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Letter

pubs.acs.org/NanoLett

Electronic Properties of High-Quality Epitaxial Topological Dirac


Semimetal Thin Films
Jack Hellerstedt, Mark T. Edmonds,*, Navneeth Ramakrishnan, Chang Liu, Bent Weber,
Anton Tadich, Kane M. ODonnell, Shaque Adam,, and Michael S. Fuhrer

School of Physics and Astronomy and Monash Centre for Atomically Thin Materials, Monash University, Victoria 3800, Australia
Department of Physics and Centre for Advanced 2D Materials, National University of Singapore, 117551, Singapore

Australian Synchrotron, Clayton, Victoria 3168, Australia

Curtin University, Perth, Western Australia 6102, Australia

Yale-NUS College, 6 College Avenue East, 138614, Singapore

S Supporting Information
*

ABSTRACT: Topological Dirac semimetals (TDS) are three-dimensional analogues


of graphene, with linear electronic dispersions in three dimensions. Nanoscale
connement of TDSs in thin lms is a necessary step toward observing the
conventional-to-topological quantum phase transition (QPT) with increasing lm
thickness, gated devices for electric-eld control of topological states, and devices with
surface-state-dominated transport phenomena. Thin lms can also be interfaced with
superconductors (realizing a host for Majorana Fermions) or ferromagnets (realizing
Weyl Fermions or T-broken topological states). Here we report structural and
electrical characterization of large-area epitaxial thin lms of TDS Na3Bi on single
crystal Al2O3[0001] substrates. Charge carrier mobilities exceeding 6,000 cm2/(V s)
and carrier densities below 1 1018 cm3 are comparable to the best single crystal
values. Perpendicular magnetoresistance at low eld shows the perfect weak
antilocalization behavior expected for Dirac Fermions in the absence of intervalley
scattering. At higher elds up to 0.5 T anomalously large quadratic magnetoresistance
is observed, indicating that some aspects of the low eld magnetotransport (B < 1) in this TDS are yet to be explained.
KEYWORDS: Topological Dirac semimetal, thin lm growth, scanning tunneling microscopy, magnetotransport
result.9 Interfacing TDS thin lms with superconductors could
realize topological superconductivity and a host for Majorana
Fermions,10 and interfacing with ferromagnets can break timereversal symmetry to produce Weyl Fermions and a variety of
topologically nontrivial states.1 However, to date the only
reports of thin lm Na3Bi have used the conducting substrates
graphene and Si[111], making electronic transport studies
impossible.11,12 An additional challenge in electrical characterization of Na3Bi is the reactivity of sodium to ambient, which
makes conventional ex situ measurement methods impossible
without suitable passivation.
Here we demonstrate high quality, c-axis oriented thin lm
Na3Bi on insulating Al2O3 [0001] substrates. We have
characterized the lms using low temperature magnetotransport and scanning tunnelling microscopy and spectroscopy
(STM and STS) in situ in ultrahigh vacuum (UHV). Films are
grown using a two-step method inspired by previous work on
the topological insulator Bi2Se3.13,14 A thin (2 nm) nucleation
layer is deposited under simultaneous Bi and Na ux at low

he topological Dirac semimetal is characterized by Dirac


points, consisting of two degenerate Weyl points with
opposite topological charge occurring at the same momentum.
It was shown that the Weyl points can be protected from
opening a gap by crystal symmetry, with the rst such TDS
compound predicted being Na3Bi,1 whose Dirac electronic
structure was experimentally conrmed by angle-resolved
photoemission spectroscopy (ARPES) on bulk single crystal
samples.2 Further transport and scanning tunneling microscopy
(STM) studies of bulk crystals have begun to address the
implications of the chirality of these Weyl points, namely, the
in-plane quadratic magnetoconductance due to the chiral
anomaly,35 though these signatures remain controversial.6
Nanoscale connement of the TDS state in thin lms opens
new possibilities to tune the topological state with thickness,7
electric eld,8 and proximity coupling to superconductors and
ferromagnets.1 In particular, detailed calculations on Na3Bi have
predicted a conventional-to-topological quantum phase transition (QPT) occurs with increasing lm thickness7 and that
the QPT can also be tuned by electric eld (by e.g. gate
electrodes) to enable a topological transistor.8 In addition, TDS
possess unusual Fermi arc surface states, and nanostructured
TDS are proposed to exhibit unusual transport phenomena as a
XXXX American Chemical Society

