First-principle study of quantum confinement effect on small sized silicon quantum

dots using density-functional theory

M. M. Anas, A. P. Othman, and G. Gopir
Citation: AIP Conference Proceedings 1614, 104 (2014); doi: 10.1063/1.4895180
View online: http://dx.doi.org/10.1063/1.4895180
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First-principle Study of Quantum Confinement Effect on

Small Sized Silicon Quantum Dots using
Density-Functional Theory
M.M. Anas, A.P Othman and G. Gopir
School of Applied Physics, Faculty of Science and Technology, Universiti Kebangsaan Malaysia,
43600, Bangi, Selangor, Malaysia.
Abstract. Density functional theory (DFT), as a first-principle approach has successfully been implemented to study
nanoscale material. Here, DFT by numerical basis-set was used to study the quantum confinement effect as well as
electronic properties of silicon quantum dots (Si-QDs) in ground state condition. Selection of quantum dot models were
studied intensively before choosing the right structure for simulation. Next, the computational result were used to
examine and deduce the electronic properties and its density of state (DOS) for 14 spherical Si-QDs ranging in size up to
~2 nm in diameter. The energy gap was also deduced from the HOMO-LUMO results. The atomistic model of each
silicon QDs was constructed by repeating its crystal unit cell of face-centered cubic (FCC) structure, and reconstructed
until the spherical shape obtained. The core structure shows tetrahedral (Td) symmetry structure. It was found that the
model need to be passivated, and hence it was noticed that the confinement effect was more pronounced. The model was
optimized using Quasi-Newton method for each size of Si-QDs to get relaxed structure before it was simulated. In this
model the exchange-correlation potential (Vxc) of the electrons was treated by Local Density Approximation (LDA)
functional and Perdew-Zunger (PZ) functional.
Keywords: Density Functional Theory (DFT), Quantum Dots (QDs), HOMO-LUMO gap, LDA-PZ, DOS plot
PACS: 31.15.es

INTRODUCTION
Research on semiconductors at nanometer scale field had nowadays caught the attention of scientist worldwide.
Predicting nanomaterial optical and electronic properties is very challenging, including its energy band gaps and
density of states. All these challenges are still an outstanding problem in this rapidly growing area. Discussions
about the challenges in predicting the size dependence of the optical band gap silicon quantum dots have been
reported in theoretical approaches [1]. Producing samples of pure, crystalline, monodispersed silicon quantum dots
are intensively difficult. Since consistent experimental data is lacking, it is highly desirable to develop an accurate
theoretical model to assist in the development of silicon QDs in supporting future technologies. In the theoretical
model, the all-electron count approach, such as density functional theory (DFT), were reported to be successfully
applied throughout 0-2 nm size regime. It relies on the approximate exchange-correlation functional which is well
known to yield accurate ground state properties, but slightly underestimating the optical gaps. Hence, the purpose of
this paper is to elaborate the ability of DFT to predict the optical energy gap, also known as energy band-gap of
silicon nanostructures, from a few to several hundred atoms.

METHODOLOGICAL BACKGROUND
In this paper, the estimation values of Silicon Quantum-Dots energy band-gap from other data were reviewed
with our DFT implementations on numerical atomic orbitals (NAOs) calculation. Iteration convergence of the
computational physical properties with plane waves (PWs) and real-space grids were well controlled by increasing
the size of the basis, hence, providing a benchmark for the electronic structure calculations. However, this approach
is at the expense of computational time and memory requirements for simulation process [3].
On the other hand, atomic orbitals (AOs) which contain basis-set can be much smaller. For instance, for a similar
quality of the calculation result, a dozen of AOs is required per atom instead of hundreds of PWs per atom.
The 2014 UKM FST Postgraduate Colloquium
AIP Conf. Proc. 1614, 104-109 (2014); doi: 10.1063/1.4895180
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Obviously, atomic orbitals are routinely used in calculation of atomic and molecular spectra, and it is becoming a
starting point to perform simulation for chemists. In addition, its convergence properties had been intensively
studied for decades [4-5], where its implementation for extended solid-state systems were successful [6]. However,
for comparison study, the use of AOs in solid-state system were less established compared with other methods.
Hence, this paper will elaborate the use of method proposed by Ozaki et al. [6] as implemented in the OpenMX
package [2], towards understanding electronic structure of Si-QDs. The selection of silicon basis-set were
corresponding to the early studies in bulk-Si [15] which have indicated that a double-zeta polarized (DZP) basis-set
may suffice for converged forces in atomic relaxations [7]. This rule of basis-set was used in this Si-QDs
calculations.

