dirac
node is gapless, consistent with the previous studies of pure Bi2 Se3 [32]. In samples
where Mn atoms are doped into the bulk [first row Fig. 7.1(d)], we observe that the
corresponding bright (red) spot at the Dirac node gradually disappears, revealing a
clear systematic spectral weight suppression (SWS) with increasing Mn concentration. In contrast, the spectral intensity at the Dirac node is observed to survive
upon systematic Zn doping except for the Zn=10% sample where some suppression
of intensity is observed. This suggests that the Dirac node remains largely intact
upon Zn doping. The observed systematic behavior of spectral evolution motivates
us to quantitatively define an energy scale, ESWS , associated with the SWS observed
at the Dirac node. The ESWS is taken as the energy spacing between the upper
Dirac band minimum and the Dirac node location along the energy axis as illustrated
in Fig. 7.1(e), which roughly corresponds to half of the surface gap magnitude. The
value of the energy scale can be quantitatively determined by fitting the ARPES measured energy-momentum distribution curves. The doping dependence of the ESWS on
samples measured at T = 20 K is shown in Fig. 7.2(c). The ESWS is observed to
increase rapidly with Mn concentration but it remains nearly zero with Zn doping.
The effect of temperature dependence on ESWS is shown in Fig. 7.2(d). The temper-
ultra-thin film limit. In this case, the top and bottom surfaces couple together and
open up a gap as electrons can tunnel from one to the other [Figs. 7.4(e)-(h)]. Such
a gap in the surfaces is not related to magnetism. It is important to know the spin
configuration associated with such a gap. In Figs. 7.4(e)-(h), we utilize Spin-resolved
ARPES to measure the spin configuration on the very top region (within 5
A) of
a Bi2 Se3 film whose thickness is three quintuple layers (3 QL 28.6
A). At large
1
[e.g. -0.10
parallel-momenta far away from
A in Fig. 7.4(g)], we observe clear
and eventually reach to 0 as one approaches the TR breaking gap by lowering the
chemical potential as discussed in theory [229], at least within the magnetic energy
scale bz (Fig. 7.5). We show that this theoretical requirement can be experimentally
achieved on the Mn-Bi2 Se3 surface via surface NO2 adsorption at various dosage levels.
Fig. 7.5(a) shows the Mn(2.5%)-Bi2 Se3 surface states with in situ NO2 adsorption.
The chemical potential is observed to be gradually shifted and finally placed within
the magnetic gap. The associated phase (GP) at each experimentally achieved sample
chemical potential [noted at the top-right corner of each panel in Fig. 7.5(a)] is found
to gradually change from to 0. The GP= 0 is the experimental condition for
realizing axion electrodynamics with a topological insulator [222, 223].
With the chemical potential moved into the magnetic gap, the time-reversal breaking in-gap state features a singular hedgehog-like spin texture [Fig. 7.5(d)]. Such
spin configuration simultaneous with the chemical potential placed within the magnetic gap [Fig. 7.5(d)] is the fundamental requirement for most of the theoretical
proposals relevant to the utilization of magnetic topological insulators in novel devices [125, 126, 222, 223, 225].
Figure 7.1: Magnetic (Mn%) and non-magnetic (Zn%) doping on Bi2 Se3 films.
(a),(b) Schematic layout and photograph of MBE grown Bi2 Se3 films used for the experiments. (c) Magnetization measurement at T = 45 K using magnetic circular dichroism
shows out-of-plane ferromagnetic character of the Mn-Bi2 Se3 film (111) surface through the
observed hysteretic response. Inset shows the measurement geometry. L(R)CP represents
left(right)-handed circularly polarized light. (d) Electronic band dispersion of Mn(Zn)
M
momentum space cut. (e) Energydoped Bi2 Se3 MBE thin films along the M
momentum distribution curves of Mn(Zn)-doped Bi2 Se3 samples. The energy scale associated with the spectral weight suppression (SWS) ESWS is observed as the energy spacing
between the upper Dirac band minimum and the Dirac point location along the energy axis.
This figure is adapted from Ref. [57].