Received: February 12, 2016


Revised: April 18, 2016

DOI: 10.1021/acs.nanolett.6b00638
Nano Lett. XXXX, XXX, XXXXXX

Letter

Nano Letters

Figure 1. Structure of Na3Bi thin lms. All data correspond to 20 nm thick Na3Bi grown at 345 C on -Al2O3[0001]. (a) Schematic representation
of device geometry showing location of Ti/Au pads used to make electrical contact to the Na3Bi lm grown on sapphire. The inset shows the crystal
structure of Na3Bi with the in-plane and c-axis lattice constants labeled, where Na and Bi atoms are colored green and purple, respectively. (b) Largescale STM image showing the morphology of Na3Bi with step height 4.7 (Vbias = 1 V, I = 100 pA, T = 5 K). Inset: Atomic-resolution STM image
of surface with lattice constant 5.45 (Vbias = 500 mV, I = 200 pA, T = 5 K). (c) LEED image taken at 17.5 eV showing the 1 1 symmetry of the
Na3Bi surface. (d) Scanning tunneling spectrum dI/dV vs V averaged over 20 nm 20 nm area. (Bias modulation rms amplitude is 5 mV). The bias
voltage position of minimum dI/dV is labeled ED = 35 mV and identied as the Dirac point energy.

(120 C) temperature, followed by additional growth at a


higher nal temperature between 250 and 390 C. Further
details regarding sample preparation, growth, and characterization can be found in the Supporting Information.
Figure 1 shows the crystalline quality of our Na3Bi thin lms.
Figure 1a shows a schematic of our device. Single crystal
Al2O3[0001] is prepatterned with electrical contacts in van der
Pauw geometry, and the Na3Bi is deposited on top, making
electrical contact. Figure 1a inset shows the crystal structure of
Na3Bi. Figure 1b shows STM topography at a temperature of 5
K, showing a large area (80 80 nm) atomically at terrace,
with a step height of 4.7 , consistent with the half-unit cell
distance of 4.83 between NaBi planes.1 Atomic resolution of
the surface (inset) shows a (1 1) termination with the
expected in-plane lattice constant of 5.45 . The 1 1
triangular lattice rather than hexagonal lattice is strongly
suggestive that the surface is Na-terminated. Figure 1c shows
low energy electron diraction (LEED) taken at 17.5 eV. The
low background and sharp hexagonal diraction pattern
conrm that the (1 1) structure is coherent across the
LEED spot size of 200 m. Faintly visible is the same pattern
rotated 30, indicating the presence of a small fraction of the
sample with that alignment. We note that similar quality LEED
patterns were observed on samples grown across the range of
nal temperatures studied. Figure 1d) shows STS (dierential
conductance vs bias voltage) averaged over an area of 400 nm2.
STS reect the energy dependent local density of states of the

sample. The sharp dip near zero energy reects the dip in
LDOS at the Dirac point,4,15 with Dirac point energy ED = 35
meV, consistent with the n-type doping we measured via
transport. We can use this value in conjunction with carrier
density measured via transport (see below, 3.8 1018 cm3)
to estimate the average Fermi velocity in our samples, F = 1.4
105 m/s, in reasonable agreement with the value 2.4 105
m/s obtained from ARPES.2
The ex situ prepared corner contacts (Figure 1a) allowed us
to make van der Pauw measurements of the longitudinal and
transverse resistivity xx and xy in magnetic eld B up to 0.5 T
at a temperature of 5 K, from which we extract the Hall carrier
dxy