SELECTION OF STRUCTURAL PROTOTYPES

In constructing structural prototypes, it started from repeating the bulk silicon single unit cell until desired
superlattice formed, then, a spherical region was choosen as this has the smallest surface area for a given number of
atoms by eliminate excess atom. The dangling bonds on the surface were saturated with hydrogen and terminated Si
atoms. Since at the surface where QDs Si atoms are fully co-ordinated, hydrogen termination led to enhance stability
in ambient environments, unlike a 'clean surface' having unpassivated surface atoms, or dangling bonds. It was
relatively inert and can be handled in air without any special care for several minutes.
Considering prototypes with Si:H terminations up to ~2 nm size regime has led to likely ideal structures
containing core of tetrahedral (Td) symmetry structure, as shown in FIGURE 2. In other cases, DFT calculations
using a plane-wave basis and norm-conserving pseudo-potentials are used to establish the equilibrium geometries
and the electronic structure of these systems. As it was observed previously, the relaxed structures are very similar
when calculated using either LDA or gradient corrected (PBE) functional and are fairly close to the original bulk
derived structures with small adjustments of the bond lengths and angles, predominantly of the surface atoms.

COMPUTATIONAL DETAILS
After each prototypes of Si-QDs was constructed, a geometry optimization using Quasi-Newton method was
performed to get an ideal relaxation structure. Quasi-Newton method used are Broyden-Fletcher-Goldfarb-Shanno
(BFGS) method [8-11], to solve non-linear optimization problem in Cartesian coordinate. Before starting to
determine the appropriate prototypes structure to do simulation, a few bare Si-QDs structure were selected to
undergo calculation. By understanding the plot of DOS and energy spectrum, it was realized that the structure need
to be passivated with the hydrogen atom on the surface of the QDs. An optimized structure were then used to
calculate the energy gap and analyzed from HOMO-LUMO data. All the computational methods were done using
numerical atomic orbital basis-set in the OpenMX implementation of Ozaki et al. [6]. Norm-conserving pseudopotentials also take into account for core electron potential.
In density of state (DOS) plotting, the MonkhorstPack k-point sampling was set on k=1 for Gamma ()
direction only (neighboring atom accounted only), while the energy at zero eV was set as the Fermi level. An
exchange-correlation was treated as Local Density Approximation (LDA) where Perdew-Zunger (PZ) [12]
functional was applied. All the relaxed structure of the Si-QD are shown in FIGURE 2. For SCF field, the electron
temperature was set to 300K as closed to room temperature. Linear Combination Atomic Orbitals (LCAO) basis-set
used in the simulation was a double-zeta polarized (DZP) basis-set for Si element while single-zeta for H.

RESULT & DISCUSSION

Through the understanding of the DOS plot, it is observed that there is a pronounced confinement effect on
hydrogen passivated structure. 3 prototypes with and without passivation were selected to observe the change on
confinement effect, from small to the largest size accordingly. The comparison between DOS on two different types
of silicon quantum dots lead to an understanding about the main role of passivation with hydrogen on the quantum
dots surface. FIGURE 1 below shows the energy gap shift and enhancement of confinement effect on the quantum

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dot. It seems that the localization of electron played an important role while the concern was about the selection of
finite sized structure. As the finite size of crystal was controlled, dangling bond were formed near the surface of the
QDs structure. It can be said that the confinement was not announced, as the electron freely move as its delocalized
in all direction including the surface of QDs.
b)

a)

d)
c)

e)

f)

FIGURE 1. DOS plot for selected structure, left side refer to bare silicon quantum dots and right side is hydrogen passivated
Silicon quantum dots. Each pair of graph contain different numbers of Silicon atom. Figure (a) & (b) is for 10-Silicon atom, (c) &
(d) corresponding to 66-Silicon atom, and figure (e) & (f) have 147-Silicon atom

In Silicon orbital configuration, s-orbital and p-orbital hybridization will promotes sp3 bonding. Hence, when
multiple sp3 Si-Si are combined to form a bulk solid, hybridically it will introduce the conduction and valence
bands. However, if a vacancy was to exist, such as those on each atom at the structure interface, it would resulted in
broken sp3 bond which has an energy equal to that of single self hybridized Si atoms. Certainly this is the most ideal
case whereas the situation would be different if bond passivation and surface reconstruction were to occur. Hence,
the passivation of Si-QDs with hydrogen will result to the termination of dangling bond with pronounced
confinement effect of electron inside the core-region of structure.
FIGURE 2 below shows selected structure of the total 14 structures modelled and visualized using VESTA [13].
All low-dimensioned silicon quantum dots were passivated by hydrogen. Then, they were optimized using QuasiNewton method before continued with an electronic calculation.

0 nm
Si1H4

0.25 nm
Si2H6

0.60 nm
Si5H12

0.70 nm
Si10H16

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0.80 nm
Si17H36

1 nm
Si29H36

1.1 nm
Si35H36

1.2 nm
Si47H60

1.4 nm
Si66H74

1.5 nm
Si71H84

1.6 nm
Si87H76

1.7 nm
Si99H100

1.8 nm
Si123H100

1.9 nm
Si147H100

FIGURE 2: Structures prototype of relaxed Hydrogenated Silicon Quantum Dots. Inner core of structure shows tetrahedral
Td symmetry arrangement. The large atom corresponding to Silicon atom while the small atom was hydrogen.

