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ELECTRON TRANSPORT STUDIES OF THE FERROMAGNETIC
SEMICONDUCTOR CALCIUM HEXABORIDE
STEPHANIE A. GETTY
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
I dedicate this dissertation to my parents for giving me the intellectual freedom to make
my own way.
I would like to express my thanks to those who have played a crucial part in my
development as a physicist. I would especially like to express my sincerest gratitude
toward the chair of my graduate committee, Professor Arthur Hebard, for his generous
support when I needed it most, for the critical reading of this dissertation, and for kindly
allowing me to participate as a member of his group. I would also like to thank the
members of my supervisory committee for having given me indispensable guidance and
support: Professor Andrew Rinzler, Professor Cammy Abernathy, and Professor Selman
I would like to express my appreciation to the department staff, in particular Janet
Germany for her infinite patience, and Darlene Latimer and Susan Rizzo for the lengths
they have gone to in my best interest. Many thanks to the Machine Shop personnel for all
their excellent work that has made my research possible: Mark Link, Bill Malphurs, Ed
Storch, Ted Melton, John Van Leer, Stephen Griffin, and Bob Fowler.
I extend my thanks to all my family and friends, who have given me
encouragement and without whom I would not be the person I am.
TABLE OF CONTENTS
A C K N O W LE D G M E N T S ............................ ............... ...............................................iii
LIST OF FIGU RE S ......... .... .. ...... ...... ......................... ............. ... ........ ..... ... vi
A B STR A C T ................................................................................................................ ix
1 IN TR O D U C TIO N ........................................... .......... ........ ... ... ........... .. 1
1.1 Electronic and Magnetic Properties of the Hexaboride Family of Compounds ....... 2
1.1.1 The D ivalent H exaborides ..................................................................... 3
1.1.2 The Rare Earth H exaborides ........................... ....... ................................ 5
1.1.3 Valence Fluctuating SmB6 and CeB6 ......................................... ............ 6
1.1.4 Ferrom magnetic EuB 6 ........................................................... .................. 8
1.2 D oping Studies of the H exaborides................................... ................................... 11
1.2 .1 C arb on D hoping of E uB 6.................................................................................... 11
1.2.2 Lanthanum and Ytterbium Doping of SmB6 ............................................ 13
1.2.3 Cerium and Thorium Doping of CaB6 ..................................................... 14
2 PREVIOUS WORK IN CaB6 AND RELATED COMPOUNDS ................................ 17
2.1 Electron Tunneling Spectroscopy in EuB6.......................................... ......... ..... 17
2.2 Recent Experimental and Theoretical Results in CaBI and SrB6 .......................... 20
2 .2 .1 T heoretical Studies .............. ............ .. ......... ...... ..... .. ............. ..... 20
2.2.2 Experim ental Studies ......... .................................... ................ ............... 25
3 PURPO SE OF EXPERIM EN T ............................................... ........................... 41
3.1 Technological M otivation.............. ........... .......... ....... .............................. 42
3.2 Electrical Conductivity in Metals and Semiconductors ...................... ..............44
3.2.1 Electrons in Applied Magnetic Field I: Magnetoresistance............................45
3.2.2 Electrons in Applied Magnetic Field II: Hall Effect .................. ........ 48
3.3 Electron Tunneling Spectroscopy.................................................. .... .. .............. 51
3.3.1 Theory of Tunneling ......... ................. ................... .................. .............. 51
3.3.2 Z ero B ias A nom alies ................................................................................. ..... 56
4 EXPERIM ENTAL TECHNIQUES ........................................ ........................... 60
4.1 Crystal Growth and D oping.................... ................................ .......................... 60
4.2 Transport M easurem ent Techniques .................................. ............ ................. 61
4.2.1 Resistivity, Hall Effect, and Magnetoresistance ................... .................62
4.2.2 Tunneling Spectroscopy ........................................................ ............. 65
5 PRESENTATION OF RESULTS........................................................ ............ 72
5.1 Resistivity M easurem ents ...................................................................... 73
5.2 H all E effect M easurem ents .......................................................................... ... ... 79
5.3 Magnetoresistance Measurements.......................... ....................... 84
5.4 T unneling M easurem ents ........................................................................................ 86
6 INTERPRETATION AND MODELING OF THE DATA ........................... ........ 91
6 .1 Interpretation of th e D ata ......................................................................................... 9 1
6.1.1 Cal-~La6B6 .................................... ................... .......... ........ 91
6.1.2 Stoichiom etric C aB 6 .............................. .. ..................................... 102
6 .1 .3 C a l-~ B 6 ...................... .................................. ................. 1 0 6
6 .2 B and Structure M odel...................................................................... .. .......... 111
7 SU M M A R Y ................................................................................... 1 15
7.1 Synopsis of Experim ental R esults................................... ................................... 115
7.2 Future D directions ................................. ...... ........ ............... ...... .. 116
L IST O F R E F E R E N C E S ....................................................................... .................... 118
BIOGRAPHICAL SKETCH..... ....................................... 125
LIST OF FIGURES
1-1. CsCl crystal structure of the hexaborides .................................... ................. 3
1-2. Tunneling conductance versus bias voltage in SmB6. ................................................ 6
1-3. R esistivity versus tem perature in EuB 6 ................................... ...................... .. ........ 8
1-4. Resistivity versus temperature in EuB6 at various magnetic fields. ........................... 9
1-5. Resistivity and dp/dT versus temperature in EuB6 ............................................ 10
2-1. Tunneling conductance versus bias voltage in EuB6. ........................................ 19
2-2. The evolution of a semimetallic band structure with excitonic ordering..................... 21
2-3. The band structure of an excitonic system with electron doping............................. 22
2-4. Magnetization versus temperature in Cao.995Lao.oosB6 showing a Tc of approximately
600 K. .............................................. 26
2-5. Magnetization versus magnetic field at various La doping concentrations ............... 27
2-6. Resistivity versus temperature in the electron doped Cal-5La6B6, Ca-deficient CaB6,
and stoichiometric Cai+6B6 (first report). .................................. .............. 28
2-7. Resistivity versus temperature in Cai+6B6 (first report)............................................... 29
2-8. Specific heat versus temperature in Cai+6B6 and Cao.995Lao.oo5B6 (first report)........... 29
2-9. Spin relaxation rate versus temperature in SrB6 at various magnetic fields.................. 31
2-10. Optical reflectivity versus frequency in Cao.995Lao.oo5B6 Cao.99Lao.o1B6, and CaB6..... 32
2-11. Angle resolved photoemission spectra in stoichiometric CaB6. ................................ 33
2-12. SXE and PFY intensities versus photon energy in various hexaborides................. 34
2-13. Electron spin resonance spectra in Cao.995Lao.oo5B6. ............................................. 35
2-14. Magnetization versus magnetic field in Ca0.995Lao.005B6 and CaB6 grown by FZ and
A l-fl u x tech n iqu es. .............................. ............. ........... ........... ... ........ ........ 3 6
2-15. Resistivity versus temperature in Ca0.995Lao.005B6 and CaB6 grown by FZ and Al-
flux techniques ............... ............. .................... .................. 38
2-16. Magnetization versus magnetic field in polycrystalline CaB6: growth conditions...... 39
2-17. Magnetization versus magnetic field in polycrystalline CaB6: ferromagnetism and
diam agnetism ......................................... ......... 39
2-18. Resistivity versus temperature in polycrystalline CaB6 ............... ..... ................ 40
3-1. Resistivity versus applied magnetic field in EuB6. ............................................ 47
3-2. Magnetoresistance versus applied magnetic field in SmB6. ........................................ 48
3-3. Contact configuration for performing Hall effect measurements .............................. 49
3-4. Schem atic of electron tunneling ........................................................................... .... 52
3-5. Normalized tunneling conductance versus positive bias voltage in a BCS
superconductor .................................................. .............. 54
3-6. Tunneling conductance versus positive bias voltage in a Pb-I-Pb tunnel junction........ 55
3-7. Zero bias anomalies in the tunneling resistance versus bias voltage for a Cr-CrOx-Ag
tunnel junction. ....................................................... .............. 57
3-8. Zero bias anomalies in the tunneling conductance versus bias voltage for
magnetically doped electrodes of (a) Ag and (b) Al. ...................................... 58
4-1. Contact configuration for simultaneous measurement of resistivity,
magnetoresistance, and Hall effect................................................ .............. 62
4-2. Depiction of 4He cryostat with pump-out port used for magnetotransport
measurements. .......................................... 64
4-3. C ross-section of tunnel junction............................................................................. .. 66
4-4. I-V characteristic of a EuB6-I-Pb tunnel junction. ............................................... 67
4-5. Circuit diagram for tunneling measurements ............................................... 70
5-1. Normalized resistivity versus temperature in CalpLa5B6........................................ 74
5-2. Normalized resistivity versus temperature in CaB6. ......................................... 74
5-3. Normalized resistivity versus temperature in CalB6................................ .............. 75
5-4. Fits of resistivity versus temperature to activated form in Cali-B6 ............................. 76
5-5. Resistance versus temperature in Cal-6B6 prior to and following 02 anneal ................ 78
5-6. High temperature region of Figure 5.5......................................... .............. 78
5-7. Carrier concentration and normalized resistivity versus temperature in Cal-6La6B6..... 79
5-8. Carrier concentration and normalized resistivity versus temperature in Cal-6B6. ......... 80
5-9. Carrier concentration and normalized resistivity versus temperature in CaB6.............. 81
5-10. Hysteresis in Hall voltage versus magnetic field in CaB6 at 4.2 K............................. 83
5-11. Hysteresis in magnetization versus magnetic field in CaB6 at 4.2 K........................ 83
5-12. Magnetoresistance versus magnetic field in Cal-5La6B6............................................. 85
5-13. Magnetoresistance versus magnetic field in CaB6............... ................... ........... 85
5-14. M agnetoresistance versus magnetic field in Ca B6. .................................................. 86
5-15. Tunneling conductance versus bias voltage in Cal-6La6B6 ........................................ 87
5-16. Tunneling conductance versus bias voltage in Cal-6La6B6 ........................................ 89
5-17. Tunneling conductance versus bias voltage in Cal-6La6B6 (a) for 15 K < T < 40 K
and (b) for 2 K < T < 20 K ............................................................................ 90
6-1. Normalized conductivity versus T1/2 in Cal-5La6B6 for 5 K < T < 24 K.................... 95
6-2. Normalized resistivity versus InT in CalpaLaaB6 for 5 K < T < 28 K ........................ 97
6-3. AR/R2 versus H1/2 in Cai-La6B6 ..................................... 100
6-4. Magnetoresistance in CaB6 versus (a) H2 for 0 T < H < 2.5 T and (b) H for 2 T < H <
6 T ............. ......... .. ............. .. ........................................................ 1 0 4
6-5. M ability versus tem perature in Cal B6. ..................................................................... 108
6-6. Magnetoresistance in Cal-5B6 versus (a) H2 for 0 T < H < 2.5 T and (b) H for 1.5 T <
H < 6 T............................................ 110
6-7. Band structure model depicting shifts in Fermi level as a function of doping level. .... 112
Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
ELECTRON TRANSPORT STUDIES OF THE FERROMAGNETIC
SEMICONDUCTOR CALCIUM HEXABORIDE
Stephanie A. Getty
Chairman: Professor Arthur F. Hebard
Major Department: Physics
Because the alkaline earth and rare earth hexaborides straddle the metal-insulator
and magnetic-non-magnetic transitions, this class of materials has consistently been a
source of interest. The discovery that CaB6, when lightly electron-doped and without any
inherent magnetic constituent, exhibits long-range ferromagnetism to a Curie temperature
of 600 K further enhances the reputation of the hexaborides for their unusual properties.
Experimental results are presented of electron transport studies of the novel
ferromagnet CaB6 in three doping concentrations: stoichiometric CaB6, electron-doped
Cal_6La6B6, and Ca-deficient Cal-6B6. In particular, dependence of electronic properties
on temperature and applied magnetic field were studied. These investigations were
conducted to advance the understanding of the origin of this unusual ferromagnetism.
Upon measurement of the quantities of resistivity, magnetoresistance, Hall effect,
and electron tunneling spectra, a band structure model consistent with our results has
been formulated. We have discovered that CaB6 single crystals, when grown in excess
Ca to counteract the tendency to form Ca vacancies, exhibit semimetallic behavior with a
Fermi level marginally crossing the conduction band separated in energy from the
valence band. This result contradicts theoretical expectations of a semiconductor or
compensated semimetal. The La-doped counterpart is metallic, as expected. The Ca-
deficient compound, however, retains a low electron concentration while exhibiting
semiconducting transport properties, implying that the Fermi level resides near the
bottom of the conduction band within the semiconducting gap.
Recent theoretical efforts, in addition to predictions of a polarized electron fluid
and the formation of a doped excitonic insulator, have proposed that an impurity-induced
magnetic moment is conceivable. The results of this work are consistent with the
presence of an impurity band and may indicate the validity of a theory of impurity-driven
Owing to the combination of a high Tc, low carrier density, and proximity to
semiconducting behavior, this novel ferromagnet may be applicable to the field of
spintronics, in which the exploitation of the spin degree of freedom aims for integration
of spin-based devices into the semiconductor industry. The control of electronic spin in
semiconducting devices suggests a variety of technologically important applications,
including spin-based transistors, light emitting diodes, and optical sensors.
Metal and rare earth hexaborides have been the focus of extensive experimental
and theoretical studies for over three decades. The source of continuing interest is the
diversity exhibited throughout this class of materials, owing in part to an unusually
sensitive band structure. Small changes in this band configuration tend to result in
profound alterations of the physical properties of these systems. Additionally, the
magnetic properties exhibited by some of the rare earth hexaborides were found to be
very sensitive to electron concentration, prompting studies of the magnetic phase
diagrams of these compounds. The discovery of magnetism in CaB6, in which there are
no magnetic constituents, is a recent example of the interesting physics displayed by the
hexaboride family. Electron-doped, stoichiometric, and Ca-deficient CaB6 comprise the
focus of this work.
This chapter will present a general introduction to the hexaborides, emphasizing
the importance of these materials in the field of correlated electron systems. An
overview of electron transport and the nature of magnetism in these compounds is given
in section 1.1. Doping studies will be discussed in section 1.2, including those that led
Young et al. to investigate La-doped CaB6.
In chapter 2, a review of experimental results obtained by other workers for EuB6,
CaB6, and SrB6, a divalent hexaboride very similar to CaB6, is presented. An
introduction to the experimental quantities probed in these studies is given in chapter 3.
