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Size and shape effects on the band gap of

semiconductor compound nanomaterials

Madan Singh, Monika Goyal & Kamal Devlal

To cite this article: Madan Singh, Monika Goyal & Kamal Devlal (2018): Size and shape effects on
the band gap of semiconductor compound nanomaterials, Journal of Taibah University for Science,
DOI: 10.1080/16583655.2018.1473946

To link to this article: https://doi.org/10.1080/16583655.2018.1473946

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Published online: 30 May 2018.

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JOURNAL OF TAIBAH UNIVERSITY FOR SCIENCE
https://doi.org/10.1080/16583655.2018.1473946

Size and shape effects on the band gap of semiconductor compound

nanomaterials
Madan Singha , Monika Goyalb and Kamal Devlalc
a Department of Physics and Electronics, National University of Lesotho, Roma, Lesotho; b Institute of Applied Sciences & Humanities, G.L.A
University, Mathura, India; c Department of Physics, Uttarakhand Open University, Haldwani, India

ABSTRACT ARTICLE HISTORY

The size- and shape-dependent band gap energy of semiconductor compound nanomaterials Received 23 May 2017
(SCNs) is formulated. The model theory is based on the cohesive energy of the nanocrystals com- Accepted 24 June 2017
pared to the bulk crystals. We have considered CdSe, CdTe, ZnS, ZnSe and ZnTe semiconductors KEYWORDS
compounds for the study of size- and shape-dependent band gap energy. It is found that the Energy band gap; cohesive
band gap energy of SCN depends upon the particle size and shape. The model predicts that the energy; semiconductors
band gap energy increases as particle size of the semiconductor nanomaterials decreases. The nanomaterials
results obtained are compared with the available experimental data, which support the validity
of the model reported.

1. Introduction
gap within the quantum confinement regime. Due to
Semiconductor nanomaterials have been a rapidly quantum confinement effect, electrons and holes in
growing area of research for scientific community the semiconductors in nanoscale are confined. There-
due to their unique electrical, optical, photonic and fore, the energy difference between the filled states and
mechanical properties [1–9]. Recently, Hassan et al. the empty states increases or widen the band gap of
[10–11] have reported the mechanical, structural, elec- the semiconductor [14]. In optoelectronics devices this
tronic, magnetic and optical behaviours in Zn1–xMnxS larger band gap drastically changes the optical and elec-
(0 ≤ x ≤ 1), which are determined by using Wein2K tronic properties of semiconductors at nanoscale [15].
code. Some of these properties are connected to the Many experiments have been performed to measure
surface area to volume ratio of the nanomaterials, which the value of band gap by means of X-ray photoemission
play an important role to characterize their properties. spectroscopy and by photoluminence [16–18]. But, the
One of the leading and important properties of semi- theoretical prediction for the band gap of semiconduc-
conductors is their band gap. Band gaps play a fun- tor compound nanomaterials (SCNs) even has its own
damental role in electrical and optical properties of qualities. Although few theoretical models have been
semiconductor materials. So, it is significant and essen- established, but the size- and shape-dependent band
tial to study the band gap expansion of the SCN to gap of semiconductors nanomaterials, which has the
understand the better way of their properties. Semicon- potential to calculate the band gap in full range free of
ductors have extensive applications due to their widen approximation, is still lacking.
band gap. Bulk silicon is limited in the application due In this study, based upon the cohesive energy a the-
to its indirect and small band gap, whereas Si pho- oretical model that does not use adjustable parame-
ton nanodevices have been widely produced and used. ters, size- and shape-dependent band gap energy of
Size-dependent band gap has been carried by many SCNs has been proposed. The theoretical prediction
experimental and theoretical researchers. The diameter is applied on the CdSe, CdTe, ZnS, ZnSe and ZnTe
dependence of the effective band gaps in the wires is semiconductors compound nanomaterials in spherical,
determined from photoluminescence spectra and com- nanowire and nanofilm shapes. It is found that the par-
pared to the experimental results for InAs quantum dots ticle size and shape can tune the band gap energy
and rods and to the predictions of various theoretical of the SCN. The model predictions are compared with
models [12]. the available experimental data. A good agreement
Barnard [13] used the electronic structure simula- indorses the validity of our proposed model throughout
tions to show that the shape of individual diamond the size range. This model may be of potential applica-
nanocrystals, which may offer a way of tuning the band tion where experimental data are lacking.