Before the simulation was performed, the accuracy of the calculation details were examined by implementing
selected parameters on the calculation of bulk silicon semiconductor. Using the same parameters as mentioned in the
computational details, this will determine the reliability of the method taken. Since LDA is well known to
underestimate band gap values, scissors operator of LDA was accounted to the well-known discontinuity issues on
Exchange-Correlation as reported by Godby et al. [14]. There is an addition of scissors operator of 0.58eV, hence
the result shows that the value of energy gap (Eg) for bulk silicon is 1.13eV, which is much close to the reported
reference, Eg =1.12eV at 300k [15]. Hence, this indicates that the computational details are acceptable to be
extended on electronic properties of Silicon crystal.

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The value of the energy gap, as observed from the energy spectrum, decreases as the size of the dot increases,
this implies weaker confinement for larger sizes. As the number of atoms in the dot was increased and its size
changed, the degeneracies pronounced to be increasingly lifted. This situation also happen when the surface
dangling bonds was saturated with hydrogen atoms, there is an enhancement of the gap energy observed
approximately 2.3 eV for 10 atom cluster as present on FIGURE 1 (b). Here is the explanation of this situation, the
degeneracies are lifted because of the presence of hydrogen at the surface of Si-QDs structure, acting like a
perturbation interaction potential. Hence, the electron were localized inside the dots resulting more degeneracies
inside and disallow electron moving to the surface as higher potential experience on the dot surface by the presence
of hydrogen atom. For smaller dots, it is observed that this effect of de-localization near the surface is lesser and
hence, the degeneracies are more pronounced. For relatively larger dot, self-hybridization occur. Hence, due to sp2
and sp3 hybridization de-localization of the electron is more and the energy spectrum is more non-degenerate.

12

P resent NAOs DFTLDA HOMO-LUMO

Energy, eV

10
Wiliamson et al P Ws
DFT-LDA HOMOLUMO [16]

Experiment- Feher
[17]

6
4

Experiment- Wilcoxon
et al [18]

Experiment- Wolkin et
al [19]

Bulk Gap

0.5

1 Diameter, d (nm)
1.5
Si-QD

FIGURE 3. Present result were compared with other theoretical data and reported experimental work.

Records for the results of simulation for the variation of energy gap for different size of the dot is as shown in
FIGURE 1, Si-QDs with hydrogen-passivation. Bigger gap with passivation is due to the localization of electron
cloud arising from the sp3 hybridization of the silicon-dangling bond with the hydrogen atom. These results are in
conformity with the earlier observation [1]. Comparison and completeness of the missing possible structure of SiQDs between 0~2nm of the newly observed result, compared with the previous theoretical LDA result by
Williamson et al. [16] and experimental study [17-19] as shown in figure 3, all showed good sign that the agreement
augured very well.

CONCLUSION
In Quantum Dots system, it was realized that there are totally different ways to treat the simulation system
compared to bulk material. From the study of DOS conducted on two types of Si-QDs (bare and hydrogen
passivated) prototype, it was noticed that there is a very important role of surface passivation on the quantum
confinement effect of the system. The presence of hydrogen on the surface of quantum dots lifts the degeneracies of
the eigenvalue spectrum and resulted in an enhancement of the gap energies. Indeed, wrong selection of structural
model will results the wrong interpretation of QDs systems. Here, the Numerical atomic orbital method was used to
calculate the electronic structure of hydrogen passivated silicon quantum dots in different sizes from 0-1.9 nm,
occupying 5 to 147 of Silicon atoms with total of 14 structure to examine the quantum size effects on the energy
gap. These results agreed that the energy gap increases as the size of the dot decreases, where stronger confinement
implies on the smaller dots. These results are in conformity with the earlier observation of Wang and Zunger [20]

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and others. The energy gap seems to increase accordingly reaching the ultraviolet region of 3.10 eV under 1.6 nm
diameter of Si-QDs. Experimentally, Wolkin et al.[19] reported that the photoluminescence characteristics are
determined by both quantum confinement and surface passivation. This implies that the passivated surface states
played important role as far as the energy gap from finite size dots are concerned.
The observed computational results showed that the use of NAOs might be an efficient method, alternative to
plane waves, to calculate the properties of small sized silicon quantum dots. It was also confirm that, although the
LDA calculations underestimate the band gap, it give the trend of quantum confinement effect in the function of
quantum dot size. Based on the research outcomes, it was also noticed that using microscopic approach to study
QDs electronic structure, its only sufficient for small sized quantum dots calculation which <500 atoms on multicore processor computer. However, it consume a lot of computational time and very difficult to be applied to large
qXDQWXPdots.

ACKNOWLEDGMENTS
Thank you to the Ministry of Education Malaysia (Higher Education) for financial support through grant of
ERGS funding ERGS/1/2012/STG02/UKM/02/3, and MyBrain15 scholarship for the candidate financial support.

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