184
Figure 7.2:
Temperature and doping dependence of magnetically induced
changes on Mn-Bi2 Se3 surface. (a) The Mn atoms on the surface of the film are
out-of-plane magnetically ordered, serving as a local magnetic field which results in the
spin texture reorientation. (b) Two independent hysteresis measurements at T = 45 K using X-ray magnetic circular dichroism reveal the ferromagnetic character of the Mn-Bi2 Se3
film surface. The lower inset shows the remanent surface magnetization as a function of
temperature. The out-of-plane magnetic hysteresis and ARPES gap were found to be correlated with each other. The upper inset shows the gap at the Dirac point in Mn(2.5%)-Bi2 Se3
film. (c) The spectral weight suppression energy scale ESWS and inverse momentum width
1/k of the surface states are shown as a function of Mn and Zn concentration measured at
T = 20 K. (d) Temperature dependence of spectral weight suppression energy scale around
the Dirac point of Mn(2.5%)-Bi2 Se3 film (as noted in Panel (c) by the dotted square). The
ESWS decreases as temperature is raised signaling gradual weakening of magnetism. This
figure is adapted from Ref. [57].
186
Figure 7.5: Chemical potential tuned to lie inside the magnetic gap. (a) Measured
surface state dispersion upon in situ NO2 surface adsorption on the Mn-Bi2 Se3 surface. The
NO2 dosage in the unit of Langmuir (1 L = 1 106 torrsec) and the tunable geometrical phase (see text) associated with the topological surface state are noted on the top-left
and top-right corners of the panels, respectively. The red arrows depict the time-reversal
breaking out-of-plane spin texture at the gap edge based on the experimental data. (b)
Geometrical phase (GP) associated with the spin texture on the iso-energetic contours on
the Mn-Bi2 Se3 surface as a function of effective gating voltage induced by NO2 surface adsorption. Red squares represent the GP experimentally realized by NO2 surface adsorption,
as shown in Panel (a). GP= 0 (NO2 =2.0 L) is the condition for axion dynamics [223]. (c)
The magnetic interaction strength bz (see text for definition), which corresponds to half
of the magnetic gap magnitude, is obtained based on spin-resolved data sets (polar angle
, momentum k) for Mn(2.5%)-Bi2 Se3 film II [see Figs. 7.3(e)-(g)]. (d) The time-reversal
breaking spin texture features a singular hedgehog-like configuration when the chemical
potential is tuned to lie within the magnetic gap, corresponding to the experimental condition presented in the last panel in Panel (a). (e),(f ) Spin texture schematic based on
measurements of Zn-doped Bi2 Se3 film (60 QL), and 3 QL undoped ultra-thin film with
chemical potential tuned onto the Dirac point energy or within the tunneling gap. This
figure is adapted from Ref. [57].
188
7.2
energy of 50 eV, the bulk conduction band is almost completely suppressed and the
only dispersive band near the Fermi level is the Dirac surface state. We subsequently
study the spectra at the momentum k1 where the ARPES signal is dominated by the
contribution from the surface states. Leading edge shifts and coherence peaks are
clearly observed from k1 , which confirms the superconductivity in the Dirac surface
states using a different photon energy. These systematic momentum-resolved measurements clearly show the existence of a superconducting helical electron gas, which
is realized on the top surface of Bi2 Se3 grown on top of an s-wave superconductor
NbSe2 .
We perform ARPES measurements around the surface state Fermi surface as a
function of Fermi surface azimuthal angle , to study the extent of anisotropy of
the surface state superconducting gap. To isolate the surface state signal from the
bulk, photon energy of 50 eV is used, where only surface states are observed near the
Fermi level as seen in Fig. 7.8(a). Five representative momentum space cut-directions
(15) are chosen as indicated by the dotted lines in Fig. 7.8(a). The helical-surface
state superconducting gap observed by ARPES at different angles and their fits are
shown in Fig. 7.8(b). The reasonably good surface state fitting results [blue curves in
Figs. 7.7(g) and Fig. 7.8(b)] indicate that the obtained surface state superconductivity
is consistent with its spin-helical and linear dispersive properties, which supports its
helical-Cooper pairing nature. The obtained magnitude of superconducting order
parameter is then plotted as a function of Fermi surface angle in Fig. 7.8(c). The
superconducting gap is found to be nearly isotropic, which is also consistent with
the time-reversal invariant helical nature of the surface state superconductivity as
expected theoretically [124, 224]. We note that the helical Cooper pairing in the
topological surface states as observed here is also different from that of in other singly
degenerate (spin-momentum locked) but non-topological systems. For example, in
a Rashba-2DEG, although the electrons are also singly degenerate, but along any
induced superconducting gap near the top surface increases with a larger the Dirac
point hybridization gap, which is realized in thinner TI films. This observation is
qualitatively consistent with the theoretical description of the superconducting proximity effect, where the Cooper pair potential on the top surface is enhanced with the
decreasing thickness of the normal metal. More interestingly, it can be seen that the
surface state superconducting gap increases at a faster rate than that of the proximity gap on the bulk band. Such contrast reveals that stronger surface-to-surface
hybridization significantly enhances the helical pairing in the surface states on the
top surface. These microscopics of the superconducting proximity effect observed in
our data will be a valuable guide in properly interpreting the vast complexity of the
transport data addressing the proximity effects in TI films and heterostructures.