CONTACT Madan Singh [email protected], [email protected] Department of Physics and Electronics, National University of
Lesotho, P.O. Roma 180, Roma, Lesotho
© 2018 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group.
This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted
use, distribution, and reproduction in any medium, provided the original work is properly cited.
2 M. SINGH ET AL.

2. Theory of analysis Or Equation (6) may be written as

The energy due to the contributions of the inte- Eg (D)/Eg (bulk) = |(Ea (D) − Ea (bulk))/Ea (bulk)|
rior atoms and the surface atoms is defined as the
total cohesive energy of the nanomaterial, which is Or
expressed as [19]
Eg (D)/Eg (bulk) = 1 − (Tmn /Tmb ) (7)
ETotal = E0 (n − N) + (1/2)E0 N, (1)
Using Equation (4), Equation (7) may be written as
where n is the total number of atoms in the nanosolid  
N
and N is the number of surface atoms. Therefore, (n − Eg (D) = Eg (bulk) 1 + (8)
N) is the total number of interiors atoms in the nano- 2n
material. E0 is the cohesive energy of the bulk material The value of N/2n differs upon the size and shape of the
per atom. To determine the cohesive energy per mole, nanomaterials [19]. For spherical nanosolids, the impli-
Equation (1) may be written as cation of N/2n is 2d/D, where d is the diameter of an
AETotal /n = AE0 (1 − (N/n)) + (1/2n)AE0 N, (2) atom, and D is the diameter of the spherical nanosolids.
The magnitude of N/2n for nanowire and nanofilm are
where A is Avogadro’s number. Here, AETotal /n is the 4d/3l and 2d/3h separately, where l is the diameter of
cohesive energy per mole of the nanomaterial En and nanowire, and h is the width of the nanofilm.
AE0 is the cohesive energy per mole of the correspond- Putting the values of N/2n in Equation (8), we obtain
ing bulk material (Eb ). On substituting in Equation (2), following expressions
one can get  
2d
En = Eb (1 − (N/2n)). (3) Eg (D) = Eg (bulk) 1 + , (9)
D
It is reported [20–21] that the cohesive energy is the lin-
ear relation to the melting temperature, we can there-  
4d
fore write the relation for melting temperature of nano- Eg (l) = Eg (bulk) 1 + , (10)
3l
materials as
 
Tnm = Tbm (1 − (N/2n)). (4) 2d
Eg (h) = Eg (bulk) 1 + . (11)
3h
Arrhenius expression [22] for the electrical conductivity
σ (D, T) which depends upon the size and temperature Equations (9)–(11) are the expression of energy
is expressed as band gap for spherical nanosolids, nanowires and
nanofilms, respectively. In this paper, we employ Equa-
σ (D, T) = σ0 exp(−Ea (D)/kB T) (5) tions (9)–(11) to study the change in band gap energy of
Here, σ0 is a pre-exponential constant and Ea (D) is the semiconductors compounds nanomaterials at different
size-dependent activation energy for electrical migra- shapes and sizes.
tion for nanocrystals, which is read as Ea (D) = Ec −
EF , where Ec is the conduction band energy and EF is 3. Results and discussion
the Fermi energy. Assuming the electrical conductivity
independent of melting temperature and size [23], one A simple model has been formulated to study the
can get σ (D, Tmn ) = σ (bulk, Tmb ), where Tmn and Tmb increase in energy band gap with shape and size of
are the melting temperature of nanomaterials and cor- semiconductor nanomaterials. The input parameters
responding bulk materials. Thus, from Equation (5) we [25–30] required in the theoretical calculations are
get listed in Table 1. The results obtained are reported
in Figures 1–12 along with the available experimen-
σ0 (D) exp(−Ea (D)/kB Tmn ) = σ0 (bulk) tal findings. Figure 1 reports the model prediction of
× exp(−Ea (bulk)/kB Tmb ). Equation (9) for the size-dependent energy band gap of
CdSe semiconductor nanomaterials in spherical shape.
Ignoring the size effect on σ0 , we reach Ea (D)/Ea (bulk) Comparisons for the predicted results and the available
= Tmn /Tmb . As we recognize that the Fermi level lies experimental values [31,32] are shown in Figure 1. The
in the mid of the band gap for mostly semiconductors,
thus the activation energy becomes Ea = Eg /2, which
Table 1. Input parameters [25–30].
implies that change in activation energy is proportional
to the energy band gap change [24]. Therefore, we have Nanomaterials E g (bulk)eV d (nm)
a more suitable expression CdSe 1.74 0.268
CdTe 1.44 0.286
Eg (D)/Eg (bulk) = |Ea (D)/Ea (bulk)|, (6) ZnS 3.68 0.234
ZnSe 2.7 0.254
ZnTe 2.39 0.189
where Eg is the difference in energy band gap.
 JOURNAL OF TAIBAH UNIVERSITY FOR SCIENCE 3

