PHYSICAL REVIEW B 95, 205414 (2017)

Unusual quantum confined Stark effect and Aharonov-Bohm oscillations in semiconductor

quantum rings with anisotropic effective masses
G. O. de Sousa,1,* D. R. da Costa,1,† Andrey Chaves,1,2,‡ G. A. Farias,1,§ and F. M. Peeters1,3,
1
Departamento de Física, Universidade Federal do Ceará, Caixa Postal 6030, Campus do Pici, 60455-900 Fortaleza, Ceará, Brazil
2
Department of Chemistry, Columbia University, 3000 Broadway, New York, New York 10027, USA
3
Department of Physics, University of Antwerp, Groenenborgerlaan 171, B-2020 Antwerp, Belgium
(Received 4 January 2017; revised manuscript received 20 April 2017; published 11 May 2017)

The effects of external electric and magnetic fields on the energy spectrum of quantum rings made out of a
bidimensional semiconductor material with anisotropic band structures are investigated within the effective-mass
model. The interplay between the effective-mass anisotropy and the radial confinement leads to wave functions
that are strongly localized at two diametrically opposite regions where the kinetic energy is lowest due to the
highest effective mass. We show that this quantum phenomenon has clear consequences on the behavior of the
energy states in the presence of applied in-plane electric fields and out-of-plane magnetic fields. In the former,
the quantum confined Stark effect is observed with either linear or quadratic shifts, depending on the direction
of the applied field. As for the latter, the usual Aharonov-Bohm oscillations are not observed for a circularly
symmetric confining potential, however they can be reinstated if an elliptic ring with an appropriate aspect ratio
is chosen.

DOI: 10.1103/PhysRevB.95.205414

I. INTRODUCTION mobility [11], thermal transport [32,33], and even mechanical

strain response [34,35], yields the possibility for designing
The possibility for obtaining atomically thin direct-gap
and engineering different electronic devices based on these
semiconductors from exfoliation of their layered bulk ver-
anisotropic properties [4,11,36–41].
sion [1–3] has brought excitement towards the search
Although a lot is known already about the physics of charge
for different materials that allow for a stable monolayer
carriers in large flakes of 2D materials, relatively little work
(or few-layer) form. Density functional theory calculations for
has been published on engineered in-plane quantum confined
some of these materials, namely, black phosphorus (BP) [4],
structures in these systems [42]. The local confinement of
arsenene [5], ReS2 [6], and TiS3 [7], among others, predict
electrons and holes into finite regions of 2D materials, either
anisotropic energy bands which, in some cases, have even
by designed electrostatic gates above the layer, or even by
been verified experimentally by angle-resolved photoemission
just cutting the layer into a desired shape, seems to be a
spectroscopy [4] and the observation of linear dichroism
natural step to be taken next in the development of this field.
and polarization-dependent absorption [8–10]. Currently, BP
For instance, current technological advances developed for
is perhaps the most prominent among the anisotropic two-
confining carriers in semiconductor-based two-dimensional
dimensional (2D) materials. It is the most stable crystal
electron gases into finite regions by gate control [43–45] or by
form of phosphorus, which has been the subject of renewed
cutting graphene into quantum dots and rings [46–48] could be
interest since its recent isolation and characterization in few
transferred to the case of general 2D materials, thus enabling
layers [4,11–14]. Just like graphene [15,16], silicene [17,18]
the study of quantum confined structures, such as planar
and germanene [19,20], monolayer black phosphorus (also
semiconductor quantum dots and rings with atomic thickness.
called phosphorene) is an elemental 2D crystal as opposed
In this paper, we theoretically investigate, within the
to the other materials that compose the layered (van der
effective-mass approximation, the energy levels of a 2D
Waals) materials zoo, such as the transition-metal chalco-
semiconductor material with anisotropic effective masses.
genides [1,3,21,22] and boron nitride [23–25]. Phosphorus
As a case study, we apply our model to electrons in the
atoms in phosphorene are organized in a puckered hexagonal
conduction band of a few-layer black phosphorus quantum
lattice, which yields a unique band structure where conduction-
ring. We demonstrate that the effective-mass anisotropy of
and valence-band minima are found at the  point of the
this system leads to an interesting quantum confinement
Brillouin zone with anisotropic effective masses separated by
effect, namely, a localization of the electronic wave function
an energy gap that, depending on the layer number, ranges
along diametrically opposite regions of the ring. This has
from 0.3 eV (bulk) to 2.15 eV (monolayer) [11,14,26–31].
consequences, e.g., in the behavior of the confined particle
Therefore, besides the interesting tunable semiconducting
under external applied electric and magnetic fields, as we will
properties of this material, its mass anisotropy, which is
demonstrate further on. The physical phenomena discussed
reflected in several of its physical properties, such as carrier
here for electrons also are expected to be shared by holes
where, e.g., in the case of phosphorene, even a much larger
* mass anisotropy is present.
[email protected]
†
[email protected] II. THEORETICAL MODEL
‡
[email protected]
§
[email protected] We consider conduction-band electrons in a material with