Experimental techniques and equipment will be detailed in chapter 4, including sample
growth and preparation, low temperature methods, and measurement procedures,
followed by a thorough account of results in chapter 5. Chapter 6 will consist of an
interpretation of the work presented in this dissertation, and chapter 7 will summarize.
1.1 Electronic and Magnetic Properties of the Hexaboride Family of Compounds
Although early work on the metal borides dates back to the early 1950s, this class
of compounds first became a focus of intense research in the late 1960s. Many of the
studies have involved the rare earth and alkaline earth hexaborides. These materials exist
in the CsCl crystal structure, in which a cage of B6 octahedra surrounds the metal atom,
as shown in Figure 1-1. Divalent hexaborides were long considered semiconducting, as
will be discussed below, and the presence of trivalent (tetravalent) cations gives rise to
metallicity with an estimated one (two) conduction electron(s) per metal atom. It follows
that these compounds are excellent candidates for the study of the metal-insulator
transition. Because the hexaborides are isostructural in the presence of different cations,
doping studies have been a major component of the experimental efforts concerning these
Subsection 1.1.1 will serve to present generally obeyed properties of the divalent
hexaborides. Subsection 1.1.2 will introduce the electronic and magnetic characteristics
of the rare earth hexaborides, while subsections 1.1.3 and 1.1.4 focus on the intermediate
valence compound SmB6 and the ferromagnet EuB6, respectively.
As the field has evolved, the experimental and theoretical investigations that have
been conducted on these compounds have become the source of much dispute. In
particular, the electronic transport properties of the divalent hexaborides, including EuB6,
are not easily interpreted to be metallic or semiconducting. The origins of long-range
magnetic order in EuB6 and the topic of this work, CaB6, are still subject to much
Figure 1-1. CsCl crystal structure of the hexaborides.
1.1.1 The Divalent Hexaborides
The electronic properties of the divalent hexaborides, represented by CaB6, SrB6,
BaB6, YbB6, and EuB6, to be discussed separately below, were long considered to be well
understood. Longuet-Higgins and Roberts  performed early calculations of the
electronic configuration of the B6 octahedron. The analysis considers that each boron
donates 3 electrons to the system; one is a 2p electron, while the other two are 2s
electrons. For a group of six boron atoms, then, there are 18 electrons that can participate
in bonding. In preparation for using the tight-binding approximation, these workers
enumerated the orbitals available for filling for each octahedron in terms of symmetry
groups. By calculating the energy contained in each bond, bonding orbitals were
differentiated from anti-bonding orbitals. Of the bonding type, there are seven, each of
which can hold two electrons of opposite spin. Combining these 14 orbitals with those
bonding between borons and the neighboring octahedron, of which there are six, the total
electron capacity required for full covalent character is 20. The implication is that the
combination in a unit cell of a divalent metal with the 18 electrons native to the B6 group
gives a fully covalent structure. Measurements of the temperature dependence of
resistivity in single- and poly-crystals of the divalent, non-magnetic hexaborides
produced activated behaviors, enforcing the apparent correctness of the semiconducting
Heat capacity studies of the divalent hexaborides reveal a small electronic
contribution at low temperatures . The magnitude of this signal is interpreted to reflect
a small density of states located at the Fermi level, which in turn reflects a low carrier
concentration, in agreement with the semiconductor-like behavior of the resistivity.
Nuclear magnetic resonance (NMR) measurements of 11B chemical shifts in
CaB6, SrB6, and BaB6 lent further credence to the claim that the alkaline earth
hexaborides are semiconducting . The B11 chemical shifts measured in powdered
samples indicate a diamagnetic response, which the author interprets to be a signature of
Owing to the excellent agreement between theory and experiment, the alkaline
earth hexaborides were somewhat neglected for a number of years. Though similar
results were obtained 18 years earlier by Hasegawa and Yanase , a re-evaluation of
electron transport behavior in these compounds was instigated in 1997 by band structure
calculations by Massidda et al. , predicting semimetallic behavior for EuB6, SrB6, and
CaB6. Due to the near-equality of the inter- and intra-B6 octahedral bond lengths in these
materials, a small, symmetry-induced overlap between the calcium d band and boron p
band at the X point of the Brillouin zone was predicted. Subsequent experimental
attempts to verify semi-metallicity in the alkaline earth hexaborides have produced
conflicting results. Recent results for SrB6 and CaB6 will be shown in chapter 2 and
compared with the results of this work in chapters 5 and 6.
1.1.2 The Rare Earth Hexaborides
The majority of the rare earth hexaborides are metallic conductors, due to the
typically trivalent cation present in the structure. Within the simple interpretation, two of
the rare earth electrons contribute to fill the outer shell of the B6 group, while the third
electron exists in a charge conducting state. Resistivity measurements indicate a clearly
metallic behavior , and measurements of the work function, especially that of LaB6,
NdB6, PrB6, and their alloys, reveal that these hexaborides are useful in applications as
thermionic emitters .
Most of the rare earth hexaborides exhibit some form of long-range order at low
temperatures. The most common of these ordering mechanisms is antiferromagnetism
through the RKKY exchange mechanism, which is strongly influenced by crystal field
effects, as is seen in CeB6, PrB6, NdB6, GdB6, TbB6, DyB6, and HoB6. Superconductivity
is seen in diamagnetic LaB6 below 1.3 K and in YB6 below 7.1 K [9,10].
1.1.3 Valence Fluctuating SmB6 and CeB6
The rare earth compound SmB6 is not easily classified as a divalent or trivalent
hexaboride, as it is a mixed-valence system. In the mid-1970s, the considerable interest
in intermetallic compounds motivated extensive studies of SmB6, in which the ratio of
Sm3+ to Sm2+ was found to be 7:3 and roughly independent of temperature . A
simple analysis dictates that this material should be metallic, since each Sm3+ ion donates
one conduction electron to the system. Resistivity measurements have instead revealed
semiconductor-like behavior initially attributed to a small insulating gap, featuring an
activated rise at high temperatures followed by a low-temperature plateau region.
-4 -2 0 2 4 /
S1.0 Voltage (meV)
0.8 \ j 49 K
',,\ 33 K
0.7 23 K
-40 -20 0 20 40
Figure 1-2. Tunneling conductance versus bias voltage in SmB6. The arrow denotes the
location of the gap edge in energy. The depletion of the density of states near zero is
evidence for a pseudo-gap .
The form of the resistivity for SmB6 is consistent with the development of a small
gap in the density of states at low temperatures suggested by several workers [12-17].
Tunneling measurements of SmB6, shown in Figure 1-2, confirm the appearance of a
pseudo-gap below approximately 40 K , where the density of states is steadily
reduced with a power-law dependence on temperature. Note the redistribution of
electronic states to energies above the gap energy, denoted by the arrow. The origin of
the gap is thought to be hybridization between the closely situated f- and d-bands, as
proposed by Mott in 1974 . Other workers have instead proposed the formation of a
Wigner crystal in which the interaction dominating the kinetic energy may not be
coulombic in nature . Later work has proposed that intra-gap impurity bands, due to
such defects as Sm vacancies, dominate the low-temperature region [20-22].
While the trivalent Sm cation carries a magnetic moment, SmB6 has not been
found to exhibit long-range order. A paramagnetic response of magnetization to the
application of magnetic field appears to persist to temperatures well below 1 K. The
most likely scenario to account for the absence of long-range magnetism is the significant
spatial separation between trivalent cations. In such a configuration and with a carrier
concentration low enough to produce semiconducting behavior, magnetic ordering is
difficult to produce by way of the RKKY interaction.
CeB6 is also classified as a valence fluctuating compound. Magnetic ordering in
CeB6 has been given special attention due to its complicated phase diagram, which
exhibits three distinct phases as the material is cooled . At high temperatures, CeB6
behaves like a typical dense Kondo system with a Kondo temperature of approximately 1
K. At temperatures between 2.4 K and 3.2 K, the material undergoes an
antiferroquadrupolar ordering. With the ground state of these moments being the F8
quartet, the Ce atoms are best described by quadrupole moments. Antiferromagnetic
ordering of these moments commensurate with the lattice is the phase in which CeB6
exists at intermediate temperatures. Below 2.4 K, CeB6 exists in a classical
1.1.4 Ferromagnetic EuB6
Until the discovery of ferromagnetism in CaB6, EuB6 was the sole ferromagnetic
exception to the generally antiferromagnetic ordering shown in the hexaborides. A
review of experimental results for EuB6 may prove helpful in determining the origin of
certain features appearing in CaB6 data.
7.0 I I I I
S5.0 / *H=
S H=15 kOe
.' 2.0 8
0.0 I I I i
0 50 100 150 200 250 300
Figure 1-3. Resistivity versus temperature in EuB6. Closed circles represent zero-field
data, while the open circles correspond to a 15 kOe applied magnetic field .
Examination of resistivity versus temperature in EuB6 reveals a sharp maximum
followed by a dramatic decline below 16 K [24,25], as shown in Figure 1-3. Since Eu
exists in a +2 valence state in this compound, semiconducting behavior was expected.
The large drop in resistivity with decreasing temperature was interpreted to indicate semi-
metallic behavior instead and was attributed to a reduction in magnetic scattering upon
moment alignment. Negative magneto-resistance corroborates this picture [26,27], as
shown in Figure 1-4.
1500 A EuE6
S 0 OkOe
4 2.7 kOe
S13 } 5.A kOe-
500 8.1 kOe
x 10.8 kOe
I IH et 16. kOe
0 10 20 30 40 50 60 70 80 90
Figure 1-4. Resistivity versus temperature in EuB6 at various magnetic fields. At low
temperatures, the magneto-resistance is clearly negative .
Further studies of the magnetic transition in EuB6 demonstrated that there exist
two critical points associated with the onset of ferromagnetic order [28-30], one
occurring at 15.1 K and the other at 12.6 K. Figure 1-5 shows that these two transitions
appear as sharp peaks in the quantity dp/dTas a function of temperature. Subsequent
work has attempted to differentiate between the origins of the two transitions.
Accompanying this work  is a series of Arrott plots of magnetization versus magnetic
field for various temperatures. These curves indicate that EuB6 is ferromagnetic, i.e.
exhibits a positive value of magnetization at zero magnetic field, up to a temperature
between 11 and 13 K. These workers assert that the lower transition represents the onset
of ferromagnetic order.
4'I 1 150
100 /C I-
0 10 20 30 0 10 20 30
(a) T (K) (b) T (K)
Figure 1-5. Resistivity in (a) and dp/dT in (b) versus temperature in EuB6 .
Initially, researchers considered the ferromagnetic order appearing in EuB6 to be
governed by the RKKY interactions that are responsible for the antiferromagnetism seen
in most of the magnetic rare earth compounds. Raman spectroscopy studies, however,
reveal evidence for the presence of magnetic polarons . Peaks in the Raman spectra
for EuB6 appear to occur at characteristic magnon energy scales and are only evident at
temperatures below Tc. Attempts to differentiate the environments corresponding to the
two transitions by way of optical measurements have not yet been conclusive.
A picture that has been proposed to describe the onset of long-range
ferromagnetism is one of magnetic percolation, in which the polarons grow in size or in
number as the temperature is lowered and eventually coalesce into a uniform
ferromagnetic state. Electrons in the polaronic state feel a considerable drag due to their
interaction with the nearby magnetic moments, an effect that may explain the local
minimum of the resistivity just above Tc. As the fully ferromagnetic state evolves, the
moments become aligned, so that the effective masses of the conduction electrons are
drastically reduced. The absence of these polarons in the fully magnetic state serves to
explain the large resistive drop below Tc discussed above.
1.2 Doping Studies of the Hexaborides
The physical properties exhibited by the hexaborides were found to be very
sensitive to electron concentration, prompting a series of doping studies to induce
electronic and magnetic transitions in these compounds. For example, by substituting a
trivalent cation for a divalent cation, the metal-insulator transition becomes accessible.
Furthermore, the dependence of the magnetic interactions on carrier concentration can be
probed by substitutionally doping the magnetic hexaborides with cations of dissimilar
size. Descriptions of C-doped EuB6, La- and Yb-doped SmB6, and the Ce- and Th-doped
CaB6 relatives of Cal_6La6B6 are given below.
1.2.1 Carbon Doping ofEuB6
The ferromagnetism exhibited by EuB6 is unique among rare earth hexaborides.
For this reason, many studies of this compound have focused on determining the
mechanism behind its ferromagnetism and how it differs from that responsible for the
antiferromagnetism typically seen in the rare earth hexaborides.
In initial efforts, carbon doping of EuB6 has been found to suppress its
ferromagnetism [32,33] and is therefore a technique that is used to facilitate the
aforementioned investigation. Carbon is incorporated into EuB6 as a boron substitution
and acts as a single electron donor. The radius of carbon is smaller than that of boron so
that, with increasing carbon concentration, the lattice parameter of the compound
decreases. This doping results in two transitions, one magnetic and one electronic.
A ferromagnet to antiferromagnet transition occurs with increasing carbon
concentration, a progression that may be equivalent to introducing a smaller cation with
increased valency. Results show a change in sign of the paramagnetic Curie temperature,
Op, as the doping level is increased from x=0 to x=0.21 . Further investigations have
yielded information about the intermediate doping regime in which the transition takes
place. Neutron diffraction data suggest the coexistence of the low-doping ferromagnetic
phase and a high-doping helimagnetic phase, a spiral structure that can be formed through
antiferromagnetic interactions .
Measurements of resistivity as a function of doping concentration reveal a
reduction in resistivity with increased carbon content, consistent with the addition of
electrons to the conduction band, which seems to dominate over any decrease in mean
free path accompanying the reduction in lattice constant. The correlation between
enhanced carrier concentration and the suppressed onset of ferromagnetism and eventual
antiferromagnetic order indicates that the higher density of conduction electrons
promotes antiferromagnetic order, as seen in the trivalent rare earth hexaborides. These
observations are supportive of an RKKY-mediated ordering.
The suggested competition between the addition of charge carriers and the
ferromagnetic state is also consistent with the polaronic mechanism for ferromagnetism
advocated by Nyhus et al . High carrier concentrations increase electronic screening
and tend to inhibit magnetic polaron formation, which would similarly suppress the
ferromagnetism characteristic of stoichiometric EuB6.
