American Journal of Nano Research and Applications

2020; 8(3): 35-41

http://www.sciencepublishinggroup.com/j/nano
doi: 10.11648/j.nano.20200803.11
ISSN: 2575-3754 (Print); ISSN: 2575-3738 (Online)

Surface and Quantum Effects in Nanosized Semiconductor

Augustine Ike Onyia, Henry Ifeanyi Ikeri, Abraham Iheanyichukwu Chima
Department of Industrial Physics, Enugu State University of Science and Technology, Enugu, Nigeria

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To cite this article:

Augustine Ike Onyia, Henry Ifeanyi Ikeri, Abraham Iheanyichukwu Chima. Surface and Quantum Effects in Nanosized Semiconductor.
American Journal of Nano Research and Applications. Vol. 8, No. 3, 2020, pp. 35-41. doi: 10.11648/j.nano.20200803.11

Received: July 29, 2020; Accepted: August 11, 2020; Published: August 19, 2020

Abstract: Novel properties of nano-scale semiconductors based on the surface and quantum effects have been studied and
applications identified. Spherical potential well model is used to study quantum effect whereas basic geometrical models are
used for the surface effect. We have shown such effects to be the fundamental factors responsible for the novel nanosized
semiconductor characteristics different from the bulk of same material. It is found that the surface area to volume ratio follows
inverse power law. Thus at nanoscale, the surface to volume ratio increases significantly to enhance chemical reactivity. In
addition, the increased surface area makes most nananocrystals highly soluble in liquid and dramatically lowers their melting
temperature. The result strongly suggests also that the shape of the nanoparticles influences the surface area which has huge
impact on their properties and performance. Our results of quantum size effect reveal that spatial confinement of charge
carriers within semiconductor nanocrystals significantly modulates their properties such as size dependent absorption and
emission spectra with non-zero discrete electronic transition energies as well as their blue shift band gaps. Thus by changing
the size of the particle, we can literally fine-tune a material property of interest such as optical, electrical, and surface area.
Specifically we found that InAs and InSb nano semiconductor optical absorption spectrum, in contrast to their bulk, can be
tuned in broad range of UV to IR regions which are favorable operating wavelengths for nano photonic technology such as IR
photo detectors and full spectrum solar cells applications.

Keywords: Nanocrystal, Quantum Confinement, Quantum Effect, Semiconductor, Surface Effect

properties of matter are related to the atoms and molecules

1. Introduction that constitute the substance and their chemical bonds [4]. A
The large surface area, discrete electronic transitions and second prime example is evident in quantum tunneling in
tunable chemical, biological and physical properties of which if a particle with energy E encounters a barrier of
semiconductor nanocrystals have, in recent times, attracted energy U the probability of finding the particle across the
research interests. Microelectronics have advanced towards barrier if E < U is not zero but finite [5]. In addition
nanoscale electronics such that microelectronics basic nanoparticles exhibit wave-like behaviour known as matter
building blocks: molecules, atoms, and even electrons, can wave introduced by de Broglie, with a wavelength that is
be manipulated. The physical laws which govern the inversely dependent on the particle's linear momentum. The
behavior of particles in nano-scale regime are significantly gravitational forces become negligible due to the small mass
different from the laws of classical physics which control in this size range whereas electromagnetic forces become
the operation of macro and microelectronic devices [1]. increasingly more important and are dominant in determining
Quantum mechanical model is better used to describe the behavior of atoms and molecules [6].
motion and energy of the system in this small length scale Nanosized semiconductors exhibit quantum structures, one
dimension [2, 3]. in which the motion of the charge carrier is confined in one
A potent example of nanoscopic phenomenon is quantum or more directions by potential barriers, such as in quantum
effect tuning of the material properties. Precisely, as the size wells, quantum wires, and quantum dots in contrast to bulk
of semiconductors are reduced to nanoscale, the properties semiconductors that have their charge carriers free to move
become size dependent contrary to the bulk in which the within their respective bands in all the three directions, [7].
When the charge carriers are confined in one-direction, the
36 Augustine Ike Onyia et al.: Surface and Quantum Effects in Nanosized Semiconductor

energy is only continuous in the two-dimensional space, we 2. Fundamental Concept