[email protected] anisotropic mass, confined in a ringlike region defined by

2469-9950/2017/95(20)/205414(7) 205414-1 ©2017 American Physical Society

DE SOUSA, DA COSTA, CHAVES, FARIAS, AND PEETERS PHYSICAL REVIEW B 95, 205414 (2017)

the x direction has a direct consequence in the wave-function

distributions over the ring as we will demonstrate in what
follows. The presence of an in-plane electric field is described
by an extra potential Vf (x,y) = eF (x cos θ + y sin ,θ ) added
to Eq. (2), where θ is the angle that the field makes with the
x (armchair) axis. Magnetic fields, on the other hand, are
included by the gauge-invariant Peierls-like transformation
in the finite difference scheme used to solve Eq. (1) as
described by Governale and Ungarelli [53]. In simple words,
this transformation consists of writing the finite difference
form of the kinetic-energy operators in Eq. (1) as
†
(x) h̄2 2δij − Ux (xi ,yj )δi+1,j − Ux (xi ,yj )δi−1,j
Ki,j = ,
2m0 mx x 2
†
(y) h̄2 2δij − Uy (xi ,yj )δi,j +1 − Uy (xi ,yj )δi,j −1
Ki,j = , (3)
2m0 my y 2

where x(y) is the grid spacing in the x(y) direction

FIG. 1. Ten lowest-energy levels of the BP quantum ring
(assumed to be regular over the entire grid) and the phase
(sketched in the inset) in the absence of applied fields as a function
of the ring width (W = Re − Ri ), keeping the average radius fixed as
factor Ux(y) (xi ,yj ) = exp[ie x(y)Ax(y) (xi ,yj )/h̄] makes the
(Re + Ri )/2 = 20 nm. kinetic-energy operator invariant for gauge transformations
of the vector potential A.  The Schrödinger equation for the
Hamiltonian Eq. (1), discretized in finite differences with the
two circles with internal (external) radius Ri(e) , as illustrated proper transformations to include external magnetic fields,
in the inset of Fig. 1. Within the effective-mass model, the then is solved numerically to obtain the energy levels and
Hamiltonian describing this system is given by wave functions.
 