1.2.2 Lanthanum and Ytterbium Doping of SmB6
The mixed valence state of SmB6 has been a major subject of study since the early
1980s, when valence fluctuating systems garnered a great deal of attention within the
condensed matter physics community. The coexistence of trivalent and divalent cations
in a single material inspired a series of doping studies to investigate the metal-insulator
transition. La and Yb were good candidates for these doping studies due to their similar
ionic size to Sm and their valence states corresponding to the metallic +3 state in LaB6
and the semiconducting +2 state in YbB6.
Kasaya et al.  incorporated La into polycrystalline SmB6 using a float-zone
technique of crystal growth. The donor was added in varying concentrations from
undoped to 50%. Semiconducting behavior is preserved with low doping, but the
resistivity value at which the low-temperature flattening sets in is reduced with increasing
La concentration. Between the doping levels of 10% and 25%, a change in behavior
from semiconducting to metallic is observed.
The Hall coefficient was also measured as a function of doping level and
temperature. In the absence of any dopant, the carrier concentration is low, hole-like at
high temperatures, and depends significantly on changes in temperature. As the electron
concentration is increased, the effect of temperature on carrier density is reduced. At
even higher carrier concentrations, where the transition in resistivity occurs, the Hall
coefficient changes sign to indicate the dominant carriers are, in this regime, electrons.
The data become nearly independent of temperature, and the behavior of the material is
interpreted to be metallic.
The results of Kasaya et al. also include studies of Yb-doped SmB6. These
workers discovered that the float-zone growth technique is inadequate for the
incorporation of Yb. For this reason, an arc melting method was used. The range of
doping spans the entire range between the parent SmB6 and stoichiometric YbB6.
The resistivity versus temperature curves for each doping concentration indicate
the preservation of semiconducting behavior. The carrier concentration, as determined
from the Hall effect, changes sign with temperature for an Yb doping level of up to 50%.
The changes in carrier sign with temperature for a single sample of lightly doped SmB6
seem to indicate that a two-band system may be responsible for the transport properties
observed. The change in charge carriers from hole-like to electron-like behavior suggests
that there are similar numbers of each type of carrier. Under this condition, the dominant
carrier type can be holes for one temperature range and electrons for another.
At higher Yb concentrations, the carriers become increasingly electron-like. This
trend indicates that, in this regime, Sm can be considered an impurity in an YbB6 lattice.
The enhancement of the electron concentration may be attributed to the evolution of a
dominant +3 valence for the Sm species at these high doping levels.
1.2.3 Cerium and Thorium Doping of CaB6
When employing as dopants cations that produce valence-fluctuating hexaborides,
such as Sm and Ce, there is the possibility of a single valence state developing at low
concentrations. Young  conducted an investigation into this question in which CaB6
served as a divalent host matrix doped with first Sm, which indicated the dominance of
Sm3+ at low doping, and then with Ce to further investigate anomalous magnetic
properties demonstrated by the Sm series. Although the non-magnetic state of Ce is
tetravalent, where all electrons are paired and there is consequently no local moment, it is
similar to Sm in that both Ce and Sm have a magnetic state that is trivalent. These
investigators explored the presence of a magnetic moment accompanied by metallic
behavior, which would indicate that the Ce cations exist in a trivalent state at dilute
Resistivity versus temperature as a function of doping level for Ce concentrations
of 0.1%, 0.25%, 0.5%, and 0.75% reveals that metallic behavior appears to correlate with
the addition of low levels of Ce doping levels. In addition, measurements of
magnetization versus magnetic field yield an unexpected hysteretic behavior. This
hysteresis is clear evidence for ferromagnetic order. The assumption that the f-type
moments originating from the Ce are responsible for the ferromagnetism conflicts
significantly with the RKKY interaction thought to mediate antiferromagnetism in the
magnetically dilute regime associated with these observations.
Efforts to simplify the problem and explore the role played by the 4-f Ce moments
prompted Young to fabricate La-doped CaB6 single crystals. The addition of La
preserved the trivalent valence state while excluding the magnetic nature of the Ce. An
exceptional result was found. In the presence of small La concentrations, ferromagnetic
hysteresis in magnetization versus magnetic field was discovered in CaB6 .
The saturation magnetic moment was found to be a maximum value of 0.07 [tB/La
ion at a doping level of 0.5% and was additionally found to persist to 600 K. These data
will be presented in chapter 2. Important evidence in support of the intrinsic nature of
this ferromagnetism was obtained by subsequent Th-doping studies. If the addition of
one electron per dopant ion gives rise to long-range order, what is the effect of doping
with a tetravalent element, thus adding two electrons per dopant ion? The results are
consistent with those seen in Cal-aLaaB6. The maximum saturation magnetization occurs
at a Th level of 0.25%. This value is half the doping concentration but corresponds to the
same electronic content required in the La doping studies.
The discovery of ferromagnetism in Cal-6La6B6 directly inspired the work
presented in this dissertation.
PREVIOUS WORK IN CaB6 AND RELATED COMPOUNDS
The occurrence of ferromagnetism in CaB6 has no true predecessor, that is, a
material composed of non-magnetic constituents that exhibits ferromagnetic order.
Section 2.1 includes a review of electron tunneling results for EuB6, the only other
ferromagnetic hexaboride to date, which may prove helpful in determining the origin of
certain features that appear in CaB6 data.
Section 2.2 will focus on recent data obtained for CaB6 and SrB6, which possess
very similar electronic and crystal structures. In fact, some workers have recently
inferred the existence of ferromagnetism within the SrB6 compound because of its
similarity to CaB6.
2.1 Electron Tunneling Spectroscopy in EuB6
Electron tunneling spectroscopy is a method by which the electronic density of
states of a material can be qualitatively measured. Features appearing in the tunneling
spectrum of a compound can provide information on how the states evolve with changes
in the external environment, examples of which are temperature variations and the
application of a magnetic field. Features important to the understanding of the electronic
structure in the material can be resolved, including gap structures, evidence for the
presence of magnons, and substantiation for the presence of other inelastic excitations. A
more in-depth discussion of tunneling is given in chapter 3.
Specific to EuB6 is the tunneling spectrum shown in Figure 2-1 . The
counter-electrode used in these tunneling studies was Pb, and the I-V characteristic of this
junction clearly features a superconducting gap at temperatures sufficiently below 7.2 K
(not shown). The appearance of this gap structure indicates that tunneling is the
dominant conduction path through the barrier, as will be described more fully in chapter
3. At temperatures above and near the ferromagnetic ordering temperature, a density of
states spectrum qualitatively common to the hexaboride class of compounds is seen. The
slope of the spectrum at higher bias voltage is characteristic of the nature of the barrier
and is not a property of the electrode.
At 43 meV, the density of states appears to be constant with temperature. Below
this bias voltage, there is a depletion in the density of states that becomes more
pronounced with decreasing temperature, while the missing states reappear at higher bias.
This indicates the formation of a pseudo-gap with an associated energy of 43 meV. It is
termed a pseudo-gap because the density of states tends to zero as a power law, as
opposed to an exponential, with temperature. Many hexaborides exhibit a similar
pseudo-gap on an energy scale specific to the material. The origin of the depletion in the
density of states may be a Jahn-Teller-like lattice distortion [18,38].
As the compound orders ferromagnetically, the tunneling conductance increases,
indicating an enhanced metallicity. These changes in the spectra are in excellent
agreement with the significant reduction in resistivity as the temperature is reduced
through the transition temperature of 16 K. In addition, an unusual group of peaks
appears about zero bias. While similar peaks are seen in other tunnel junctions featuring
a ferromagnet as the electrode of interest, their appearance can be a result of any
collective inelastic mechanism present in the electrode. These structures are commonly
referred to as zero bias anomalies. Owing to the appearance of the zero bias peaks being
concurrent with magnetic ordering, it is believed, though not universally accepted, that
these features may be a signature of ferromagnetism. A more detailed discussion of zero
bias anomalies is given in chapter 3, while comparison of this data to the results of this
work is presented in chapter 5.
I i I I I I I I I I I I I I I
-200 -100 0 100 200
Figure 2-1. Tunneling conductance versus bias voltage in EuB6 .
2.2 Recent Experimental and Theoretical Results in CaB6 and SrB_
In this section, a collection of results obtained for SrB6 and CaB6 are provided.
Comparison of CaB6 to SrB6 reveals that the compounds are isovalent and similar in bond
lengths. Following the discovery of ferromagnetism in CaB6 , long-range order was
inferred to exist in SrB6 . As a result, experimental data and theoretical results for
both materials are compiled here.
2.2.1 Theoretical Studies
Since the discovery of novel ferromagnetism in lightly electron-doped CaB6, there
has been a surge of experimental and theoretical work that forms the basis of current
knowledge pertaining to this system. Theoretical efforts have been undertaken by a
number of workers. While there are a few avenues that have been pursued in attempting
to describe the ferromagnetism, special attention has been given to an excitonic insulator
picture. The theoretical foundation of the excitonic insulator model was published nearly
simultaneously in 1965 by two independent efforts: Keldysh and Kopaev  and des
Cloizeaux . The model has been recently revived in applications to CaB6 and the
closely related compound SrB6.
Initial theoretical efforts focused on a prediction made by Bloch in 1929 , in
which a polarized electron fluid forms at electron densities between the upper limit of a
free electron gas and the lower limit of an insulating Wigner crystal. This intermediate
state occurs for a particular range of carrier concentrations, where electron exchange
interactions are dominant over Coulomb interactions, the bounds of which have been
calculated by several workers [43-46] with a large variation in results. There are two
characteristics of the system under scrutiny that appear to be fatal to the success of this
theory in application to CaB6. The first is that the electron densities at which
ferromagnetism appears are rather high with respect to the calculated values. In addition,
the polarized electron fluid is treated for one type of carrier, and the transport properties
of the divalent hexaborides are generally governed by a combination of electrons and
holes. Because of these pathologies, the intermediate density polarized electron fluid was
somewhat neglected in favor of the excitonic insulator [47-52].
An excitonic insulator is theorized to form in compensated semimetals where
Coulomb interactions are significant in the absence of substantial screening. The band
structure corresponding to such a semimetal is illustrated in Figure 2-2 (a). The
symmetry between the electron and hole bands makes possible a pairing of electrons and
holes in the same k-state. These excitons are bosonic in nature and form what is known
as an excitonic condensate. The energy required to form an electron-hole pair is reflected
in the formation of a small energy gap in the band structure, at the middle of which lies
the Fermi level, as shown in Figure 2-2 (b). This band structure defines the excitonic
\t / 0
Figure 2-2. The evolution of a semimetallic band structure with excitonic ordering:
(a) Band structure for a compensated semi-metal.
(b) Band structure upon formation of an excitonic insulator, where the Fermi
level lies at mid-gap .
There are degenerate singlet and triplet states that correspond to a charge density
wave (CDW) and a spin density wave (SDW), respectively. This degeneracy can be
lifted in two ways. In the event that electron-phonon interactions are important, the
CDW state lies lower in energy and implies that charge is the relevant degree of freedom
in the system. Conversely, short-range coulomb interactions can dominate, forming a
spin-modulated state. The latter possibility is thought to be the ground state of the
excitonic insulator in the hexaboride materials, owing to the long mean free paths and
low defect content of these compounds.
/ N\ <^
X(a) I (b)
Figure 2-3. The band structure of an excitonic system with electron doping:
(a) Semi-metallic band structure in the absence of excitonic condensation.
(b) Band structure showing the excitonic gap for one spin species .
The semiconductivity originally observed in CaB6 in the absence of La has been
thought to correspond to the insulating state described above. When carriers are then
added to the system, the excitonic condensate becomes slightly unstable. For low doping
concentrations, the electron-hole pairing can be maintained by reducing the insulating
gap. Additionally, the lowest energy state for the excitonic condensate occurs when all
added carriers are placed into one spin band. The cost in energy of accepting electrons
unpaired with holes into the system is compensated by a reduction in the excitonic gap
for that spin species. The position of the Fermi level is correspondingly raised in the
process of doping, and same-spin electrons are responsible for conduction within the
doped triplet excitonic insulator. This is shown in Figure 2-3 (a), which shows the band
structure for the doped system in the absence of excitonic order, and (b), which shows the
band splitting for one spin species in the presence of excitonic order .
There is only a narrow doping range in which the excitonic state is stable, which
is shown to be in agreement with experimental results by Young et al., presented below.
Specific to CaB6, it is not established that the valence and conduction bands are
sufficiently symmetric to each other to enable excitonic condensation. It is also not clear
whether CaB6 is a fully or partially compensated semimetal or a direct band-gap
semiconductor. The prediction of this dissertation is given in chapter 6.
An experimental signature of excitonic condensation of this type can be seen in
far infrared (FIR) spectroscopy. In the purely insulating regime, there should occur one
minimum in the reflectivity, denoting a gap that is of equal value for the spin-up and
spin-down bands. If asymmetry is introduced into the valence and conduction bands with
respect to each other, or if the system is driven from full compensation, as with doping,
for example, the gap values will become different for the two spin species. In this case,
two minima in the optical conductivity are expected to appear, which represent the
energy gaps for each spin species. These FIR studies have been performed by
experimental workers and are outlined below.
In addition to the excitonic insulator model, other theoretical proposals have been
made. In an argument made by Hirsch , the minima of two sub-bands, possibly
identifiable with opposite spin species, lie at the same energy, but the curvatures are
different. The theory relies on a broadening of one spin band with respect to the other
upon ordering. This loss of kinetic energy, Hirsch has argued, drives the ferromagnetism,
and because of the difference in curvatures of the two spin bands, one becomes a majority
band and the other a minority band at the Fermi level through differences in effective
Jarlborg has advanced a theory that gives a spontaneous paramagnetic splitting of
the conduction band . The Stoner model includes a criterion typically used to predict
the occurrence of magnetic order and compares the relative magnitudes of the electronic
kinetic energy to the potential produced by the static ions and felt by the conduction
electrons. In the limit that the potential energy dominates, the system favors magnetic
order. Correction terms to the Stoner model can arise from potential energy gains upon
ordering. The potential energy supplements and enhances the exchange energy that
exists between electrons. Including this effect can produce a paramagnetic splitting and
subsequent spin polarization.
The most recent band structure calculations  solve Dyson's equation for the
self-energy operator in terms of the Green's function, G, taking into account the
dynamical Coulomb interaction, W. This method is called a GW calculation. The
resultant band structure features a rather large energy gap of roughly 0.8 eV at the Fermi
level, a finding that is contrary to the results ofMassidda et al, as discussed in chapter 1.