have quantum wells or quantum films. Also, if the carriers
are confined in the two-directions and the energy is The properties of semiconductors vary as their size
continuous in one dimension, we have quantum wires or approaches the nanoscale dimension and as the greater
quantum rods. In the same way if the charge carriers are proportion of atoms at the surface of the material becomes
confined in all three spatial directions and there is zero significant leading to dramatic change in the physical and
dimensional degree of freedom, the resulting material is chemical properties of the material contrary to their
termed quantum dots (QDs) [8]. equivalent chemical compound in large dimensions making
Among the family of the confined structures, the properties of nanoparticles strongly size-dependent.
semiconductors QDs have emerged as the ultimate limit in These novel properties stems from the quantum and surface
charge carrier confinement due to the 3D space carrier effects that matter exhibits at the nanoscale, which serves as
confinement. In such structures, energy bands display fundamental tools to push the basic scientific and engineering
discrete electronic states reminiscent of isolated atoms and knowledge in many area of modern science and technology
electrical and optical properties change significantly from enabling novel applications and interesting materials.
those of bulk materials [9] and the fundamental band gap of In a bulk semiconductor, the valence and conduction bands
the system becomes size-dependent contrary to the bulk in are close and it is easy to excite an electron into the
which band gap maintains its original value due to the conduction band where they can move around. Once the
continuous energy state. QD band gap is thus tunable [10]. electron is excited into conduction band it leaves an empty
Thus by changing the size of the particle we can literally space behind in the valence band called a hole as shown in
fine-tune material properties thereby allowing the Figure 1. The negatively charge electron and positively
engineering of new materials that have their bandgaps at charged hole interact through the electrostatic Coulomb
custom designed energies to suite device applications [11]. potential to form a bound state known as exciton.
The surface area of the semiconductor nanocrystal also
plays a key role on the properties of the material. The
nanocrystals have a relative larger surface area when
compared to the same volume of material made up of bigger
particles [12]. The increased surface area presents more
atoms for increased chemical and physical activity such as
catalysis and detection reactions [13-15].
In addition, increased surface area has the following effect:
(i) it increases the surface energy and hence decreases the
melting point:- 3nm CdSe nanosized semiconductor melts at
700K whereas the bulk counterpart melts at 1678K (ii) it
makes most nano semiconductors highly soluble in liquid
which found applications in pigments, paints, medicine pills
etc (iii) it increases the adsorption processes which is useful
in applications like water purification device, waste recovery
techniques, manufacturing of perfumes and kadhesive among
others [16]. Other researchers have shown that the shape of
the nanoparticles influences the surface area which may have
Figure 1. Semiconductor energy band diagram.
huge effect on their properties.
Many benefits of semiconductor depend on the fact that it The exciton behaves like a hydrogen atom in which a hole
is possible to tailor the material structures to extremely small instead of the proton forms the nucleus. The average distance
scales to achieve specific properties. Using quantum or between the excited electron in the conduction band and hole
surface effect, materials can effectively be made more it leaves behind in the valence band is defined as the exciton
reactive, better electrical conductors, stronger, lighter or Bohr radius mathematically expressed as (18):
more durable. The size effect and surface effect are the two
fundamental effects that modulate the behavior of = ∗ + ∗ (1)
semiconductors in nano size regime. The unique physical and
chemical properties of semiconductor nanocrystals make ∗
where ℎ, , , ∗ are plank constant, dielectric
them suitable for applications in emerging technologies, such
constant, electronic charge, effective masses of electron and
as catalysis, nanoelectronics, nanophotonics, energy hole respectively. A central concept in quantum physics is
conversion, non-linear optics, solar cells, detectors etc [17]. the wave-particle duality, introduced by de Broglie, in which
In this paper we have provided a comprehensive theoretical a nanoparticle can be associated with a matter wave with a
study of the impact of surface and quantum effects on the wavelength known as de Broglie wavelength expressed in
physical and chemical properties and applications of terms of the particle linear momentum p and Planck constant
semiconductor nanocrystals. h as:
 American Journal of Nano Research and Applications 2020; 8(3): 35-41 37