( )

density n = ed dB

and the Hall mobility = (nexx)1,

where d = 20 nm is the thickness, and e is the elementary


charge. We note that xy(B) showed no deviation from linear
eld dependence in the entire range of eld measured: the
slope is reported as the Hall carrier density, and we omit
plotting these data. Figure 2 shows (Figure 2a) and n (Figure
2b) plotted against the nal growth temperature for each
sample. Samples with a nal temperature above 380 C had a
substantial reduction in measured mobility and intermittent
electrical contact problems, probably indicating dewetting of
the lm on the substrate at these growth temperatures.
Therefore, we discount these samples from further analysis.
We observe a trend of decreasing n and increasing with
increasing growth temperature, up to 360 C. The highest
B

DOI: 10.1021/acs.nanolett.6b00638
Nano Lett. XXXX, XXX, XXXXXX

Letter

Nano Letters

The only materials parameters are the ne structure constant


= e2/F and the spin/valley degeneracy product g = 4.5 We
estimate the eective ne structure constant for Na3Bi to be
17
between = 0.060.17, based on 120+10
and a Fermi
30,
5
velocity between F = 1.4 10 m/s from STS (Figure 1d), and
F = 2.43 105 m/s from single crystal ARPES experiments.2
Our data lie close to, but somewhat below ( an order of
magnitude) the theoretical prediction of the mobility. There are
several possible reasons for this. First, we may have assumed an
incorrect value for alpha. If we take alpha as a t parameter in
the theory, the best t to the data (green line in Figure 2c)
yields = 0.44, 2.57 times higher than expected. Second, the
theory disregards other contributions to disorder in our
samples, notably point defects, structural incoherence due to
grain boundaries or strain eects, all of which should be
expected to some degree for a large area, van der Waals
epitaxial lm. Third, the theory assumes nimp = n; however, the
presence of both positively and negatively charged will cause
nimp > n. For the latter two reasons, the theoretical prediction is
an upper bound. Electrostatic control of the chemical potential
through, e.g., gates, is one possible route to deconvolving the
contributions of nimp and n to the conductivity and better
understand what factors are currently limiting the mobility of
our lms.
Figure 3a shows the transverse MR xx(B)/xx(B = 0)
plotted as a function of perpendicular applied eld, labeled
according to the nal growth temperature. An overall positive
magnetoresistance (MR) is observed, with a cusp below 0.1
T. We rst discuss the high eld MR. For eld values above 0.1
T the data are well-described by a quadratic dependence:18,19

Figure 2. Hall mobility and Hall carrier density of Na3Bi thin lms
measured at a temperature of 5 K for samples grown with dierent
thermal proles. (a) Mobility and (b) Hall carrier density (n-type) are
plotted against the nal growth temperature for the various samples.
The 120345 C growth prole achieves the highest measured
mobility (6310 cm2/vs) and lowest carrier density (4.6 1017 cm3).
The gray shaded region represents the range of nal growth
temperatures for which the sample quality signicantly degrades. c)
Loglog plot of experimental mobility vs carrier density (black
squares). The red hashed region was calculated using eq 18 in ref 16
for best estimates of the eective ne structure constant = 0.06
0.17. The green dashed line is a t to the experimental data yielding an
eective ne structure constant = 0.44.

xx (B) = xx (B = 0)[1 + A(B)2 ]

Figure 3b shows the prefactor A determined from ts to eq 1


plotted as a function of carrier density n.
In the simplest instance, a single band, two-dimensional
system evinces zero transverse MR.20 There are several possible
origins for the quadratic MR we observe. Multiple conduction
bands of diering mobility and/or carrier density can produce
quadratic low-eld MR,21 however we exclude this possibility
due to the close proximity of the Dirac point as measured by
both Hall eect and STS. Another possible explanation is
spatial inhomogeneity, for example in carrier density, known to
give a quadratic MR at low eld. However, to our knowledge all
theories of spatial inhomogeneity give A < 1.18,2226 This strict
limit contrasts with the values we have obtained in the present
work, ranging from 0.14.5 (Figure 3b). Notably, measurements on single crystal samples show similar unusually large
quadratic MR coecients A > 1 in the low eld regime (B
1).5 Recent theoretical eorts have been made to understand
charge inhomogeneity in a Dirac semimetal system27,28 and
propose that in the spatially inhomogeneous regime the Hall
carrier density overestimates the average carrier density, and
hence the mobility is underestimated and A overestimated.
While the inhomogeneous theory can be made to be consistent
with both the observed mobility and the large apparent A,28 we
nd this explanation very unlikely for our samples. The
inhomogeneous regime is very small in Na3Bi (with 0.1);
the characteristic carrier density inhomogeneity is only a few
percent of the impurity density, requiring donor and acceptor
concentrations to also be balanced within a few percent. We
nd this scenario unlikely to occur generically in all our samples