This result, however, seems to agree well with angle-resolved photoemission
spectroscopy data to be mentioned in the following subsection. The formation of a band
gap is also consistent with the results of this work, to be presented in chapter 5.
The theoretical results outlined above seem to be variations on a general model.
All predictions can be interpreted to indicate a spin-split conduction band separated from
the valence band by a finite energy gap. The possible appearance of this spin splitting
will be revisited in the interpretation portion of this work.
A recent theoretical result proposed recently by Monnier and Delley 
investigates a possible off-stoichiometry effect in which the single crystals contain boron
vacancies. These workers have performed calculations within the local density
approximation (LDA) of density functional theory (DFT) to produce theoretical values of
the formation energy and magnetic moment associated with plausible types of defect.
The defects studied include various substitutions of La and Al (from the flux growth
technique of Young et al.) for Ca and B6, interchange of Ca and B6, and Ca, B, and B6
vacancies. Their findings imply the presence of a magnetic moment associated with B6
vacancies and Ca substitutions on B6 sites. Ca substitution for B6 is predicted to produce
a moment roughly half the size of that associated with a B6 vacancy. It was also
predicted that the substitution of La or Al for B6 quenches the moment, an observation
that is consistent with a decrease in magnetic moment with La doping at concentrations
above 0.5% , as is described below.
Monnier and Delley suggest that the most likely source of B6 vacancies is the
 set of crystal surfaces, since the cleaving process of single crystal hexaboride
surfaces occurs through severing of inter-octahedral bonds at the surface. This region
appears to be a good approximation to the B6 vacancy density corresponding to the
experimentally determined magnitudes of magnetic moment. The viability of this
argument will be related to the results of this work in chapter 6.
2.2.2 Experimental Studies
The experimental investigations that have been performed to date on the CaB6-
like divalent hexaborides have produced a multitude of unclear results. Contradictory
effects are seen, and even the compositions of samples are often ambiguous, as a result of
disagreeing behaviors between crystals that are labeled by the same stoichiometry. For
these reasons, care must be taken in the interpretations applied to the results outlined
The discovery of ferromagnetism in La-doped CaB6 arose out of analogous
studies by Young  using Ce as a dopant, as described in chapter 1. In an attempt to
simplify the compound and understand the effect of a trivalent, non-magnetic dopant on
the CaB6 system, single crystals of Cal_6La6B6 were grown. Surprisingly, a small
magnetic moment of 0.07 [tB/La ion was discovered .
CaI La B
SCa 0.995 La0.005 6
Figure 2-4. Magnetization versus temperature in Ca0.995Lao.005B6 showing a Tc of
approximately 600 K .
Figure 2-4 shows the preservation of a finite magnetization in this material to a
temperature of at least 600 K, a Tc that is astounding in its own right because of the
extremely small moment. Recent workers have quoted the Tc to occur as high as 900
K.With variations in 6, it was found that there exists a narrow region in doping
I I I I ______
concentration above which the ferromagnetism disappears. This is shown in Figure 2-5,
where the saturation magnetization reaches a maximum at a nominal doping level of
2. / -x= 0.005 -- -
0.5 -x=O11025 __ -
.S x = 0.15
0.0 "f"'--*-- o ..
0 5 10 15 20
H (x10 G)
Figure 2-5. Magnetization versus magnetic field at various La doping concentrations.
The maximum signal is observed for 0.5% La content .
Since CaB6 is expected to be an intrinsic semiconductor or fully compensated
semimetal, an attempt was made to prepare a hole-doped analog of the electron-doped
ferromagnet. To discover ferromagnetism in the hole-doped material would establish
electron-hole symmetry. An attempt to fabricate hole-doped crystals was carried out by
using a self-doping technique. Ca vacancies were purposefully introduced, with the
intention that the vacant Ca site would act as an electron acceptor. It was subsequently
found that a hole-doped analog is not achieved by depleting the Ca content of the crystal,
and interpretations of this result indicate that no ferromagnetism is observed in the Ca-
deficient compound. This assertion is not universally accepted, but Hall effect studies
that corroborate this conclusion are presented in chapter 5.
Transport and optical studies were undertaken to investigate the possible
appearance of evidence for the excitonic insulator picture [56,57]. The single crystals of
these studies were grown under the same conditions as those of Young's work, namely
by Z. Fisk's group, as were the samples studied for the purposes of this dissertation.
According to these workers, the samples called Cai+1B6 are thought to be stoichiometric,
and the crystals labeled CaB6 are thought to be hole-doped. Measurements of resistivity,
shown in Figure 2-6, asserted that stoichiometric CaB6 is semiconducting. The La-doped
and Ca-deficient compounds were proclaimed to be metallic, due to assumptions that the
Ca deficiency corresponds to hole doping. It should be emphasized that the transport
results to be presented in chapter 5 disagree with these conclusions for the stoichiometric
and Ca-deficient compounds, specifically in that the transport properties of the crystals
seem to be interchanged.
10-2 Cal_1LaSB6 _
0 100 200 300
Figure 2-6. Resistivity versus temperature in the electron-doped CalpLa5B6, Ca-deficient
CaB6 (to be denoted Cal-5B6), and stoichiometric Cai+6B6 . Note that these
identifications conflict with the results of our work for the stoichiometric and Ca-
101' a.--'- -~ ,---.. Lal+6-6
_p = 8.8 + 730 TV
0 le-3 2e-3
10-1 100 101 102
Figure 2-7. Resistivity versus temperature in Cal+6B6. The log-log scale emphasizes the
low-temperature decrease in resistivity at roughly 0.2 K. The inset shows a fit to T 3 at
the lowest temperatures .
Figure 2-8. Specific heat versus temperature in Cal+6B6 and Cao.995Lao.oo5B6. Note the
local maximum at roughly 0.2 K .
Low temperature resistivity measurements by Vonlanthen et al. of the
semiconducting material show a slight decrease with decreasing temperature below a few
tenths of Kelvin. This is shown in Figure 2-7, the inset of which emphasizes a T3
dependence of low-temperature resistivity. When compared to specific heat versus
temperature data in the same temperature range, a concurrent local maximum is observed,
as shown in Figure 2-8. Similar behavior of these quantities has been observed in SrB6
Gavilano et al. performed 11B nuclear magnetic resonance studies (NMR) to
measure the spin-lattice relaxation rates in SrB6 and Cal_6La6B6 . The results were
compared to NMR spectra in LaB6. The workers discovered no discernable difference in
the spin echo intensity of all three materials at low temperatures. It is therefore apparent
that the drastically different resistivities, and in turn, the electron densities, have no direct
relation to the rate of spin relaxation. Furthermore, it was noted that the intensities are
too large to be accounted for by itinerant electrons alone.
The relaxation rates for SrB6 at various magnetic fields are plotted versus
temperature in Figure 2-9. The field dependence of T'1 was found to be of the form 1/H
(not explicitly shown). Data for LaB6 at H=0 are shown as a constant-slope solid black
line for comparison and exhibit a linear dependence on temperature, as is expected for
metallic materials. In contrast, SrB6 demonstrates what may be a linear dependence on
temperature below a few Kelvin accompanied by a crossover temperature labeled by To.
Above To, the relaxation rate appears to be independent of temperature. The constancy of
the relaxation rate suggests that phonons are not the mechanism behind the spin
Fits to various relaxation mechanisms, such as localized moments, itinerant
magnetic moments, and paramagnetic impurities, were performed and yielded
unsatisfactory results. A viable possibility involves scattering of conduction electrons
from localized electronic states that only a fraction of the material's electrons occupy.
These circumstances would produce a temperature-independent effect and would give a
magnetic field dependence proportional to 1/H, in agreement with the field dependence
10-1 100 101
Figure 2-9. Spin relaxation rate versus temperature in SrB6 at various magnetic fields.
The solid black line represents data for LaB6 at H = 0 .
The transport and NMR work discussed above indicate a transition below 1 K in
CaB6 and SrB6, the exact stoichiometries of which are ambiguous. The transition is
accompanied by the activated rise in the resistivity data giving way to a region of
decreasing resistivity and enhanced metallicity. In addition, the specific heat in the
alkaline earth hexaborides exhibits a local maximum at roughly the same temperature
indicating a possible increase of electronic contribution. A transition of the electronic
environment to a more metallic state is consistent with these observations. A
discouraging detail is the similarity in low-temperature specific heat between the
stoichiometric and La-doped materials. The dissimilarity in resistive behaviors at low
temperature seems to preclude the association of the specific heat maximum with the
reduction in resistance. It is necessary, then, to assert that the specific nature of the
transition and final configuration is not clear at this time. The possible appearance of a
transition in Cal_-La6B6 will be discussed in later parts of this dissertation.
Work by Vonlanthen et al. presents FIR spectra as a function of La concentration
. Results of optical reflectivity versus wavevector are shown in Figure 2-10 and have
been related to the excitonic insulator model, since a minimum in the reflectivity
spectrum indicates the presence of a gap. In semiconducting CaB6, there appear two
narrow minima close to each other in energy at frequencies 240 and 275 cm-1. These
features are shown in higher resolution in the inset and may imply the presence of gaps
for each spin species. Excitonic ordering in a material with a small degree of incomplete
nesting of the Fermi surface can produce a similar effect resulting from asymmetry-
induced band splitting. The possibility of such asymmetries in the Fermi surface cannot
be excluded for this material.
r so -
1 40 00 200 300 400
0 .. *1 2....
10 10 10 10 10
Frequency (cm1 )
Figure 2-10. Optical reflectivity versus frequency in Cao.995Lao.005B6 (dash),
Cao.99Lao.o0B6 (dot/dash), and CaB6 (solid) .
Upon examination of the reflectivity in 0.5% La doped CaB6, we find two clear
minima in the spectrum at higher energies of 700 and 1200 cm-1. With further La doping
to a level of 1%, the features broaden considerably but appear to preserve the energy
scale set by the 0.5% La-doped material. As the doped excitonic insulator model requires
different gap values for the different spin flavors, these minima may be evidence for a
physical manifestation of the model. It is troubling, however, that these features are very
far from the energy scale of the undoped material. This large shift in energy is not
predicted to accompany slight doping of an excitonic insulator.
The results of band structure calculations by Massidda et al. that predict an
overlap between the conduction and valence bands and form the foundation for the
excitonic insulator seem to be contrary to the findings of several workers, the results of
which indicate a gapped band structure. Among these is angle resolved photoemission
spectroscopy data  that provides evidence for a band gap of the order of 1 eV. The
ARPES technique is a direct probe of the band structure, which is shown for CaB6 in
Figure 2-11. The band structure in solid black represents the calculations performed by
Tromp et al. that are in good agreement with the experimental findings. It is worthwhile
to note that the valence band image differs significantly from the doubly peaked band that
is predicted for an excitonic insulator, and the band gap is substantially larger than an
excitonic instability is expected to yield.
F X r
0.0 0.5 1.0 1.5
Figure 2-11. Angle resolved photoemission spectra in stoichiometric CaB6. The
theoretical GW-calculated band structure is shown in the dotted lines .
The recent ARPES work is accompanied by techniques more sensitive to bulk
properties, soft x-ray emission (SXE) data and partial fluorescence yield (PFY), shown in
Figure 2-12. These data show the positions of the valence band maximum (VBM) and
Fermi level for selected hexaborides. It is clear from these data that, in CaB6 and SrB6,
the VBMs and Fermi levels occur at distinctly different energies, and the Fermi levels
intersect a marginally populated region of the band structure. The conclusions are that
there appears to be electron density at the Fermi level, and the divalent hexaborides of
CaB6-type may be semimetallic.
S\ SXE_ -PFY
........ .... mB
I I S^.B
186 188 190
Photon Energy (eV)
Figure 2-12. SXE and PFY intensities versus photon energy in various hexaborides.
Positions in energy of the Fermi level and valence band maximum are shown for each
From de Haas-van Alphen measurements of the Fermi surface in SrB6, CaB6, and
Cal_6La6B6, Donovan Hall et al.  report the appearance of two pockets in the similar
Fermi surfaces of SrB6 and CaB6. There is a higher frequency resonance attributed to an
electron pocket, while these workers have identified a dominant lower frequency
resonance as a hole pocket with an effective mass five times larger than that of the
electron pocket. As electrons are added to the system, to a La doping level of 6 = 0.0025,
the low-frequency signal apparently disappears. Further addition to electrons, to a La
concentration of 6 = 0.005, reveals the appearance of an additional high-frequency
resonance, with an effective mass slightly differing from the aforementioned electron
pocket. While the association of the lower resonance with hole-like carriers appears
straightforward, problems arise when these measurements are compared with those of
Denlinger et al., in which the curvature of the bands can be resolved, and no hole
component is observed to be present at the Fermi level of SrB6. The identification of the
low-frequency signal will remain tentative for the purposes of this dissertation.
Electron spin resonance studies undertaken by Kunii provide supportive evidence
for anisotropy in the electronic Fermi surface . By rotating a disk-like crystal of
0.5% La-doped CaB6 with respect to the applied RF and static magnetic fields, the
resonance field shifts. In addition, the sharpness of the peak varies with sample
orientation. This data is shown in Figure 2-13, where the angle is between the plane of
the disk and the direction of the static, or external, magnetic field. It is important to
acknowledge that the shape of the sample may produce inherent asymmetries, due to
considerations such as demagnetizing factors.
0 67" 82 840 86
123 1 2 3 3 4 5 678 789
Magnetic Field (kOe)
Figure 2-13. Electron Spin Resonance spectra in Ca0.995Lao.005B6. The angle is defined to
be that between the plane of the disk and the external static magnetic field .
-4 1: Al-flux La 0.5% #7
2: Al-flux La 0.5% #1
-8 3: FZ La 0.5%
0 T "FZ CaB,
-10 -5 0 5 10
Magnetic Field (kOe)
Figure 2-14. Magnetization versus magnetic field in Cao.995Lao.oo5B6 and CaB6 grown by
FZ and Al-flux techniques .
Other workers have recently grown single crystals of electron-doped and
stoichiometric CaB6 by two methods: out of an Al flux, the method used by Young et al.,
and a floating-zone (FZ) method . Comparisons of crystals grown by the different
methods are somewhat conflicting. A ferromagnetic signal was detected in one of the
La-doped crystals grown by the Al-flux method, as shown in Figure 2-14 (curve 1).
Another of the flux-grown La-doped crystals (curve 2) exhibited no hysteresis but finite
magnetization, as did a La-doped crystal grown by FZ (curve 3). Magnetization versus
field is also given in the lower plot for stoichiometric CaB6 grown by FZ as a reference.