= (2) This energy term represents the infinite potential spherical

well contribution due to quantum confinement of charge
The exciton Bohrs radius and de Broglie wavelength are carriers in 3D. While the above equation is for one particle in
characteristic length scales that delineate the transition a quantum sphere, we extend the same concept to the two
between the bulk state and nanoscale regime upon which the particle exciton (electron and a hole) and obtained:
quantum effects are used to describe the particles behaviour.
Thus whenever the dimension of semiconductor materials is = ∗ + ∗ (6)
$
reduced to a size comparable with de Broglie wavelength or
exciton’s Bohr radius they become small enough to confine This energy term is derived from the particle-in-a-
their charge carriers and produce quantum effects [19], and spherical box solution of the Schrödinger equation that has
the size-dependent properties become apparent resulting to been expanded to a sphere with an electron particle and a
novel properties different from their bulk values. The corresponding hole, where ∗ and ∗ are the effective
quantum effect describes the physics of material properties in masses of the electrons and holes, respectively. Columbic
nanoscale regime. This effect is not significant going from interaction between the negatively (electron) and positively
macro to micro dimensions. Its only becomes dominant when (hole) charged each with charge of magnitude e according to
the nanometer size range is reached. Thus materials reduced Coulomb’s law, is on the order of:
to the nanoscale can suddenly display very different * .
= (7)
properties compared to what they exhibit on a macroscale , -$
which represents a significant step forward.
The energy levels of the semiconductor nanocrytals can be where; 1.8 is a coefficient due to wave function overlap
between the electron and hole in the first excited state
understood by solving Schrodinger equation of quantum
whereas the minus sign indicates that two particles (electron
mechanics for the electrons and holes in the potential wells
and hole) are of opposite charges. This energy third term
located by the band discontinuities. This is a real life scenario of
represents the electrostatic energy contribution due to
the famous particle in a box, whose energy level is given as [20]: coulomb’s attraction between the electron and the hole. The
last energy term contribution is the infinite crystal bandgap
= (3) energy ./01234 of the host semiconductor which is a
This energy term represents the infinite potential well characteristic of the material. The ground state excitation
energy of semiconductor nanocrystals is the sum of the three
contribution due to confinement of the charge carriers. Here
energy contributions thus given as:
L is the length of the confinement region, m is the mass of
the particle, h is the planck constant and n is the quantum .
./567 4 = ./01234 + ∗ + ∗ − (8)
number that labels the different confined energy levels of the $ , -$
particle in the well. In general, charge carriers (electrons and
holes) in a semiconductor nanocrystal are confined in all The fundamental relationship between the excitation
spatial 3D [21]. So we considered these charge carriers energy ./567 4 and the optical absorption wavelength
trapped in an infinite 3-dimensional potential well. The /567 4 of semiconductor nanocrystals is expressed as:
simplest shape of a three-dimensional box considered is 9
/567 4 = (9)
sphere. We therefore extend the concept of energy in a one- :;/<=7 4
dimensional potential well to the case of a sphere of interest
applying the necessary boundary conditions and obtained the The other crucial aspect of nanocrystals responsible for
lowest allowed energy level (kinetic energy) as: their novel behaviour is the surface effect. Thus surface area
to volume ratio for a material or substance made of
!",#
, = ℎ% (4) nanoparticles has a significant effect on the properties of the
$
material. Nanoscale materials have a relatively larger surface
where: area when compared to the same mass of material in bulk
1) & %, is the mth root of the spherical Bessel function of form [22]. This makes nanocrystals more chemically reactive
quantum number n (in some cases materials that are inert in bulk form are
2) ' is the radius of the QD reactive in their nanoscale form), which has significant
3) μ is the reduced effective mass impact on their strength or electrical properties [23]. We
4) , is the confinement energy (energy state) of the considered spherical and cubic nanocrystals geometries and
electron and hole. applied basic geometric formulas to establish a fundamental
The ground state kinetic energy which is the commonly surface area to volume relationship. For spherical shape
observed state corresponds to (β21, 0 = π and n = 1) and is semiconductor nanocrystal the Equation for the surface area
given as: S of the sphere of radius r is expressed as:

= (5) > = 4@ %
(10)
,) $
Volume of the sphere V is defined as:
38 Augustine Ike Onyia et al.: Surface and Quantum Effects in Nanosized Semiconductor

A= @ B
(11) to ascertain the novel properties of semiconductors in
B
nanoscale regime. The input parameters used in the theoretical
Then the surface area to the volume ratio C becomes: calculation have been listed in Table 1.’ We have also used the
Equations 11 and 14 for the computation of surface area per
D
C= E F (12) unit volume of various sizes of the nanocrystal for the
D spherical and cubic nano semiconductors respectively
F

Thus Table 1. The material parameters used for the Study.