measured mobility (6310 cm2/(V s)) and lowest carrier density


(4.6 1017 cm3) were measured on a sample grown at 345 C.
This lowest carrier density is still about an order of magnitude
larger than the lowest reported bulk crystal value,3 however our
observed range of doping (4.6 1017 to 1.7 1019 cm3) falls
within the range observed in bulk crystal values.5 Given the
Fermi wavevector kF =

6 2n
g

1/3

( )

(1)

we can calculate the mean

free path l, which ranged between 75 and 135 nm for our


samples.
Increasing mobility with decreasing carrier density is
consistent with expectations assuming that the impurities that
give rise to doping are also responsible for the disorder limiting
the mobility. To better understand the relationship between the
mobility and carrier density, we plotted them against one
another (Figure 2c). The red hashed region is the theoretical
prediction for a TDS using the random phase approximation
(RPA)16 assuming that all the impurities are dopants of a single
sign; i.e., the impurity density nimp equals the carrier density n.
C

DOI: 10.1021/acs.nanolett.6b00638
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Figure 3. Transverse magnetoresistance (0.5 T) of Na3Bi thin lms at a temperature of 5 K. (a) Normalized magnetoresistance xx(B)/xx(B = 0)
as a function of B for samples prepared at nal growth temperatures indicated in the legend. 345* no ux indicates growth without the postgrowth
anneal in Na ux. Lines are ts to eq 1. (b) Quadratic coecient of MR A from ts to eq 1 in (a) as a function of carrier density for the various lms
measured. (c) Residual magnetoconductance = (B) (B = 0) vs B after subtraction of t to eq 1 from data in (a). Fits are to the strong spin
orbit limit of the HLN theory (eq 2).29 The single tting parameter, the coherence length L, is plotted against carrier density in (d). The colors of
the points in (b) and (d) correspond to the sample growth temperatures indicated by the legend in (a).

the samples (20 nm), consistent with the assumption of twodimensionality. (Eorts to t our data using a threedimensional theory for weak localization30,31 yielded poor ts
regardless of the limiting cases in temperature and magnetic
eld used.)
The coherence length L at densities above 6 1018 cm3
exceeds 1 m but is suppressed in lower carrier density
samples, a phenomena that has been previously observed in
other Dirac materials such as graphene32 and the Dirac surface
state of bismuth selenide.33 The fact that our weak eld MR is
well-described by the HLN formula indicates that our Na3Bi
lms are well-described by noninteracting Dirac cones; i.e.,
intervalley scattering is weak.31 However, more careful study of
the MR, including temperature and (electrostatically controlled) carrier density dependence, is necessary to make a
quantitative assessment of the intervalley scattering rate, as well
as any role of spinorbit disorder.34
In summary, we have demonstrated the growth of electrically
isolated, highly oriented, large area thin lm Na3Bi on Al2O3[0001] substrates. The high sample quality is reected in
a record high mobility and near-ideal weak antilocalization
behavior. High-quality TDS thin lms on insulators open a
route toward novel topological phenomena and devices,
including electric eld control via gate electrodes, and
interfacing with magnetic or superconducting materials.

across a range of growth conditions, where the observed Hall


carrier density varies by almost 2 orders of magnitude.
As mentioned above, spatial inhomogeneity has also been
proposed as the origin of large MR, and in particular linear
nonsaturating MR, in a number of systems.22,25 However,
spatially inhomogeneous conductors still exhibit a quadratic
MR [eq 1] at low enough elds B 1, and in this regime
experiment and modeling nd that A is always less than
1.22,25,26 Again, the possibility remains that the mobility is
underestimated, and A overestimated, due to inhomogeneity;
this possibility requires further investigation.
Lastly we discuss the low-eld MR. Figure 3c shows the MR
after subtracting the quadratic MR from ts to eq 1). We replot
the low eld data as the change in 2D conductivity ( = (B)
(B = 0)), in units of e2/h, where h is the Plancks constant.
We nd that the low-eld MR data are well-described by the
strong spinorbit coupling limit of the Hikami-Larkin-Nagaoka
(HLN) formula:29
(B) (0) =

1
B
e 2 B
ln +

2
2h B
B

(2)

where the only t parameter is the phase coherence eld B.