Speculating on the origin of these apparently conflicting results, Terashima et al.
have suggested the presence of an inhomogeneous ferromagnetic phase, containing
magnetic domains separated by paramagnetic regions. These workers point out the
possibility that there is a lower critical limit on ferromagnetic domain size required for a
material to exhibit hysteresis. For sufficiently small domains, then, the response of the
material to an applied magnetic field may be superparamagnetic in nature, a model in
which the magnetization exhibits no hysteresis. These interpretations are consistent with
the existing data.
The recent theoretical predictions given by Monnier and Delley , discussed
above, combined with the magnetic domain structure suggested by Terashima et al. may
serve to explain the variation in moment size as a function of growth technique and even
among separate attempts of the same technique. The magnetic domains may represent
clustering of B6 vacancies or substitutions so that domain size could account for the
reported discrepancies in moment magnitude. This model is discussed relative to our
work in chapter 6.
Terashima et al. also performed resistivity measurements on these samples, giving
results shown in Figure 2-15 that appear to be uncorrelated with the crystal composition.
The crystals grown by FZ are characterized by a high resistivity. Interestingly, the La-
doped resistivity extrapolates to a higher value than that of CaB6 at zero temperature.
The Al-flux grown crystals instead show a low and metallic resistivity with an anomalous
drop off at low temperatures. This feature was attributed to the superconductivity of Al
inclusions, a conclusion supported by the magnetic field induced suppression of the
In response to the contradictory results for the same nominal doping
concentrations, Morikawa et al. undertook a systematic study of CaB6 in an attempt to
isolate the effect Ca vacancies have on the electronic properties of the material . The
crystals were prepared by reacting CaO with B at various temperatures and at various
growth rates and resulted in polycrystalline samples. By manipulating the growth
temperature and rate, the workers asserted the ability to control the Ca content of the
crystals. The assumption was that a lower growth rate enabled the escape of Ca from the
crystal. The results of the study indicated that there was no correlation between the
inferred crystal stoichiometry and the resistivity of the sample.
Al-flux La 0.5% #7 /
2.0 FZ La 0.5%
t 1./ i"/ --FZ CaEB
1 .6 ----- (a) -
S 030 I I I
a 0.5 -026 -
0.4 o0 1i 2.0
Al-flux La 0.5% #1
0 50 100 150 200 250 300
Figure 2-15. Resistivity versus temperature for Ca0.995Lao.005B6 and CaB6
(a) grown by FZ technique and
(b) grown by Al-flux technique .
Magnetization versus magnetic field data is shown in Figure 2-16, where samples
(1) through (4), which were grown at either 1200 C for 12 hours or at 1500 C for one
hour, are diamagnetic, and (5) through (8), which were grown at 1500 C for longer
times, exhibit ferromagnetism. In Figure 2-17, the magnetization for a ferromagnetic
sample (9) and a diamagnetic sample (1) is shown. Comparison with the resistivity
versus temperature for diamagnetic samples (2) through (4) and ferromagnetic sample (9)
in Figure 2-18 indicates no correspondence between ferromagnetism and metallic or
semiconducting behavior. Morikawa et al. therefore assert that ferromagnetism in this
I I I I
2 (1) (8)
----(4) /o "
I I ,, I
0 1000 2000 3000 4000 5000
Figure 2-16. Magnetization versus magnetic field for polycrystalline CaB6: growth
conditions. Diamagnetic samples (1)-(4) were grown at a high rate or low temperature
compared to the ferromagnetic samples (5)-(8), grown at a low rate and high temperature
Figure 2-17. Magnetization versus magnetic field in polycrystalline CaB6:
ferromagnetism and diamagnetism. (1) was synthesized at a 1200 C for 12 hours and (9)
at 1500 C for 6 hours. The inset shows ferromagnetic hysteresis in sample (9) .
'-- 2 4 6 8 10
1) ^H (kOe)
I I11 11 11 1
system is independent of carrier concentration and is instead related to a reduction of
symmetry in the crystal.
10-1- (2) _
I I ,
0 100 200 300
Figure 2-18. Resistivity versus temperature in polycrystalline CaB6. Samples (2)-(4) are
diamagnetic and sample (9) is ferromagnetic .
Another possibility can be derived from the results of Terashima et al. If there are
variations in magnetic domain size, then a lower growth rate might be expected to
produce larger grains and perhaps larger magnetic domains. This may justify the
appearance of ferromagnetism in only samples (5) through (9). More difficult is relating
this effect to the electrical resistivity, but the variations in Ca content suggested by these
workers is insufficient to account for the wide variations in transport data accompanying
this work. For example, it is difficult to see how samples (2), (3) and (4) exhibit such
different behaviors, and in particular, why (3) is more resistive than sample (9), if (2)
through (4) are nominally stoichiometric. It is apparent that fabricating crystals with
stoichiometric precision currently limits coherent progress in the field.
PURPOSE OF EXPERIMENT
To investigate the nature of the ferromagnetism in CaB6, a series of electron
transport studies were performed on electron-doped, Ca-deficient, and on-stoichiometry
CaB6. Electron transport measurements are expected to give information about the novel
magnetism observed in these compounds for two reasons. The first is that, in the event
that there are no local moments native to this material, it is natural to expect the
ferromagnetism to be entirely itinerant. In addition, the magnetic properties of the
hexaborides are very sensitive to the electronic environment and content. Manipulation
of parameters such as doping level and external electric and magnetic fields and the
response of the material to these variations should give insight into the mechanism
responsible for ferromagnetism. The questions this work has attempted to answer include
(1) Is CaB6 semimetallic or semiconducting in accordance with the latest band
(2) How does the electron transport change in magnetic field and with doping?
(3) How does the carrier concentration change as a function of temperature and
(4) Can ferromagnetism be detected through tunneling techniques?
A number of experimental techniques have been used in the investigation of the
CaB6 system. The combined information that has been obtained through resistivity,
magnetoresistance, Hall effect, and electron tunneling measurements has suggested a
self-consistent picture of the electronic environment within these compounds, as will be
presented in chapters 5 and 6. This chapter contains a description of the technological
motivation for our studies, followed by brief theoretical descriptions of electrical
conductivity and electron tunneling microscopy.
3.1 Technological Motivation
The quest to integrate the spin degree of freedom into the semiconductor-based
electronics industry is the driving force of the emerging field of spintronics. Through the
use of spin-polarized carriers, both the electronic and magnetic responses of
semiconductor devices can be exploited.
The materials that are applicable to the field of spintronics must satisfy a number
of criteria. The usefulness of a candidate material depends on the degree of electron spin
imbalance, the operating temperature relative to Tc, and the ability to effectively transfer
spin-polarized current into the materials used in the existing semiconductor-based
industry. Future progression of the field of spintronics relies exclusively on the ability to
develop a compound satisfying the above requirements.
Spin-polarization of electrons is associated with ferromagnetic materials. The
known ferromagnetic metals were employed as the first attempt to inject spin-polarized
current into semiconductors. While these ferromagnetic metals have high ordering
temperatures and do produce spin-polarized current, they lack the ability to effectively
transfer this current to a neighboring semiconductor. The band structures of the two
materials differ to such an extent that the wave vector mismatch across the boundary
significantly hinders the transmission of current. Efforts now focus on another approach:
to develop a ferromagnetic semiconductor.
The applicability of a ferromagnetic semiconductor to the field of spintronics
depends on a number of properties. The candidate must display a low carrier
concentration, a low spin-flip scattering rate, a way to externally control the degree of
spin-polarization, by electric field gating, for example, and ferromagnetism at operating
temperatures above 300 K.
Many magnetic semiconductors are now known. Mn doping of III-V
semiconductors, such as InMnAs , has been the predominant method for inducing
ferromagnetism in these materials. The relevant challenge is that of ordering
temperature. Applicability necessitates device operation at room temperature, a Tc that
has not been historically attainable.
A new candidate system has been developed recently. Recent work by
Theodoropoulou et al. indicates that Mn-doped GaN at a nominal doping level of 3 to 5
atomic percent is ferromagnetic with a Tc of approximately 250 K . Theoretical
predictions suggest that improved film quality at a Mn concentration of 5 at. % may
produce ferromagnetism that persists to room temperature. The ferromagnetic ordering
temperature is predicted to be proportional to the band gap of the host semiconductor,
and the large gap value for GaN of roughly 3.5 eV is consistent with the prediction of a
high Tc with the addition of Mn moments.
The discovery of ferromagnetism in the CaB6 system has spawned interest in the
compound for possible application to spintronics, in light of its high ordering
temperature, long mean free path, and the sensitivity of its ferromagnetism to carrier
density. With a low enough carrier concentration, CaB6 thin films may ultimately be
Electric field gating of magnetic semiconductor thin films is highly desirable, as it
provides a way to externally control the magnetism. The gated material essentially forms
one of the electrodes of a capacitor. The opposite electrode is metallic. By controlling
the voltage across the structure, charge carriers can be drawn into the insulating layer,
thus depleting the semiconducting electrode of conduction electrons, a procedure
requiring a low carrier density and minimal screening. Since the extent of magnetic order
in CaB6 is highly dependent on carrier concentration, field gating would enable a high-
resolution study of the ferromagnetic-non-magnetic transition in CaB6.
3.2 Electrical Conductivity in Metals and Semiconductors
One of the simplest ways to probe the electronic properties of a solid is by
measuring the motion of electrons under the influence of an applied electric field. The
conductivity of a rudimentary metal is given by the Drude formula in Equation 3-1,
where o is the conductivity, n is the electron density, e is the electron charge, m is the
electron mass, and c is the scattering time, a quantity that takes into account finite
temperature and scattering processes.
This expression can be modified to account for realistic band structure effects by
replacing m with m*, the effective mass, and remains approximately correct in the
presence of electron-electron correlations.
The inverse of the conductivity is the resistivity, and is commonly measured as a
function of temperature for material characterization purposes. Metallic systems exhibit
a resistivity that is reduced with decreasing temperature. At high T, the behavior is
typically linear, with a correction term that approaches T5 at lower T, containing
information about electron-phonon scattering, which contributes a T3-dependence, and
small-angle electron-electron scattering, which contributes a factor of T2. At the lowest
temperatures, there is insufficient thermal energy to excite phonon modes, and ultimately,
the dominant scattering mechanism is that of electron-impurity scattering. In a perfect
crystal at zero temperature, the resistivity vanishes.
In contrast, perfect semiconductors exhibit infinite resistivity at zero temperature.
At finite temperature, these materials rely on thermal energy to promote valence band
electrons across an energy gap into the conduction band. The resistivity in the presence
of thermal excitation follows an exponential form as a function of temperature, as in
p(T)= pO e A/
In the following subsections, the effect of an applied magnetic field on the
electron transport in metals and semiconductors will be presented.
3.2.1. Electrons in Applied Magnetic Field I: Magnetoresistance
The magnetoresistance of a material refers to the effect of an applied magnetic
field on its electronic transport properties. There are two main configurations commonly
used to measure the magnetoresistance: longitudinal, and transverse. In the longitudinal
configuration, the current is injected, the magnetic field is applied, and the voltage is
recorded along the same crystal direction. In the transverse orientation, the field is
applied in a direction perpendicular to that of the parallel current injection and voltage
A simple metal in which there is one type of carrier and has a perfectly spherical
Fermi surface exhibits no change in resistance with applied magnetic field. In this simple
metal, an electric field is set up by the charge carriers that is transverse to both the current
direction and the magnetic field and perfectly cancels the Lorentz force due to the applied
magnetic field. This transverse electric field makes Hall measurements possible, as will
be discussed below.
In the presence of anisotropy in the Fermi surface or when more than one type of
carrier is responsible for the charge transport, the resistivity of a typical metal will
become enhanced when placed in a magnetic field. This phenomenon is known as
magnetoresistance, and to first order follows a positive H2 dependence on magnetic field.
This dependence can be easily understood from symmetry arguments in the sense that the
magnetoresistance should be symmetric with respect to the sign of the magnetic field. To
complicate matters, when dealing with correlated electron systems, there can be
significant contributions from other sources.
In many ferromagnets, it is common to observe a reduction in sample resistance
with the application of a magnetic field. This occurs due to the alignment of moments
along the direction of the field. The state of lower disorder leads to reduced spin-
dependent scattering and increases the electronic mean free path, thus reducing
resistivity. At the saturation field, the moments are completely aligned, so that no further
reduction of the resistivity is attained by the application of additional field. At fields
sufficiently above the saturation field, the negative effect becomes overpowered by the
standard positive H2 behavior, and the magnetoresistance turns over and approaches
positive values. A relevant example of negative magnetoresistance is exhibited in EuB6
, as shown in Figure 3-1. The negative signal features a saturating effect at the
highest fields, implying an eventual turnover. The positive component at low field may
be due to magnetic hysteresis.
350 T = 4.2 K
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Figure 3-1. Resistivity versus applied magnetic field in EuB6 .
Another mechanism by which a negative magnetoresistance can be attained is
observed in semiconducting systems. The resistivity of the semiconductor can be
reduced due to the application of a magnetic field and the subsequent paramagnetic
splitting of the conduction band. The resultant band structure features one spin band
closer to crossing the valence band. Since the conduction of this band is exponentially
dependent on its proximity to the valence band, it will dominate the transport and give
rise to a lower resistivity resulting from the reduced gap. This effect is clearly
represented by the high-field magnetoresistance of semiconducting SmB6 , shown in
-0.4 T=4 K
-0.54 \ I
0 10 20 30 40 50
Figure 3-2. Magnetoresistance versus applied magnetic field in SmB6 .
3.2.2. Electrons in Applied Magnetic Field II: Hall Effect
The Hall effect is a widely used method for measuring the carrier concentration in
a material. While the magnetoresistance, as discussed above, is the change in resistivity
along the direction parallel to the current, or longitudinally, in the presence of a magnetic
field, the Hall effect is the change in resistivity along the direction perpendicular to both
the current direction and the magnetic field. In Cartesian coordinates, if the current flows
in the y-direction, the Hall voltage is measured along the x-direction, and the magnetic
field is applied in the z-direction, as shown in Figure 3-3.
Figure 3-3. Contact configuration for performing Hall effect measurements.
The Hall effect is a manifestation of the manner in which the magnetic field exerts
forces on different charge carriers. The electrons are pushed to one side of the crystal,
and the holes are pushed to the other. The transverse voltage can be interpreted to give
the carrier concentration by Equations (3-3) and (3-4), applicable to a system with a
majority carrier type.