1 px2 py2
H = + + V (x,y), (1)
2m0 mx my III. STARK EFFECT

where Figure 1 shows the first ten low-lying energy levels of

  electrons in a BP circular quantum ring as a function of
0, Ri  +
x2 y2  Re ,
V (x,y) = (2) the ring width. As expected, all energy states decrease as
∞, otherwise.
the width increases, and they are all doubly degenerate.
Such a confining potential in a gapped 2D material can Surprisingly, even the ground state is doubly degenerate,
approximately be achieved experimentally, e.g., by using which is unusual for quantum rings where the ground state is
designed electrostatic gates over the layer [49]. Quantum normally a nondegenerate state with angular momentum l = 0.
rings cut out from an infinite layer would also provide infinite Throughout the remainder of this paper, internal and external
potential barriers for electron confinement within the system, ring radii will be assumed to be Ri = 10 and Re = 20 nm,
but in this case, effects due to zigzag, armchair, or skewed [50] respectively, unless otherwise stated.
edges would also play a role in the energy spectrum, leading Figure 2 shows the wave functions of the first six low-
to edge localized states whose energy lies inside the gap [51]. lying electron states confined in the BP quantum ring.
The band-structure anisotropy is reflected in the effective The symmetric/antisymmetric natures of the pairs of states
mass, which is different for each in-plane direction. We are reminiscent of a double quantum well structure along
assume the material parameters for phosphorene, but similar the y direction, which explains the double degeneracy of
qualitative results are expected for any of the other anisotropic the states observed in Fig. 1. In fact, electrons and holes are
materials mentioned in the Introduction. In fact, the use of expected to have their wave functions localized in the upper
such an effective-mass model as described here is justified and lower sides of the ring with an almost zero wave function
when we investigate low-energy quasiparticles around a around y = 0: The sectors of the potential around y ≈ 0 and
band minimum in a system where bands are sufficiently y ≈ ±(Re + Ri )/2 can be seen as separate quantum wells
separate in energy. In the four-band tight-binding model of along the vertical and horizontal directions, respectively. Since
phosphorene, for example, this would be the case at the the effective mass is larger in the y direction, the confinement
energy gap around the  point: Conduction and valence energy for a horizontal well is lower, hence the preference of
bands are separate by an ≈2 eV gap, whereas the top and the wave functions for the y ≈ ±(Re + Ri )/2 regions. This
bottom bands are separate from them by ≈ 5 eV [39]. In is thus a purely quantum-mechanical effect, coming from the
this situation, it is safe to assume electrons populate a single nonzero lowest kinetic energy of the confined particles, which
conduction band around . The electron effective masses in is inversely proportional to their effective masses. Another
the x and y directions, respectively, are mex = 0.0826m0 and feature that is a consequence of the quantum confinement
mey = 1.027m0 for monolayer phosphorene [52]. The fact that nature is the increase in the number of nodes in the wave
the effective mass in the y direction is larger than that in function with higher states.

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UNUSUAL QUANTUM CONFINED STARK EFFECT AND . . . PHYSICAL REVIEW B 95, 205414 (2017)

(a) (b) (c)

(d) (e) (f)

Min 0 Max

FIG. 2. Wave functions for the first six low-lying states in the
absence of electric and magnetic fields, being (a), (c), and (e) FIG. 4. Splitting E2 − E1 (right scale) of the first low-lying two
symmetric and (b), (d), and (f) antisymmetric. The ring width is energy levels E1 and E2 (left scale) of a BP quantum ring as a function
fixed as W = 10 nm with internal (external) radii of Ri = 10 nm of the in-plane electric-field amplitude F for θ = 0 [see Fig. 3(a)]
(Re = 20 nm). along with the wave functions for the (I) first and (II) second states at
F = 200 kV/cm.

This peculiar double-well-like wave function has interest-

ing consequences on the behavior of the electron and hole x direction, a regular quadratic quantum confined Stark
energy levels under applied in-plane electric fields. As shown shift (QCSS) occurs as expected for quantum rings or dots.
in Fig. 3(a), if the field is applied along the (armchair) However, if the field is applied along the (zigzag) y direction,
the electric-field dependence of the energies becomes linear
with a series of crossings between excited states, thus forming
a spectrum that exhibits a close resemblance with the QCSS of
a double quantum well [54]. This behavior persists even when
considering different values of W . In fact, core-shell quantum
wires with eccentricity deformations also exhibit a very similar
phenomenon [55] where the resemblance is explained as due to
the analogy between a situation where the confining potential
is elliptic but the kinetic-energy band is a paraboloid (in
quantum wires) and a situation where the confining potential
is a circle but the kinetic energy is an elliptic paraboloid (in BP
quantum rings). This analogy will be discussed in greater detail
further on.
The slopes of all curves in Fig. 3(b) for different eigenstates
eventually converge to the linear function En = −eF (Re +
Ri )/2 + En0 , where En0 is a constant, which is different for
each state n. This is a consequence of the strong confinement
at yt = −(Re + Ri )/2, even for low fields so that the effect of
the applied field culminates just in shifting down the electron
energy by an amount of eF yt .
A more careful analysis of the ground and first excited states
in Fig. 3(a) shows that their degeneracy is lifted as the electric
field increases. This is illustrated in Fig. 4 where the difference
E2 − E1 significantly increases after F ≈ 30 kV/cm. In fact,
higher fields push electron wave functions towards the left part
of the ring out of the pockets where they were localized in the
absence of fields [see Figs. 2(a) and 2(b)] as one can verify by
the color maps of the wave functions for these states, shown
FIG. 3. Lowest ten energy levels of a BP quantum ring as a in the panels labeled (I) and (II) in Fig. 4. The energy due to a
function of the in-plane electric-field amplitude F , being (a) θ = 0 F ≈ 30-kV/cm field is enough to overcome the kinetic-energy
and (b) θ = π/2 the angle between the x axis and the vector F (see barrier around y = 0 created by mass anisotropy and, once the
the insets of the figures). The ring width is W = 10 nm with internal electron wave function is no longer in the double-well-like
(external) radii of Ri = 10 nm (Re = 20 nm). configuration, there is no longer a reason for the ground and