Figure 3d shows the phase coherence length L =

h
8eB

as a

function of carrier density for the various lms. In each instance


the coherence length is substantially larger than the thickness of
D

DOI: 10.1021/acs.nanolett.6b00638
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(20) Hall, E. H. Am. J. Math. 1879, 2, 287292.


(21) Ziman, J. M. Principles of the Theory of Solids; Cambridge
University Press, 1980
(22) Parish, M. M.; Littlewood, P. B. Nature 2003, 426, 162165.
(23) Adam, S.; Hwang, E. H.; Galitski, V. M.; Das Sarma, S. Proc.
Natl. Acad. Sci. U. S. A. 2007, 104, 1839218397.
(24) Cho, S.; Fuhrer, M. S. Phys. Rev. B: Condens. Matter Mater. Phys.
2008, 77, 081402.
(25) Kozlova, N. V.; et al. Nat. Commun. 2012, 3, 1097.
(26) Parish, M. Private Correspondence, 2015.
(27) Skinner, B. Phys. Rev. B: Condens. Matter Mater. Phys. 2014, 90,
15.
(28) Ramakrishnan, N.; Milletari, M.; Adam, S. Phys. Rev. B: Condens.
Matter Mater. Phys. 2015, 92, 245120.
(29) Hikami, S.; Larkin, A. I.; Nagaoka, Y. Prog. Theor. Phys. 1980, 63,
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(30) Kawabata, K. Solid State Commun. 1980, 34, 431432.
(31) Lu, H. Z.; Shen, S. Q. Phys. Rev. B 2015, 34, 431432.
(32) Ki, D. K.; Jeong, D.; Choi, J. H.; Lee, H. J.; Park, K. S. Phys. Rev.
B: Condens. Matter Mater. Phys. 2008, 78, 125409.
(33) Chen, J.; et al. Phys. Rev. Lett. 2010, 105, 14.
(34) Adroguer, P.; Liu, W. E.; Culcer, D.; Hankiewicz, E. M. Phys.
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ASSOCIATED CONTENT

* Supporting Information
S

The Supporting Information is available free of charge on the


ACS Publications website at DOI: 10.1021/acs.nanolett.6b00638.
Detailed sample preparation methods, lm growth
parameters, and characterization technique specics
(PDF)

AUTHOR INFORMATION

Corresponding Author

*E-mail: mark.edmonds@monash.edu.
Author Contributions

J.H. and M.T.E. contributed equally to this work. J.H., M.T.E.,


and M.S.F. devised the experiments. J.H. and M.T.E. performed
the growth, STM and transport. B.W. and C.L. aided the UHV
experiments. J.H., M.T.E., C.L., A.T., and K.M.O. performed
the LEED and growth of samples at the Australian
Synchrotron. N.R. and S.A. assisted with the theoretical
understanding and interpretation of the transport data. J.H.,
M.T.E., and M.S.F. analyzed the data and composed the
manuscript.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
This work was performed in part at the Melbourne Centre for
Nanofabrication (MCN) in the Victorian Node of the
Australian National Fabrication Facility (ANFF). LEED
measurements were performed at the Soft X-ray Beamline of
the Australian Synchrotron. J.H., M.T.E., B.W., and M.S.F. are
supported by M.S.F.s ARC Laureate fellowship
(FL120100038). M.T.E. and B.W. garner additional support
from their respective ARC DECRA fellowships (DE160101157
and DE160101334). S.A. and N.R. are supported under the
National Research Foundation of Singapores fellowship
program (NRF-NRFF2012-01).

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E

DOI: 10.1021/acs.nanolett.6b00638
Nano Lett. XXXX, XXX, XXXXXX

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