In order to test the time-reversal invariant character of surface state superconductivity of Bi2 Se3 required by its helical nature, we study manganese (Mn) doped
Bi2 Se3 grown on top of NbSe2 . Mn atoms are introduced into Bi2 Se3 throughout the
film during the MBE growth. ARPES studies on 4QL Bi2 Se3 films with two different
Mn doping (4% and 10%) levels are presented in Figs. 7.10(a)-(f). Bulk manganese
doping is found to hole dope the system, thus bringing the chemical potential closer
to the Dirac point. In principle, Mn impurities can affect the induced superconductivity in several different channels, all leading to the suppression of proximity
superconductivity: The major effect is that Mn impurities introduce (either random
or ordered) magnetism into the TI, which is destructive to the helical pairing; Another minor effect, which can also contribute, is that impurities generate random
disorder reducing the electron mean free path. As shown in Figs. 7.10(a)-(f), the
superconducting coherence peak is strongly suppressed in the heavily Mn-doped samples. These momentum-resolved measurements allow us to isolate the strength of
the effect on helical surface states and bulk bands, thus directly demonstrating that
magnetic impurities lead to strong pairing breaking in both conventional and helical
gap in Bi2 Se3 near the interface. It is worth noting that unlike ARPES, which is
mostly sensitive to the top surface, the point-contact transport probes deeper into
the superconductor, similar to the electron mean free path, which is estimated to be
16 nm in our films. The induced gap in Bi2 Se3 at the Bi2 Se3 /NbSe2 interface is 0.8
meV at 3 K from the point-contact measurement, which is in reasonable agreement
with the fitted gap value extracted from the ARPES measurement (see data on 3QL
sample). Our results thus suggest that the combination of ARPES and point-contact
transport together provides a powerful method for probing superconducting proximity effect which can be used to correlate the proximity gap on the top surface and the
buried interface if film thickness is not too large (not larger than the superconducting
coherence length).
In contrast to idealized theoretical models [124, 224] of topological superconductivity where only Dirac surface states cross the Fermi level, real samples exhibit a
complex phenomenology due to the coexistence of multiple bands at the chemical
potential, as demonstrated in our data above. Thus, the interpretation of experimental studies must take into account both the desirable Cooper pairing from the
Dirac surface states and conventional superconductivity from the bulk, trivial surface
states and impurity surface states. The coexistence of multiple bands at the Fermi
level means that any superconductivity realized in actual TI materials consist of not
only the desirable helical Cooper pairing from the Dirac surface states but also conventional superconductivity from the bulk states, as shown above in our data. We
note that although progress has been reported by using conventional transport and
STM experiments [52,54,234242], those studies do not have the spin and momentum
resolution necessary to distinguish the helical Cooper pairing from that of the conventional superconductivity from other bands that intermix at the interface making
interpretation of Majorana fermions unreliable or complex. Hence a direct experimental demonstration of the existence of superconductivity in the helical Cooper
tification of helical-Cooper pairing. One exciting scenario is to realize supersymmetric phenomenon in our experimental setup [127] by further improvement of the film
quality and magnetic doping process. As shown in Fig. 7.11(d), magnetic doping
or an external in-plane magnetic field is necessary to drive the system to the critical
point between the helical superconductivity and the normal Dirac gas states, with the
chemical potential tuned to the Dirac point [demonstrated in Fig. 7.11(b)]. Under this
condition, theory predicts that topological surface states (a fermionic excitation) and
the fluctuations of superconducting order (a bosonic excitation) satisfy supersymmetry relationship, and therefore, strikingly, possess the same Fermi/Dirac velocity and
same lifetime or self-energy [127]. While the superpartners of elementary particles
in high energy physics have never been experimentally observed, the experimental
methodologies, artificial sample fabrication control and experimental observations reported here pave the way for simulating and testing supersymmetric physics concepts
in future sub-Kelvin nanodevices fabricated out of sample configurations discussed
here.