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DE SOUSA, DA COSTA, CHAVES, FARIAS, AND PEETERS PHYSICAL REVIEW B 95, 205414 (2017)

FIG. 5. Average position of the ground state as a function of

the in-plane electric-field amplitude F applied in the (a) x and (b)
y directions. Two different mass ratios were considered: the one
of BP (the solid black line) and mex /mey = 1 (the dashed red line)
with mex = mey = 1.027m0 . The inset exhibits a zoom around the
low electric-field amplitudes for F pointing towards the y direction,
showing that for any field value, the wave function in the y direction
moves immediately to such a preferred region inside the quantum
ring for the BP case.

first excited states to be degenerate. On the other hand, the

lifting of the degeneracy is very different in Fig. 3(b), and it
happens instantaneously when applying the field, that is due
to the strong double-well-like confinement.
The average position of the ground-state electron is shown FIG. 6. Energy levels of a circular BP quantum ring as a function
as a function of the external field intensity F by solid lines of the perpendicular magnetic-field B for different ring widths:
in Fig. 5. If the field is applied along the positive x direction, (a) W = 10 nm, (b) W = 20 nm, and (c) W = 40 nm. The average
Fig. 5(a) shows that x linearly decreases as expected for radius is kept fixed as (Re + Ri )/2 = 30 nm.
circularly confined electrons, such as in atoms and quantum
dots. This is however not the behavior found for regular
IV. AHARONOV-BOHM OSCILLATIONS
isotropic quantum rings as shown by the red curves for
mex /mey = 1 depicted in Figs. 5(a) and 5(b) for comparison, A ubiquitous feature of semiconductor quantum rings
which exhibit a smooth decay. Moreover, if the field points is its adequacy for the study of Aharonov-Bohm (AB)
towards the positive y direction, the average position y oscillations. It is well known that energy levels of a regular
abruptly decreases to y ≈ −14 nm, roughly the average isotropic ring enclosing a magnetic flux φ oscillate with
radius of the ring. This is a consequence of the double-well-like period φ = (n + 1/2)φ0 with an increasing perpendicularly
structure of this anisotropic mass confinement system where applied magnetic field, where n = 0,±1,±2, . . . is the angular
even the weakest applied field immediately makes the lower momentum index [56,57]. However, as previously discussed,
region of the ring more energetically favorable, thus confining the mass anisotropy in BP localizes the wave function so that
the whole wave function to this region as shown by the inset it no longer covers the whole ring and, consequently, AB
in Fig. 5(b). oscillations are suppressed as illustrated in Fig. 6 for different

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UNUSUAL QUANTUM CONFINED STARK EFFECT AND . . . PHYSICAL REVIEW B 95, 205414 (2017)

40
(a)

35
Min 0 Max

E (meV)
30

25
W = 10 nm
20
FIG. 7. (a) Elliptical quantum ring potential with (b) two eccen- 15 (b)
tricities: ε = 0 (circular) and ε = 0.9. (c) The ground (black solid)
and the first excited (red dashed) states energies as a function of the
external magnetic field, assuming different values of eccentricity,
for a fixed ring width of W = 40 nm and an average radius of 12

E (meV)
(Re + Ri )/2 = 30 nm.

values of ring width. For a ring as wide as W = 40 nm in 9

Fig. 6(c), AB oscillations still are observed for excited states
with higher energy, but the lowest-energy states exhibit no such W = 20 nm
oscillations and just have their energies increased quadratically 6
with the field (i.e., diamagnetic shift) as in the case of quantum 8
dots in the presence of a magnetic field [58]. Nevertheless,
(c)
one can bring back the oscillations, even for the ground
state, by designing an elliptic quantum ring as sketched in
Fig. 7(a) composed of concentric ellipses so that the potential 6
eccentricity “corrects” the eccentricity of the kinetic-energy
paraboloid band, coming from mass anisotropy. Figure 7(b)
E (meV)