B NO P∗Q P∗R ST
C= (13) QDs
D InAs 0.36eV 0.02mo 0.40mo 15.15
1 InSb 0.17eV 0.02mo 0.40mo 16.80
→ C ∝ GaAs 1.42eV 0.06mo 0.51mo 12.90

Similarly for cubic shape semiconductor nanocrystal of the 4. Result and Discussion
length of a side L the Equation. of the surface area S of the
sphere is: Figure 2 shows the excitonic kinetic energy as a function of
semiconductor nanocrystal size. Thus as the confinement length
> = 6K% (14) is reduced charge carriers assume higher kinetic energies
Volume of the cube V is: resulting in increased energy levels. As the kinetic energy is
inversely dependent on the effective mass this implies that
A = KB (15) lighter particles experience stronger effect which in turn means
that light and heavy hole states possess different energies in
Then the surface area to the volume ratio & becomes: contrast to parental bulk. The spatial confinement of charge
L carriers within the quantum box has two fundamental
&= F (16)
consequences that significantly modulate the carrier states.
Firstly, it causes the electronic states to become discrete with
Thus
controllable atomic-like states which shift the effective band
L
&= (17) edge to higher energies in sharp contrast to the bulk whose
electronic energy levels are distributed in continuous bands.
1 Thus energy level spacing increases sharply with decreasing
→ & ∝
K nanocrystal size. Secondly, confinement brings electrons and
hole closer and therefore enhances the radiative recombination
The radius r and length L are both referred here as sizes likelihood compared to the bulk where electron and hole are not
hence surface to volume ratio for both spherical and cubic spatially confined and can be easily dissociated enhancing the
geometrical nanocrystals indicates that the surface area probability of non radiative recombination.
increases faster relative to the volume as crystal size
decreases Maximum exposed surface area signifies an
improved reactivity thus greater percentage of the material
atoms are exposed for potential reaction.
In nanoscience the shape of the nanoparticles also plays
critical role on the surface area of the material and influences
their properties. Given Equ. 10 the surface area per unit
B
volume for a sphere C = and Equ. 14 for the cubic shape,
D
L
& = , therefore between a spheric and cubic shapes of same
volume there will be larger increased surface area in the cube
relative to the sphere and for this particular reason not only
the size of the nanoparticles is vital but also their shape.

3. Materials and Methods

The verified experimental parameters we used for the this
study are: effective masses of electron ∗ , and hole, ∗ ,,
dielectric constants and bandgap energy M for GaAs, InSb Figure 2. Excitonic kinetic energy versus nanocrystal size for InSb, InAs and
and InAs QDs as shown in the Table 1 whereas the constant GaAs QDs.
parameters used in the computation are listed in the appendix.
Variation in excitonic kinetic energy, excitonic excitation As the dot radius increases, the kinetic energy for all
energy and optical wavelength as a function of nanocrystal size nanocrystal decrease exponentially but never reaches zero. It
was computed using Equation 3, 6 and 7 respectively, in order means that charge carriers in the nanocrystals can never be in
 American Journal of Nano Research and Applications 2020; 8(3): 35-41 39

a state of rest and even in the ground state the charge carriers 700nm to 2500nm can be absorbed indicating excellent
possess a non-zero minimum kinetic energy. absorption wavelengths in UV to infrared IR region. As a
In the Figure 3 showing the excitation energy as a function result, their light absorption can be tuned throughout the UV,
of nanocrystal size, a substantial increase in the exciton visible and IR ranges which are favorable operating
excitation energy and hence the separation between the wavelengths for photonic technology such as IR photo
valence and conduction bands with decreasing crystal size is detectors and solar cells applications.
observed. The increase of excitation energy is due to
quantum confinement. This therefore implies that
fundamental bandgap energy of a nanoscale semiconductor is
size-dependent and can be tuned by varying the crystallite
size. Accordingly, a large optical blue shift is observed in the
excitation energy spectrum as compared with the bulk
materials that are characterized by composition-dependent
bandgap energy. As earlier stated nanosize semiconductors
have quantized energy levels and as a result electron transfer
can only occur between these discrete electronic states.
Consequently only light of certain dimension can be
absorbed leading to monochromatic emissions. The
structures with such a discrete energy spectrum are the basis
for the development of new types of nanoelectronic devices.
The tunable excitation energy allows nanosize
semiconductors to be optimally engineered for the different
applications particularly in solar cells in which they can be Figure 4. Nanocrystal size versus wavelength for InSb, InAs and GaAs QDs.
tuned to harvest the full broad spectrum of solar radiation.