Figure 7.6: Sample layout and characterization. (a) A schematic layout of ultra-thin
Bi2 Se3 films epitaxially grown on the (0001) surface of single crystalline s-wave superconductor 2H-NbSe2 (Tc = 7.2 K) using the MBE technique. (b) High resolution transmission
electron microscopy (TEM) measurements of the Bi2 Se3 /NbSe2 interface at 200 keV electron energy. An atomically abrupt transition from NbSe2 layered structure to the layered
quintuple layer structure of Bi2 Se3 is resolved, showing a good atomically flat interface crystal quality. (c) Momentum-integrated ARPES intensity curves over a wide binding energy
window (core-level spectra) taken on a representative 3QL Bi2 Se3 ( 3 nm) film grown
on NbSe2 before and after removing the amorphous selenium capping layer (decapping).
(d) A low-energy electron diffraction (LEED) image on a 4QL Bi2 Se3 film shows six-fold
pattern providing evidence that the thin Bi2 Se3 film is well-ordered. (e) High-resolution
ARPES dispersion map of a 4QL Bi2 Se3 film on NbSe2 after decapping using incident photon energy of 50 eV. The white circle and cross schematically show the measured direction
of the spin texture on the top surface of our 4QL Bi2 Se3 film shown in Panel (f ). (f )
Spin-resolved ARPES measurements on 4QL Bi2 Se3 as a function of binding energy at a fix
momentum which is indicated by the white dotted line in Panel (e). (g) High-resolution
ARPES dispersion map of a 6QL Bi2 Se3 film on NbSe2 at T = 12 K. The white arrow indicates the momentum for the temperature dependent EDC in Panel (h). (h) Temperature
dependence of the ARPES spectra in Panel (g). This figure is adapted from Ref. [60].
200
Figure 7.8: Surface superconducting gap and helical pairing. (a) Fermi surface map
taken at incident photon energy of 50 eV. The white dotted lines indicate the momentumspace cut-directions chosen to study the surface state superconducting gap as a function of
Fermi surface angle around the surface state Fermi surface. (b) Symmetrized and normalized ARPES spectra along 1 through 5 respectively (red) and their surface gap fittings.
(c) Fermi surface angle dependence of the estimated superconducting gap around the surface state Fermi surface. (d) Illustrations for helical-Cooper pairing in a spin-momentum
locked helical electron gas and (e) The conventional s-wave Cooper pairing in an ordinary
superconductor. Note that the superconductivity in a Rashba-2DEG can be visualized also
in the same schematic [Panel (e)] but with the length of the k-vector for spin up and spin
down electrons being different (spin-split). However, for a Rashba-2DEG, it is still true
that along any k-direction, both spin up and spin down electrons cross the Fermi level and
are available for the Cooper pairing. (f ) Model calculation results of a topological insulator
film in proximity to an s-wave superconductor shows the calculated total superconducte S ) and triplet (
e T ) components on
ing pairing amplitude and its decomposed singlet (
the top surface of a 4-unit-cell thick TI interfaced with an s-wave superconductor, which
further confirms the helical (topologically nontrivial) nature of the induced surface state
e is a dimensionless, we denote a tilde
e
superconductivity in our Bi2 Se3 films. Since
to differentiate from the superconducting gap measured in experiments. This figure is
adapted from Ref. [60].
202
Figure 7.9: Hybridization dependence of superconducting gap. (a) ARPES dispersion map of a 3QL Bi2 Se3 film measured at T = 12 K using incident photon energy of
50 eV. (b) ARPES spectra at the fixed momentum of k1 at different temperatures. (c)
Symmetrized ARPES spectra at different temperatures. (d) ARPES dispersion map of a
7QL Bi2 Se3 film measured at T = 12 K using incident photon energy of 18 eV. (e),(f )
ARPES spectra at the fixed momenta of k1 and k2 . (g) ARPES measured superconducting
gap for topological surface states (k1 ) and for the bulk conduction states (k2 ) as a function
of Dirac point gap value (surface-to-surface hybridization strength). The dotted lines are
guides to the eye. (h) Surface-to-surface hybridization dependence in calculation. Since
e TI in calculation is a dimensionless number, we normalize it by the
the pairing amplitude
e Substrate (a constant). This figure is
pairing amplitude of the substrate superconductor
adapted from Ref. [60].
Figure 7.10: Destruction of the helical Cooper pairing via time-reversal symmetry breaking magnetic doping. (a) ARPES dispersion map of a 4QL Mn(4%)-doped
Bi2 Se3 film measured at T 1 K. (b),(c) ARPES spectra at the fixed momenta of k1 (topological surface states) and k2 (bulk conduction states). (d)-(f ) Same as Panels (a)-(c) but
for 10% Mn doping. The Mn concentrations indicated here are nominal, which means they
are estimated by the flux ratio of Mn flux : Bi flux during the MBE growth. This figure is
adapted from Ref. [60].
204
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Appendices
231
(2014).