presents a scheme of ellipses with two different eccentricities

in order to visualize the effect of high eccentricity. In fact, 4
regions of higher curvature in an elliptic ring are expected
to confine particles [59,60], which can thus be used to
counterbalance the effective-mass-induced confinement of the
W = 40 nm
circular ring and thus provide more evenly distributed wave 2
functions and, consequently, bring back the AB oscillations.
In this case, the confining potential in Eq. (2) has to be 0 2 4 6 8 10
replaced by
  B (T)
√
V (x,y) = 0, R i  x 2 + (y/ 1 − ε2 )2  Re , (4)
FIG. 8. Energy levels of an elliptic (ε = 0.9) BP quantum ring as
∞, otherwise, a function of perpendicular magnetic-field B for ring widths (a) W =
where the eccentricity is given by ε = 1 − ai /bi = 1 − ae /be 10 nm, (b) W = 20 nm, and (c) W = 40 nm. The average radius is
[ε = 0 in the circular case, see Fig. 7(b)]. i and e denote the kept fixed at (Re + Ri )/2 = 30 nm. The insets show the ground-state
inner and outer ellipses, and ai,e and bi,e are the semiminor wave functions for the three different widths and B = 0 T. The red
axis and semimajor axis, respectively [see Fig. 7(a)]. (blue) color represents high (low) wave-function amplitude.
Figure 7(c) shows more pronounced AB oscillations in the
ground and first excited states as a function of a magnetic in the same sub-band exhibit periodic crossings, whereas
field with increasing eccentricity. Figure 8 shows that, in the different sub-bands are separated by anticrossings. Notice that
elliptical (ε = 0.9) confinement case, as the width increases, the period of AB oscillations in Fig. 8 is slightly different
the wave function spreads out more over the ring. The for each ring width as a consequence of the different areas
lowest-energy levels in Fig. 8(a) are almost independent of the enclosed by rings with different widths. The same is true for
magnetic field, but, as the ring is made wider, the energy levels rings with different eccentricities in Fig. 7(c). The minima
exhibit the AB oscillatory feature [see Figs. 8(b) and 8(c)]. of the ground-state oscillations in Fig. 8(c) rise in energy
Nevertheless, the mass anisotropy effect is stronger, and the as the magnetic field increases (black line). This is expected
wave function (insets) still keeps its two peaks so that the since, as the magnetic field increases, the magnetic length
energy levels group into twofold oscillating sub-bands. States is reduced, squeezing the electron towards the central region

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DE SOUSA, DA COSTA, CHAVES, FARIAS, AND PEETERS PHYSICAL REVIEW B 95, 205414 (2017)

and, consequently, increasing its energy. Notice the width of mass in the y direction (zigzag direction). Thus, this feature
the circular ring in Fig. 6(b) is the same as the one for the can be used, e.g., to analyze the crystal directions of the
elliptic ring in Fig. 8(b). Yet, only the latter exhibits clear system.
AB oscillations, especially for excited states, thus proving the Furthermore, in the presence of a perpendicular magnetic
importance of the ring eccentricity in observing the AB effect field, our results also show that a circular anisotropic mass ring
in quantum rings made out of BP. does not exhibit AB oscillations in the energy spectrum, which
also is attributed to the anisotropy-induced wave-function
V. CONCLUSIONS localization. However, if the electron is confined rather by
an elliptical potential ring, the localization effect is reduced,
We have investigated the effect of applied electric and and it becomes possible to recover the AB oscillations.
magnetic fields on the energy levels of conduction-band Our numerical results were obtained using parameters for
electrons confined into a quantum ring made of an anisotropic monolayer black phosphorus, although the same qualitative
material. Due to the mass anisotropy, the probability density features are expected for any system with effective-mass
is demonstrated to be not evenly distributed along the ring anisotropy, such as arsenene ReS2 and even multilayer black
but rather concentrated in two diametrically opposite regions phosphorus.
of the system. As a consequence, our results show that, if the
applied electric field points towards the armchair direction, the
ACKNOWLEDGMENTS
energy-level and wave-function behaviors are reminiscent of
that of a pair of stacked (independent) quantum dots (quadratic This work was financially supported by CNPq under the
Stark shift), whereas if the same field points towards the PRONEX/FUNCAP grants, CAPES Foundation, the Flemish
zigzag direction, the system behaves as coupled quantum Science Foundation (FWO-Vl), and the Brazilian Program
wells (linear Stark shift). This is related to the higher effective Science Without Borders (CsF).

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