VH =RH IH/d (3-3)
RH = (ne)-, (3-4)
where VH is the Hall voltage, RH is the Hall coefficient, Iis the longitudinal current, His
the applied magnetic field, d is the thickness of the crystal, n is the carrier concentration,
and e is the charge of the particle. The sign of the Hall coefficient conveys the nature of
the charge carriers. A positive value corresponds to holes, and a negative value indicates
Corrections to this simple analysis are required for a compensated system, in
which both electrons and holes participate in conduction. Complications arise because
the Hall coefficient is dependent not only on the carrier concentrations for each type of
carrier, n andp, but also on the corresponding mobilities, [in and [p, as shown in Equation
(3-5). As a result, the Hall coefficient reveals the sign of the dominant carrier type, but
quantitative results are difficult to extract.
e e(p kp + n pn)2
The presence of interacting magnetic moments in a material can further
complicate the Hall effect. In addition to the externally applied magnetic field, the
magnetism of the material itself influences the trajectories of the charge carriers. Under
these conditions, the anomalous Hall effect appears. Instead of a linear dependence of
Hall voltage on magnetic field, a hysteretic component can contribute to the signal.
In a ferromagnet that displays hysteresis in magnetization versus field, the Hall
voltage will also be hysteretic at fields less than the saturation field. The origin of this
behavior is easily explained. When an external magnetic field is applied, the magnetic
moments become increasingly aligned with increasing field. The fraction of aligned
moments determines the magnitude of the internal field experienced by the charge
carriers. Since the Lorentz force is proportional to magnetic field, the internally induced
component of the Hall voltage should follow the response of the magnetization to applied
field. The observed Hall resistivity, the ratio of Hall voltage to longitudinal current, takes
the form of Equation (3-6):
PH = RB +Rs 4nM, (3-6)
where Ro is the conventional Hall coefficient, B is the applied magnetic field, Rs is the
anomalous Hall coefficient, and Mis the sample magnetization, which is field-dependent
until saturation of the moments.
3.3 Electron Tunneling Spectroscopy
The density of states of a material contains valuable information that can advance
the understanding of the physical properties of that material. One method by which the
density of states can be probed is electron tunneling spectroscopy, in which the quantum
mechanical transmission of electrons across a thin insulating barrier can be monitored
and used to interpret the distribution of electronic states within a solid. The technical
aspects of tunneling will be presented in chapter 4. Subsection 3.3.1 will serve to
introduce the basic theory of tunneling, while subsection 3.3.2 will discuss features
known as zero bias anomalies that can appear in tunneling spectra.
3.3.1 Theory of Tunneling
A tunnel junction consists of a sandwich structure, where a thin insulating
material separates two electrodes. Many variations of tunneling spectroscopy exist, in
which the electrodes can have very different electronic environments. Commonly, the
electrodes are normal metals, superconductors, or magnetic materials, and the type of one
electrode can differ from that of the opposite electrode. The appearance of the spectra
may differ with type of electrode, but what it represents to first order is characteristic of
the material, in the sense that the choice of barrier does not influence the form of the
normalized tunneling spectra but may superimpose a linear or quadratic background onto
the conductance signal.
The quantity measured in a tunneling experiment is the conductance across the
tunnel barrier, dI/dV. By applying a DC bias voltage across the junction, the chemical
potentials of the electrodes can be shifted with respect to each other, as depicted in Figure
3-4 . The tunneling conductance represents the product of the densities of states of
the two electrodes, and the bias voltage indicates the energy level with respect to the
Fermi energy that is being investigated.
Ev I E 2= 0
0 1 x
Figure 3-4. Schematic of electron tunneling. The electronic wavefunction tunnels from
electrode 1 to electrode 2 through an insulating barrier of height U. The bias voltage, V,
is applied to shift the densities of states with respect to one another .
One arrives at the conclusion that the tunneling process reveals information about
the density of states through a calculation of transition probability per unit time .
This quantity is approximately obtained by treating the tunneling Hamiltonian as a
perturbation with respect to the Hamiltonians, H1 and H2, of each electrode. There is
assumed to be no electron-electron interaction across the barrier. The conserved
quantities in tunneling spectroscopy are taken to be the transverse momentum and total
energy. Based in these approximations, Fermi's golden rule can be used to obtain the
transition probability per unit time between electrodes 1 and 2. The transition probably
differs from the tunneling current by a prefactor, denoted as A in the following
112 =A | TI2N1E )(E)N(E (E+eV)[1-f(E+eV)] dE
1 = 1-2 2-1
=A ITI 2 N(E) N (E+eV)[f(E)-f(E+eV)]dE
The expression, as shown in Equation 3-7 , is intuitive. Ni and N2 are the
densities of electronic states in electrodes 1 and 2, respectively. An electron with energy
E is annihilated in electrode 1, leaving a vacant state. An electron with energy E+eVis
created in electrode 2, filling an empty state and conserving transverse momentum. The
product of these densities of states is multiplied by the tunneling probability 17]2 and the
corresponding Fermi distribution functions, so that the expression is valid at finite
temperature. At zero temperature, dI/dVis simply proportional to the product of the
densities of states. At finite temperature, the tunneling conductance is, to first order,
proportional to the product of the densities of states of the two electrodes, and correction
terms only become important when the thermal energy becomes comparable to the Fermi
energy, which is typically tens of thousands of Kelvin. The form of this product, and in
turn the appearance of the tunneling spectrum, depends on how the densities of states of
the electrodes vary with bias voltage.
3 0 T=O
1 dI ns
0 1 2 3
Figure 3-5. Normalized tunneling conductance versus positive bias voltage in a BCS
A normal metal has a density of states that is roughly constant in energy at
moderate bias voltages. A metal is commonly used as the counter-electrode to study a
material that is not well characterized because the tunneling spectrum of such a structure
is proportional to the density of states of interest. The density of states for a
superconductor, however, reveals the gap structure about zero bias and, for a BCS
superconductor at zero temperature, follows the form given in Equation (3-8) , where
Ns is the superconducting density of states and Nn is the normal density of states. An
illustration is given in Figure 3-5 at zero temperature and at finite temperature, where
there is thermal smearing of the gap edge.
0 El (< A
Under certain circumstances, inelastic excitations can couple to the quasiparticles
in the electrode and appear as broad features at characteristic energies in the tunneling
conductance versus bias voltage . An example of this phenomenon can be found in
so-called strong-coupling superconductors like Pb and Hg. In these materials, electron-
phonon interactions induce a spreading of the single-particle states so that they are no
longer eigenstates of the BCS Hamiltonian. The signatures of these states appear as
deviations centered about 7 meV and 11 meV in the tunneling spectrum as shown in
Figure 3-6 for Pb.
0 4. 8.0 12.0
Figure 3-6. Tunneling conductance versus bias voltage in a Pb-I-Pb junction. The
coupling of phonons to the quasiparticle spectrum is seen as maxima in the broken data.
The solid curve represents BCS theory .
In a manner similar to the phonon structure discussed above, evidence for other
types of inelastic excitation can be seen in tunneling. For example, a ferromagnetic metal
may reveal magnons or magnetic polarons in the form of smoothly varying bumps or
wiggles . The identity of the feature depends critically on the energy scale at which
the features appear.
3.3.2 Zero Bias Anomalies
Sharp features centered about zero voltage in the tunneling conductance known as
zero bias anomalies (ZBAs) have been associated with inelastic mechanisms present in
the electrode . The concept of a ZBA was introduced in chapter 2 during the
discussion of tunneling results in EuB6, and it was noted that the appearance of the zero
bias peak is simultaneous in temperature with ferromagnetic ordering. It is important to
mention that there is no consensus concerning the origins of these features, and the term
anomaly certainly suggests incomplete understanding.
One type of ZBA is known as the giant resistance peak and is the least understood
of all types of ZBA. This type of feature has appeared in work on Cr-CrOx-Ag tunnel
junctions , as shown in tunneling resistance (dV/dl) versus bias voltage (Figure 3-7).
Initial observations noted that there are most likely magnetic moments present in the
barrier, as CrO2 is ferromagnetic and CrO3 is antiferromagnetic. Mezei and Zawadowski
presented a Kondo-like effect as a possible mechanism leading to the increase in
resistance . This mechanism explained a logarithmic dependence of the resistance on
temperature but was inadequate to explain the magnitude of the effect, which can be two
orders of magnitude larger than the resistance at 100 meV. A guideline provided by this
model is that conductance peaks are produced by moments in the barrier and dips are a
result of moments in the electrode. Artificial implantation of magnetic Ni into Al
electrodes gave a giant resistance peak  of the correct magnitude, but no conclusions
have been reached as to the actual mechanism responsible for the effect.
-6 -4 -2 0 2 4 6
Figure 3-7 Zero bias anomalies in the tunneling resistance versus bias voltage for a Cr-
CrOx-Ag tunnel junction  at
(a) T = 0.9 K
(b) T = 20.4 K
(c) T = 77 K
(d) T = 290 K
In metals, conductance peaks and dips can appear for various reasons. In an
experiment undertaken by Cooper and Wyatt (1973) , magnetic and non-magnetic
dopants were introduced into host electrodes chosen to be Al and Ag separated by a thin
layer of A1203. When the dopants were confined to the Ag electrode, conductance peaks
were observed only for Ti and Ni, as shown in Figure 3-8(a). When Al was chosen to be
the host electrode, a conductance peak was seen for all dopants except Mn, as shown in
Figure 3-8(b). These conflicting results indicate that the host electrode into which the
dopants are introduced is highly influential on whether or not zero bias peaks are seen.
Interpretation of the results presented above within the Mezei and Zawadowski
model suggests that impurities in Ag are more likely to produce a magnetic moment
within the metal, while in Al, it is suggested that the moments are more likely to be
situated in the barrier. This scenario is somewhat awkward in its viability. An alternate
picture, given by Wyatt (1974) , relies on an estimate of the magnetic coupling
strength as a product of the s-d exchange energy and density of states of the electrode at
the Fermi level.
4 (a) Ti-
C448 .44.1 1
5- 11 160 C
-- 38 _8 ___ 75 Undoped
-60 -40 -20 0 20 40 60 -60 -40 -20 0 20 40 60
Voltage (mV) Voltage (mV)
Figure 3-8. Zero bias anomalies in the tunneling conductance versus bias voltage for
magnetically doped electrodes of (a) Ag and (b) Al. The data are expressed in the same
units of conductance but shifted with respect to each other for presentation purposes. The
zero bias conductance is given as the number corresponding to each curve .
Table 3-1 lists the dopants used, the number of 3d electrons each possesses,
whether a moment exists when incorporated into the host electrode, as interpolated by the
presence or absence of a zero bias peak, and the strength of the moment. The s-d
exchange constant is inversely proportional to both the magnitude of the moment and the
energy of the d-band relative to the Fermi level. The presence of a magnetic moment is
expected to correspond to a lower limit of the coupling strength, JN(O). It is known that
Ag has a smaller density of states at the Fermi level than does Al. Since J is inversely
proportional to the product of the total spin of the impurity and the energy of the d-band
relative to the Fermi energy, a qualitative prediction can be made. Small spins
accompanied by low d-band energies give large values for J, which apparently
collaborate with the small N(O) in Ag to give local moments, as observed experimentally
for spin-1 Ti and Ni. The larger N(O) in Al accommodates larger spin values and d-band
energies, giving a smaller J, to satisfy the requirement for local moment formation.
These predictions are consistent with experiment, as moments appear to be formed in the
Al electrode for a broad range of dopant spin.
Table 3-1. Dopants purposefully implanted into metallic tunnel junction electrodes and
corresponding properties .
This brief discussion of zero bias anomalies is intended to form the framework
within which comparisons can be made between the data from intentionally doped
electrodes presented above and tunneling spectra of ferromagnetic compounds such as
EuB6 (see chapter 2) and, in a preliminary way, CaB6, as will be presented in chapter 5.
Further information on zero bias anomalies in compounds less related to this work can be
found in Principles of Electron Tunneling Spectroscopy by E. L. Wolf .
Dopant n (3d) Junctions Nominal Spin
Ti 2 Y Y 1
V 3 N Y 3/2
Cr 4 N Y 2
Mn 5 N N 5/2
Fe 6 N Y 2
Co 7 N Y 3/2
Ni 8 Y Y 1
In this chapter, the technical aspects of this work will be discussed. First, a brief
description of the growth of the CaB6 crystals will be given, followed by sample
preparation methods prior to our transport measurements, including resistivity, Hall
effect, and magnetoresistance. An overview of electronic, magnetic field, and data
acquisition equipment will follow. In addition, a presentation of planar tunneling
techniques, as well as the low-noise electronics required for these investigations, will be
4.1 Crystal Growth and Doping
Single crystals of CaB6 were grown and provided by Z. Fisk's group at Florida
State University. The samples were grown out of a molten Al flux using high-purity
starting materials, encapsulated in an alumina crucible. Stoichiometric CaB6 required an
excess of Ca that was incorporated into the melt, due to the suggestion of a tendency of
this material to form Ca vacancies. In the initial growth process, it was believed that the
excess Ca is not incorporated into the resultant crystal. Further discussion of this
assumption is given in the conclusions presented in Chapter 6.
Electron doping was achieved by substitution of La for Ca. The data presented in
this work were obtained from samples that were La doped at a level of roughly 0.5%. A
second doping procedure involved the exclusion of a small amount of Ca from the melt,
in an effort to intentionally incorporate Ca vacancies into the material. In the discussion
of experimental findings, the electron-doped system will be denoted by Cal_-La6B6, the
intended stoichiometric material will be labeled CaB6, and the Ca deficient compound
will be referred to as Cal-6B6.
These single crystals form in a rectangular shape with typical dimensions being
approximately 2mm x 0.5mm x 0.5mm. However, we believe that electron transport may
be confined to a fraction of the crystal smaller than the physical size would suggest. As
an adequate means of measuring these reduced dimensions is absent, an attempt has been
made to conduct all transport measurements corresponding to a particular doping
concentration on the same crystal, so that the results can be related within the data set.