4. M. Neupane, A. Richardella, J. Snchez-Barriga, Su-Yang Xu et al., Observation of Quantum-Tunneling Modulated Spin Texture in Ultrathin Topological
Insulator Bi2 Se3 Films. Nature Commun. 5, 3841 (2014).
5. Anjan A. Reijnders, Y. Tian, L. J. Sandilands, G. Pohl, I. D. Kivlichan, S.
Y. Frank Zhao, S. Jia, M. E. Charles, R.J. Cava, Nasser Alidoust, Su-Yang Xu et
al., Optical evidence of surface state suppression in Bi based topological insulators.
Phys. Rev. B 89, 075138 (2014).
6. Chang Liu*, Su-Yang Xu* et al., Spin correlated electronic state on the
surface of a spin-orbit Mott system (Layered Iridates). Phys. Rev. B 90, 045127
(2014).
7. Su-Yang Xu et al., Fermi-level electronic structure of a topological-insulator/cupratesuperconductor based heterostructure in the superconducting proximity effect regime.
Phys. Rev. B, 90 085128 (2014).
8. M. Neupane*, Su-Yang Xu* et al., Saddle point singularity and topological phase diagram in a tunable topological crystalline insulator (TCI). Preprint at
http://arXiv:1403.1560 (2014).
9. M. Neupane*, Su-Yang Xu* et al., Observation of a topological 3D Dirac
semimetal phase in high-mobility Cd3 As2 . Nature Commun. 5, 4786 (2014).
10. N. Alidoust, G. Bian, Su-Yang Xu et al., Observation of monolayer valence
band spin-orbit effect and induced quantum well states (QWS) in MoX2 . Nature
Commun. 5, 4673 (2014).
11. Su-Yang Xu et al., Observation of a bulk 3D Dirac multiplet, Lifshitz transition, and nestled spin states in Na3 Bi. Preprint at http://arXiv:1312.7624 (2013).
12. M. Z. Hasan, Su-Yang Xu, D. Hsieh, L. A. Wray & Y. Xia, Topological
Surface States: A New Type of 2D Electron Systems (Book chapter). in Topological
Insulators edited by M. Franz and L. Molenkamp (Elsevier, Oxford 2013).
22. Su-Yang Xu et al., Hedgehog spin texture and Berrys phase tuning in a
magnetic topological insulator. Nature Phys. 8, 616-622 (2012).
23. M. Brahlek, N. Bansal, N. Koirala, Su-Yang Xu et al., Topological-Metal
to Band-Insulator Transition in (Bi1x Inx )2 Se3 Thin Films. Phys. Rev. Lett. 109,
186403 (2012).
24. M. Neupane, Su-Yang Xu et al., Topological surface states and Dirac point
tuning in ternary topological insulators. Phys. Rev. B 85, 235406 (2012).
25. D. Zhang, A. Richardella, D. W. Rench, Su-Yang Xu et al., Interplay between ferromagnetism, surface states, and quantum corrections in a magnetically
doped topological insulator. Phys. Rev. B 86, 205127 (2012).
26. Su-Yang Xu et al., Dirac point spectral weight suppression and surface
gaps in nonmagnetic and magnetic topological insulators. Preprint at http://arXiv:1206.0278
(2012).
27. Su-Yang Xu et al., Anomalous spin-momentum locked two-dimensional
states in the vicinity of a topological phase transition. Preprint at http://arXiv:1204.6518
(2012).
28. Helin Cao, Su-Yang Xu et al., Structural and electronic properties of highly
doped topological insulator Bi2 Se3 crystals. physica status solidi 7, 133-135 (2012).
29. M. Neupane, C. Liu, Su-Yang Xu et al., Fermi-surface topology and lowlying electronic structure of the iron-based superconductor Ca10 (Pt3 As8 )(Fe2 As2 )5 .
Phys. Rev. B 85, 094510 (2012).
30. H. Ji, J. M. Allred, N. Ni, J. Tao, M. Neupane, A. Wray, Su-Yang Xu et
al., Bulk intergrowth of a topological insulator with a room-temperature ferromagnet.
Phys. Rev. B 85, 165313 (2012).
31. Su-Yang Xu et al., Topological Phase Transition and Texture Inversion in a
Tunable Topological Insulator. Science 332, 560-564 (2011).
32. L. A. Wray, Su-Yang Xu et al., A topological insulator surface under strong
42. M. D. Schroer, Su-Yang Xu et al.,Development and operation of researchscale IIIV nanowire growth reactors. Rev. Sci. Instrum. 81, 023903 (2010).