Figure 5. Surface area per unit volume versus spherical and cubic
Figure 3. Excitonic excitation energy vrsus nanocrystal size for InSb, InAs nanocrytal size.
and GaAs QDs.
The Figure 5 shows surface area per unit volume for
The Figure 4 shows semiconductor nanocrystal size as a different crystal sizes both for the cubic and spherical shape
function of optical wavelength. The absorbance wavelength nanocrystals. It is found that the surface area to volume ratio
shows positve correlation with the crystalline size. As the scales as inverse power law and increases as the size of the
cryatal decreases in size absorption edge shift towards shorter particle decreases. This also implies for a given volume of
wavelengths (blue shift) which demonstrate size dependent material made up of smaller particles, the surface area of the
absorption and fluorescence spectra. Thus tuning the size of material increases and thus has a relative larger surface area
semiconductor nanocrystal means tuning the wavelengths of when compared to the same volume of material made up of
absorption and fluorescence by the nanocrystal, which in turn larger particles. Generally, the higher the surface area implies
means same material emits different colours at various higher surface atoms. Thus greater portion of their existing
crystallite size and are being studied as alternative light atoms are found at the surface. This leads to nanoscale
emitting sources. By varying GaAs, InSb and InAs QDs in semiconductors being more chemically reactive. As chemical
broad range, wavelengths covering the whole of Ultraviolet reactions occur between particles that are on the surface, a
UV to visible spectra were observed. However, increasing given mass of nanomaterial will be much more reactive than
the radius further for InAs and InSb, wavelength covering
40 Augustine Ike Onyia et al.: Surface and Quantum Effects in Nanosized Semiconductor

the same mass of material made up of large particles. In Additionally, the increased surface to volume ratio makes
general perspective physical and chemical properties of a most nananocrystal highly soluble in liquid and dramatically
material greatly depend on the surface atoms, and the fact lowers their melting point, which found applications in many
that a significant number of atoms exist at the surface in chemical industries.
nanocrystals implies tremendous effects on the reactions that We have also shown that properties of nanoparticles are
occur at interface (surface) such as catalysis and detection not only determined by size but also by their shape. These
reactions. The active site in the catalyst where the reaction unique properties are due the quantum and surface effects
takes place is significantly favored by the surface effect and that matter exhibits at the nanoscale, and have shown great
thus increases with the decreased in the size of the value for application in emerging technologies, such as
nanocatalysts. This dramatically enhances the ultimate goal nanoelectronics, nanophotonics, energy conversion, non-
of catalysis processes to increase the rate of a given reaction. linear optics, miniaturized sensors detectors and many others.
Nanomaterias also play critical role in detection However, in this work we did not account on the
applications like biosensors or chemical sensors for detection mathematical relationship to aid the fabrication of
of a specific biological and chemical compound within a nanoparticles to optimize their shape for specific property.
mixture. The detection reaction like catalysis also occurs at Therefore more efforts should be focus on the formulation of
the material surface. The increased surface to volume ratio as model that controls specific property for a given shape.
matter is reduced to nanoscales increases the surface area
available for detection. This strongly indicates that further Appendix
reduction in the crystal size creates more detection sites
thereby enabling multiple detection of analytes. In this way it Table 2. Approximate values of some physical constants.
is possible to engineer super small multiplex detection device Quantity Value
that can test and detect more than one analyte at a time. Electronic Charge (e) 1.6 x 10-19C
Further consequence of the increased surface area on Speed of light (c) 3 x 108m/s
nanoparticles is that it will have tremendous effect on the Planck’s constant (h) 6.63 x 10-34 J.S
melting temperature owing to the fact that surface atoms are Electron rest mass (m0) 9.11 x 10-34 kg
Electron volt (eV) 1.6 x 10-19 J
easily ionized than the bulk atoms, thus the total energy
Permittivity of free space 8.85 x 10-12 fm-1
required to surmount the intermolecular forces that hold the Pi (π) 3.142
atoms fixed will be less which have a dramatic depression on
their melting point. Furthermore, the increased surface area
makes most nananocrystal highly soluble in liquid which
found applications in many chemical industries. The results
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