4.2 Transport Measurement Techniques
The oblong crystal shape adopted by these samples suggests a natural orientation
for contact formation. The contact configuration shown in Figure 4-1 was found to be
suitable for resistivity, Hall effect, and magnetoresistance simultaneously. A significant
advantage to this permanent configuration became apparent during studies of the Ca
deficient compound, where it was discovered that repeated processing of this material
generates small cracks in the crystal, drastically altering the transport properties of the
sample. Tunneling experiments employed a tri-layer structure that will be described in
1 7 -v-
V- I I-
magneto-resistance Hll ct
Figure 4-1. Contact configuration for simultaneous measurement of resistivity,
magnetoresistance, and Hall effect.
4.2.1 Resistivity, Hall Effect, and Magnetoresistance
Initial efforts to establish electrical contact to the crystals entailed submersion into
a weak nitric acid solution for 5 minutes, followed by a rinse in water, and manual
application of conductive silver paint in the desired contact configuration. Upon the
observation that the contacts deteriorated with thermal cycling, it was apparent that a
more careful process would be required. Good-quality, low-resistance contacts were
formed in a high vacuum chamber with a base pressure of 5x10-7 Torr. To clean the
surface and improve sticking probability, the crystal was exposed to a high-purity Xe
plasma at a beam voltage of 450 V. This was followed by thermal evaporation of 20 nm
of Au in the pattern discussed above defined by a shadow mask. Subsequent 8- to 12-
hour annealing in an inert Ar environment at temperatures of approximately 100 C
further established the low-resistance character of the contact pads.
The Hall effect and magnetoresistance studies, for which a magnetic field is
required, were conducted in a 4He cryostat, as shown in Figure 4-2. The dewar is
equipped with a pump-out port, making possible a base temperature of 1.6 K, as well as
an American Magnetics, Inc. (AMI) superconducting magnet with a maximum field of 8
Tesla. The cryostat is equipped with temperature sensors, a small resistive heater for low
temperature regulation, and a power resistor with which temperatures near 300 K can be
attained. Two layers of vacuum provide good thermal isolation of the sample stage from
the liquid helium bath making high temperature measurements in magnetic field possible.
Temperature regulation was performed using a LR-400 resistance bridge coupled with a
LR-130 temperature controller. At low temperatures, the small 50 Q resistor provided
adequate heating. Above roughly 15 K, the 5-Watt power resistor served to bring the
equilibrium temperature up, while the small resistor functioned as a fine control.
A smaller 4He probe with one layer of vacuum isolating the sample from the
helium bath was employed for resistivity measurements. The temperature was varied in a
very simple way. Cold N2 gas was first circulated through the N2 jacket, without
collecting liquid. Liquid He was transferred into the dewar only until the sample reached
4.2 K. With the aid of automated data acquisition, which will be described below, the
measurement can be performed without supervision, as the dewar slowly warms. The
voltage output of the LR-400 is used to record the sample temperature.
Figure 4-2. Depiction of 4He cryostat with pump-out port used for magnetotransport
(a) Measurement leads.
(b) Flange to mate with top of dewar, pressure fitting to adjust height.
(c) Vacuum can with Ag solder seal (first layer of vacuum).
(d) Thermal insulation of stage from He bath.
(e) Cu sample stage with 0-rotation capability.
(f) Outer vacuum jacket with pump-out port (second layer of vacuum).
All transport measurements were performed in an RF shielded room using analog
electronics, including a Princeton Applied Research (PAR) 124A lock-in amplifier
equipped with a PAR 116A preamplifier and accompanied by low-noise Ithaco 1201
preamplifiers. The sample was driven with an AC level out of the lock-in. Constant
current was achieved by placing in series with the sample current leads a dropping
resistor of value Rdrop = 100 x Rsample or greater. The current through the sample was
measured during data acquisition to confirm its constancy. The voltage across the sample
was first fed into an AC-coupled preamplifier, whose output was followed by the lock-in
amplifier. The output of the lock-in, as well as the independent parameter (temperature,
magnetic field) were measured and transmitted out of the shielded room to an automated
data-acquisition LabVIEW program by fiber optic cable.
For the Hall effect and magnetoresistance measurements, an AMI
superconducting magnet was used to produce fields up to 8 Tesla. The magnet was
employed using an AMI 4Q-05100 four-quadrant power supply and an AMI 420 power
supply programmer. Data points were taken by ramping the magnet to a specific field
and recording a number of points, usually 5 points/field, to be averaged in data analysis.
This eliminated two undesirable effects: not only is there a high level of noise associated
with field ramping, but this technique also corrects for a lag in sample voltage with
respect to field due to the time interval intrinsic to the data acquisition technique.
Attempting to measure the anomalous Hall effect is an exception to this static-field
procedure. During these measurements, the magnet ramp rate was sufficiently low that
the time lapse between recording the field and recording the sample voltage was taken to
Data analysis was performed using Origin. Since magnetoresistance tends to
contain contributions from the Hall effect, and vice-versa, it was important to take
magneto-transport data at both positive and negative magnetic fields. In this way,
accurate results were obtained by eliminating any anti-symmetry seen in the
magnetoresistance and any symmetry in the high-field Hall voltage. This procedure is, in
effect, the van der Pauw method of correctly measuring said quantities .
4.2.2. Tunneling Spectroscopy
Further investigation of the electronic structure in the form of planar tunneling
spectroscopy was performed on a crystal of the La doped material. Tunneling is a
technique by which one can measure the density of electronic states at energies away
from the Fermi level. The tunneling structure is a tri-layer junction formed by the
material to be investigated and a well-characterized material separated by an insulating
layer a few tens of angstroms thick, as depicted in Figure 4-3. The tunneling
conductance, dI/dV, across this device is approximately proportional to the product of the
density of states of the two electrodes. Typically, the counter-electrode of choice has a
constant density of states, as in the case of a metal or superconductor above its Tc, so that
the tunneling conductance is proportional to the material being studied. By applying a
variable DC bias to the junction, the Fermi levels of the two electrodes are shifted with
respect to one another, and the density of states at energies away from the Fermi level can
be probed. For an in-depth discussion of tunneling spectroscopy, see chapter 3.
\ /- nCounter- ele ctrode
Figure 4-3. Cross-section of a tunnel junction. An area of roughly 20 trm2 has been
exposed and developed in the photoresist, defining the area of the junction. This figure is
For all tunneling results presented in this work, the counter-electrode was Pb,
which has a Tc, convenient for working at liquid He temperatures. The advantage of
using a superconducting counter-electrode is the diagnostic capability of measuring its I-
V curve below T,. The quality of the tunnel barrier can be determined by the sharpness
of the gap, an example of which for EuB6 is shown in Figure 4-4. Here, the gap edge can
be clearly seen as a change in slope at a bias voltage roughly equal to the value of the
superconducting gap. Another test of junction quality is to determine the ratio of the
four-terminal dynamical resistance at energies less then the gap to that at energies greater
than the gap. A ratio of RA = 100 at T < Tc/2 is considered an indication of a good-
quality barrier. Additionally, phonon modes, which appear as local extrema in the
tunneling conductance, can be detected at bias voltages 7 mV and 11 mV. In the
presence of inelastic tunneling mechanisms, which are highly undesirable when present
in the barrier, this phonon structure will be undetectable.
-4 -2 0 2 4
Figure 4-4. I-V characteristic of a EuB6-I-Pb tunnel junction. The gap about zero bias is
clearly seen, as is the break in slope occurring at roughly +2 mV.
The most significant difficulty has been to fabricate a high-quality insulating
barrier. Many variables contribute to the success of a barrier. Not only must a
fabrication method be optimized, which is a challenging process, but the surface of the
crystal must be smooth, the Pb counter-electrode must be protected against shorting to the
electrode, and the method of defining the junction area must be able to withstand cold
temperatures without cracking.
The process that was found to be optimal for tunneling into CaB6 was preceded by
a 5-minute etch in a weak nitric acid solution. This was designed to remove residual Al
left by the growth process from the crystal surface. The next task was to define the
junction area. This consisted of the selection of a smooth portion and an increase in the
likelihood of forming a uniform barrier. The remainder of the crystal is electrically
isolated during this step by spinning a layer of 1350J photoresist at 4000 rpm for 30
seconds. After baking the photoresist layer at 75 C for at least 20 minutes, optical
lithography was used to expose a region of the surface roughly 20 Mtm2 in area. The
photoresist was then developed in AZ351, a sodium boride-based developer, for 20
seconds and rinsed in water. A thin insulating layer was then formed on the bare surface
of the crystal by a 20-minute exposure to a reactive ion etch of CC12F2 at 20 Watts. This
procedure is believed to remove boron from the surface of the crystal, leaving the Ca-rich
surface free to oxidize upon exposure to the atmosphere. Using a Cu evaporation mask to
limit coverage of the counter-electrode, the sample was loaded into a high vacuum
chamber with a base pressure of 5x10-7 Torr, and 500 nm of Pb were thermally deposited
to form the counter-electrode.
While photoresist is used to not only define the junction area but also to
electrically isolate the crystal from the Pb, cracks can easily develop along the crystal
edges at low temperatures. The material found to be well suited to withstand low
temperatures is a mixture of one part Duco cement to three parts n-Butyl Acetate. A drop
of green paint was commonly added to make the adhesive visually distinguishable during
manual application. Once the contacts are confirmed to be electrically isolated from each
other and from ground, the sample is mounted onto the 4He probe. Thin Au wire is
attached to the contact pads in a four-terminal configuration such that current is injected
across the barrier, and voltage is measured independently across the barrier. This
eliminates the voltage contribution from the leads that would be present in a two-terminal
When conducting tunneling measurements, the quantities of interest are typically
very small in magnitude. It is essential, therefore, to perform these studies in a low-noise
environment. All data sets to be presented were taken in an RF shielded room with
analog electronics. Care must be taken to prevent voltage transients across the junction,
which can easily destroy the thin barrier. For this reason, shorting the junction leads is
necessary when setting up the measurement and electrically connecting the sample to the
There are two components of the voltage applied to the junction. One is a DC
level produced by a completely passive analog circuit with ramping capabilities as well
as a manual voltage adjustment. A small AC voltage at a frequency of roughly 1 kHz,
but not a harmonic of 60 Hz, originates from a PAR 124A lock-in amplifier and is added
to the larger DC signal. This circuit is shown in Figure 4-5. The DC voltage is the bias
voltage. For high-resolution spectroscopy, the AC voltage must be much smaller in
amplitude than the DC level, VAC < 0.05 VDC, since we will be using this configuration to
measure the dynamical resistance, or the inverse of the tunneling conductance, versus
bias voltage. The objective is to keep a constant current, with the use of a dropping
resistor, as described above, so that the recorded dynamical resistance of the junction is
proportional to the voltage response. The DC voltage drop across the junction is
recorded as the bias voltage. The need for low-noise conditions is now apparent when we
consider the magnitude of the sample response to the small AC excitation.
Power Output to sample
20 kQ SET
10 k 0 Rdrop
+12 15 nmF
Figure 4-5. Circuit diagram for tunneling measurements. The ramp and set functions
manipulated the bias voltage. A lock-in amplifier, set at roughly 1 kHz, produces the
small AC excitation.
All tunneling measurements were performed in the simple liquid He probe
without magnetic field capabilities, as described above. Diagnostic evaluation of the
quality of the superconducting Pb structure is best done at T < T,/2, where the gap has
sufficiently developed. By utilizing the pumping port, we were able to reduce the
pressure in the He space and, consequently, the temperature of the system. Base
temperature for this process is 1.6 K, where 4He approaches a superfluid, and its vapor
pressure is very low. Temperatures above 4.2 K were achieved by varying the vertical
position of the sample within the dewar, taking advantage of the vertical temperature
It is useful to take tunneling data for a broad range of temperatures. In this way, it
is possible to investigate the progression of the density of states as the temperature is
altered, an ability especially valuable in the neighborhood of a phase transition. These
very sensitive measurements are best taken with an x-y plotter, advantageous for its high
resolution. The spectra were then converted into a set of x-y points using Un-Scan-It.
Analysis of the data was finally performed using Origin.
PRESENTATION OF RESULTS
In this chapter, the results of this work on CaB6 and its electron-doped and Ca-
deficient variants will be presented. The contents included here will be the foundation
for the interpretation to follow in chapter 6. Section 5.1 is devoted to a description of the
electronic resistivity as a function of temperature and electron content. In section 5.2,
Hall effect data are provided in the form of the Hall voltage versus field and carrier
concentration versus temperature and doping concentration. Magnetoresistance data are
the subject of section 5.3, and electron tunneling spectra are presented in section 5.4.
One fundamental complication with attempting to measure transport properties in
the single-crystal samples has been the variation in sample dimension and in sample
composition. The absolute values of the resistivity are difficult to determine because the
effective sample thickness, where the current is uniform, is suspected to be smaller than
the physical crystal thickness. In addition, the variations in composition occur even
within a single batch of crystals. To compensate for these sources of error, resistivity
data that is normalized to the value at 300 K is presented for the electron-doped and Ca-
deficient compounds and to the value at 50 K for the stoichiometric material. The issue
of non-uniformity within a crystal batch has been addressed by using a single sample
where possible throughout our series of measurements. In this way, the resistivity, Hall
effect, and magnetoresistance data shown below correspond to representative samples of
the same crystal stoichiometry and physical dimensions for each doping concentration.
5.1 Resistivity Measurements
Resistivity measurements are of importance in the effort to identify the electronic
environment in these materials. In the process, the consistencies of various band
structure predictions with experimental data have been inspected and will be addressed
further in the next chapter. As will be demonstrated here, however, behaviors in the
resistivity can be complex, with physical interpretations that are not immediately
Figure 5-1 shows resistivity versus temperature for the electron-doped material.
The metallic nature seen here is in agreement with that reported earlier. The resistivity,
normalized to the value at 300 K, shows a decrease of roughly 30 percent in the
temperature range studied. At the lowest temperatures, there is a small upturn that may
indicate a type of charge carrier localization. The nature of the interaction will be
revisited in the following chapter of this work.
The stoichiometric material was expected to exhibit semiconducting behavior,
according to a portion of the previously published work. Resistivity versus temperature,
as shown in Figure 5-2, instead appears to retain marginal metallicity. The temperature
dependence of the resistivities of roughly a dozen crystals grown from the same melt
were measured to verify the seemingly contradictory behavior. Small variations are
observed within the sample batch since the transport behavior of these crystals are highly
dependent on the ratio of Ca to B6, but the data shown corresponds to a representative
CaB6 crystal. At high temperature, an initial decrease in resistivity is seen, followed by
an increase, a small maximum at 50 K, and another minimum at lower temperature. In
fact, the form of the resistivity appears to indicate a competition between high and low
Normalized resistivity versus temperature in Cal-6La6B6.
0 50 100 150 200 250
Normalized resistivity versus temperature in CaB6.
0 50 100 150 0 2 250 300
O I I (a)
9 100- I I
I I II
I I I I I I I
0 50 100 150 200 250 300
Figure 5-3. Normalized resistivity versus temperature in Cal-6B6. The high temperature
fit in Figure 5-4(a) is confined to region (a), and the low temperature fit in Figure 5-4(b)
is confined to region (b).
Interestingly, semiconducting behavior was found to be present in the resistivity
of crystals that were Ca-deficient. A large number of same-batch samples were
measured. Data taken on a sample representative of the batch are shown in Figure 5-3
and indicate a sharp resistive rise around 175 K, followed by a low-temperature plateau.
The low-temperature and high-temperature regions were fit independently to an activated
form, p(T) = po exp(A/kBT), where po is the value of the resistivity when Tis large. The
results of this fit, as shown in Figure 5-4, are in excellent agreement with the
semiconducting model, where the high temperature fit (a) yields a gap value of roughly
3500 K, or 350 meV, and the low temperature fit (b) gives a much smaller gap of roughly
0.5 K, or 0.05 meV. The temperature ranges to which these fits have been confined are
shown in Figure 5-3 as regions (a), for the high-T fit, and (b) for the low-T fit. The
0 -- Linear fit of Ca1 _gB at high T
In (p Po) = -12.48 + 3457/T
0.0036 0.0040 0.0044 0.0048
In (pip 0)
0.01 -- Linear fit of CaIgB6 at low
In (p Po) = -0.0013 + 0.5303/T
0.00 1 ,
0.02 0.04 0.06 0.08 0.10 0.12
Figure 5-4. Fit of resistivity versus temperature to activated form in Cal_-B6.
(a) High temperature limit.
(b) Low temperature limit.
deviation from these fits at intermediate temperatures may represent interactions poorly
described by the independent two-component model employed to investigate the
asymptotic limits of the resistivity results in Cal-sB6.
To ensure that the activated behavior in the Ca-deficient material is due to Ca
vacancies, a post-growth method was developed to further deplete the Ca concentration.
Annealing in an oxygen atmosphere exploits the low vapor pressure of CaO to remove Ca
from the surface of the crystal. This anneal was conducted at a temperature of roughly
250 "Celsius. A subsequent anneal in an inert Ar environment at a slightly higher
temperature was performed in an effort to restore uniformity to the crystal, thus
enhancing the concentration of Ca vacancies in the bulk.
The effect of the annealing procedure on the behavior of resistivity with
temperature is shown in Figure 5-5. The data in black were taken on a Ca-deficient
crystal prior to anneal. After anneal, as shown in red, the same crystal displays no
detectable change in the value of the high-temperature resistivity, as can be seen in
Figure 5-6, which is a magnified view of the high-temperature region of Figure 5-5. The
values of the high- and low-temperature gaps do exhibit a 2-3 percent enhancement after
anneal. The change in gap values implies that, by removing the electron donor cations
from the system, the Fermi level has been shifted downward in energy and apparently
deeper into a band gap. These data suggest the presence of the thermal excitation of
carriers from a source in addition to the valence band.
-=-- before anneal
--- after anneal
0 50 10
Figure 5-5. Resistance versus temperature in Cal_6B6 prior to (black squares) and
following (red circles) 02 anneal.
U3 -" -- before anneal
Su -a- after anneal
Figure 5-6. High temperature region of Figure 5-5.
5.2 Hall Effect Measurements
A series of Hall effect measurements was performed with the intention of
determining not only the sign of the carriers in each doping regime but the carrier
concentration as a function of doping level. We initially expected that in the La-doped
system the carriers would be electrons, that in the stoichiometric system there would be
equal numbers of electrons and holes, and in the Ca-deficient system the carriers would
be exclusively holes. The data contradict these expectations but are consistent with the
resistivity versus temperature behaviors presented above. A band structure model
incorporating this information will be fully developed in chapter 6. An alternative motive
of pursuing these measurements was to investigate the possible appearance of the
anomalous Hall effect as a signature of ferromagnetism.
1.6 8 S
C Carrier Concentration 3
0.6 -0 o Io I I o
0 50 100 150 200 250 300
Figure 5-7. Carrier concentration (red) and normalized resistivity (black) versus
temperature in Cal-6La6B6.
The Hall effect has been studied as a function of temperature for each of the three
doping concentrations. Figures 5-7 through 5-9 display the results of Hall effect
measurements in red. The resistivities versus temperature for the same samples are
included for comparison and are shown in black. The La-doped material exhibits a
carrier concentration of roughly 5x1019 electrons/cm3, as seen in Figure 5-7. This
electron concentration is approximately independent of temperature, indicating that the
conduction electrons reside in the conduction band and are not thermally excited from a
band lower than the Fermi level.
300- 2 -
Ca 1 gB M
0 Carrier Concentration -
S 50 100 150 200 250 300
Figure 5-8. Carrier concentration (red) and normalized resistivity (black) versus
temperature in Cal-6B6.
Figure 5-8 shows data for the Ca-deficient material, with the carrier concentration
shown in red and accompanied by the resistivity in black for comparison. The electron
concentration is and is found to be an order of magnitude lower than that seen in the
electron-doped analog. Notice, however, that the Ca-depleted compound retains
electron-like carriers. This indicates that the mid-gap position has not been crossed in
reducing the Fermi level in energy. The electron concentration is found to decrease in the
region of increasing resistivity, as to be expected. As the resistivity levels off, the
electron density demonstrates a simultaneous leveling. The concomitant behaviors of
resistivity and carrier concentration are consistent with a standard interpretation. Here
the increase in resistivity is due to a combination of phonon freeze-out and a reduction in
thermally excited electrons about the Fermi level.
SCarrier Concentration C
0 50 100 150 200 250 300
Figure 5-9. Carrier concentration (red) and normalized resistivity (black) versus
temperature in CaB6.
The stoichiometric material exhibits an interesting behavior in carrier
concentration versus temperature, as seen in red in Figure 5-9. The carrier concentration
is found to be approximately 1x1019 electrons/cm3. This value agrees with a Fermi level
reduced in energy at a reduced electron density with respect to the La-doped system.
Interestingly, the behavior of the carrier concentration with temperature mirrors that seen
in the resistivity. Because of the low carrier density present in this material, it may be
that electron-electron correlations dominate over electron-phonon scattering. Such a
scenario might give rise to a directly proportional relationship between resistivity and
The anomalous Hall effect is a manifestation of spin-dependent scattering and is
commonly observed in materials that exhibit long-range ferromagnetic order. In the
presence of an external magnetic field, the moments in the solid align accordingly. As a
result, the internal magnetic field and associated Lorentz forces acting on the spin-
polarized electrons will be field-dependent until the saturation field is attained. The
observable result is that the Hall voltage exhibits a hysteresis that mirrors that seen in
The possible appearance of hysteresis in the Hall voltage was investigated in an
attempt to further verify the presence of long-range magnetic order in CaB6. The results
are shown in Figure 5-10, where an unusual kind of hysteretic behavior is seen. These
data were taken on the initial zero-field cool-down of the crystal. With subsequent field
sweeps, the effect seems to disappear. Magnetization data on a collection of crystals
grown from the same melt but randomly oriented with respect to the applied field are
shown in Figure 5-11. The good agreement in saturation field seen in the two
independent measurements is convincing that the effect observed in the Hall voltage is
not only consistent with but is related to the magnetic state of the material. That the
0 500 1000 1500 2000 2500
Magnetic Field (Oe)
Figure 5-10. Hysteresis in Hall voltage versus magnetic field in CaB6 at 4.2 K. The
saturation field is roughly 2500 Oe, or 0.25 T.
-2000 0 2000
Figure 5-11. Hysteresis in magnetization versus magnetic field in CaB6 at 4.2 K The
saturation field is roughly 2500 Oe, or 0.25 T (data provided by Bianchi and Fisk).
hysteresis persists in the multi-crystal data may be accounted for by intra-batch non-
uniformity arguments. These will be presented in the following chapter.
5.3 Magnetoresistance Measurements
Magnetoresistance measurements can provide a good deal of information about
the electronic interactions present within our system. As has been discussed in chapter 3,
a typical metal displays a positive H2 dependence of resistance on magnetic field.
Oftentimes, deviations from this behavior can reflect the importance of electron-electron
In magnetoresistance studies of the CaB6 system, negative signals were found for
all three doping concentrations. In Figure 5-12, magnetoresistance, in terms of fractional
change, versus magnetic field is given for La-doped CaB6 at various temperatures. A
small negative magnetoresistance of roughly 0.6% is observed at 5 K, the lowest
temperature for which data has been taken, and at a field of 6 T. With increasing
temperature, the magnitude of the magnetoresistance begins to diminish, a trend seen in
all three materials.
An effect similar in magnitude to that of the La-doped compound is observed in
the stoichiometric material, a material that retains some degree of semimetallic nature as
suggested by the preceding resistivity and Hall effect data. The magnetoresistance for
stoichiometric CaB6 is shown in Figure 5-13. A maximum effect is observed at 5 K and
6 T of roughly 0.5 %. Again, the signal becomes smaller as the temperature is increased.
It is rather noticeable that, at temperatures below 30 K, the electron-doped material
Magnetic Field (T)
Figure 5-12. Magnetoresistance versus magnetic field in Cal_6La6B6.
--- T = 5 K
T = 50 K
T1 = 100 K
Magnetic Field (T)
Figure 5-13. Magnetoresistance versus magnetic field in CaB6.
-*- T = 10 K
T = 22 K
-v- T = 36 K
-.- T *-
-0.005 -K 4 -
-* *"- _
-0.010 -- T=5K -., '.
--'- T = 10 K = 10.
-0.015T = 16 K E a
--4- T = 31K K .
T = 40 K
-0.020 T = 60 K
T = 75 K Cal- B6 "
-0.025 I I I
0 1 2 3 4 5 6 7
Magnetic Field (T)
Figure 5-14. Magnetoresistance versus magnetic field in Cal-6B6.
exhibits a magnetoresistance of a different functional form than that seen in the
stoichiometric compound. This observation will be addressed in chapter 6.
Data for the vacancy-doped compound is shown in Figure 5-14. These data
indicate a much larger effect than that seen in the two metallic materials. The maximum
value of the negative magnetoresistance at 5 K and 6 T is nearly 2.5%, a signal that is
approximately five times larger than that seen in the electron-doped and stoichiometric
analogs. The trend of decreasing signal with increasing temperature is preserved in this
5.4 Tunneling Measurements
Tunneling measurements were performed in advance of the transport studies
discussed above. The initial goal in undertaking tunneling experiments was to investigate
the possible appearance of zero-bias anomalies, in analogy with the features seen in the
spectra of ferromagnetic EuB6 below its Curie temperature. Additional information
provided by these measurements has been influential in the analysis of the Cal-6La6B6
In early measurements, a sharp feature at zero bias in a tunneling spectrum of La-
doped CaB6 was observed at very low temperature, as shown in Figure 5-15. Many
external conditions can influence the appearance of these features, including stray
magnetic fields, temperature variation, and even the passage of time. Therefore, while
the detection of this feature is supporting evidence for ferromagnetism, the data cannot
stand alone as a convincing signature of magnetic order. Additionally, it is important to
20- --T = 11K 4
10- T=20K 0
T T = 25 K U
0- -T=30K __T=2K
T = 40 K -2.0 -115-11 -015 o i 05 l0 1.5 210
10IV 40 Voltage (mV)
-10 i i i i
-100 -75 -50 -25 0 25 50 75 100
Bias Voltage (mV)
Figure 5-15. Tunneling conductance versus bias voltage in Cal-6La6B6.
note that the I-V characteristic, shown as an inset, appears to be of a lower quality than is
typically desired. While it is possible that the conductance peak at zero bias may be
washing out the Pb structure, contributions due to undesirable inelastic transport
mechanisms may also be present.
It is also noticeable that the peak diminishes rather quickly with increasing
temperature and appears to be completely absent for temperatures above 25 K. Whether
this reduction in intensity indicates a transition, magnetic or otherwise, is not definite.
These results may be interpreted to be evidence for a second transition well below the Tc
of the material that has no bearing on the bulk ferromagnetism. While a double transition
is reminiscent of that seen in ferromagnetic EuB6, we hesitate to draw parallels between
the two systems based on these data.
Subsequent tunneling spectra on additional crystals are shown in Figures 5-16 and
5-17. Figure 5-16 is accompanied by the I-V characteristic in the inset for this particular
junction and exhibits a well-defined gap region about zero voltage. In the tunneling
conductance, the superconducting Pb gap appears at zero bias for temperatures below To
= 7.2 K. There is an unusual feature in the center of the gap, however. It seems that
there may exist a zero bias component to the low-temperature spectra that is unrelated to
the superconducting gap. Due to the absence of this feature in the tunneling spectra of
Figure 5-17, it is clear that more extensive studies are required to ascertain its origin.
The spectra exhibited in Figure 5-17(a) represent higher temperature behavior and
may indicate the formation of a pseudo-gap centered about 22 mV, a feature and energy
scale common to many of the previously studied hexaborides. The low-temperature data
do not display a clean zero bias peak, as seen previously. There are many maxima in the
0.007- 1 T=2K
S 0.006- o0
S 0.005- s -5 .
-6 -4 -2 0 2 4 6
T T=4.2 __K Voltage (mV) _._
S 0.004- -- T = 10 K
T =25 K
T =30 K Cal-6LagB6
-40 -20 0 20 40
Figure 5-16. Tunneling conductance versus bias voltage in Cal-6La6B6.
spectrum at low temperatures, as shown in Figure 5-17(b), but the width and energy
scales are rather large to be attributed to a zero bias phenomenon. In the bias range
shown, there appear to be features centered about 10, 20, and 30. These features are
reminiscent of a system in which some type of inelastic excitation couples to the
conduction electrons of the system. A discussion of what these excitations may represent
will be given in chapter 6.
- T = 15 K
S T = 20 K
T =25 K
T =30 K
T =35 K
- T =40 K
-40 -20 0 20 40
Bias Voltage (mV)
-20 0 20
Bias Voltage (mV)
Figure 5-17. Tunneling conductance versus bias voltage in Cal-6La6B6 (a) for 15 K < T <
40 K and (b) for 2 K < T < 20 K.
-3 -2 -1 0 1 2 3