1.90

2.2
1.85
CdSe CdTe Nanosphere
1.80
Nanosphere
2.1
1.75

1.70
Eg(D)eV

Eg(D)eV
2.0
1.65

1.60
1.9

1.55

1.8 1.50

1.45
2 4 6 8 10 12 14 16 18 20 22 0 2 4 6 8 10 12 14 16 18 20 22
D(nm) D(nm)

Figure 1. Variation of energy band gap of CdSe nanosphere Figure 4. Variation of energy band gap of CdTe nanosphere
with size. The values calculated in the present study using with size. The values calculated in the present study using
Equation (9) are shown by the continuous line, and the exper- Equation (9) are shown by the continuous line, and the exper-
imental results are shown by solid circles [31] and triangles imental results are shown by solid circles [35] and triangles
[32]. [36].

1.75
2.10

CdSe Nanowire CdTe Nanowire

2.05 1.70

2.00 1.65
Eg(L)eV

Eg(L)eV

1.95
1.60

1.90
1.55

1.85
1.50
1.80

1.45
2 4 6 8 10
2 4 6 8 10
L(nm)
L(nm)

Figure 2. Variation of energy band gap of CdSe nanowire with Figure 5. Variation of energy band gap of CdTe nanowire with
size. The values calculated in the present study using Equation size. The values calculated in the present study using Equation
(10) are shown by the continuous line, and the experimental (10) are shown by the continuous line, and the experimental
results are shown by solid circles [33] and triangles [34]. results are shown by solid circles [34].

1.90
1.58

1.88 CdSe Nanofilm

1.56 CdTe nanofilm
1.86
1.54
1.84
Eg(h)eV

Eg(h)eV

1.52
1.82

1.50
1.80

1.78 1.48

1.76 1.46

2 4 6 8 10 12 14 2 4 6 8 10
h(nm) h(nm)

Figure 3. Variation of energy band gap of CdSe nanofilm with Figure 6. Variation of energy band gap of CdTe nanofilm with
size. The values calculated in the present study using Equation size. The values calculated in the present study using Equation
(11) are shown by the continuous line. (11) are shown by the continuous line.
4 M. SINGH ET AL.

4.6 3.5
ZnS Nanosphere
4.5 3.4

4.4 ZnSe Nanosphere

3.3
4.3
3.2
Eg(D)eV

4.2

Eg(D)eV
4.1 3.1

4.0 3.0

3.9
2.9
3.8
2.8
3.7
2 4 6 8 10 12 14 16 18
2.7
D(nm) 2 4 6 8 10 12 14 16 18 20 22
D(nm)
Figure 7. Variation of energy band gap of ZnS nanosphere with
size. The values calculated in the present study using Equation Figure 10. Variation of energy band gap of ZnSe nanosphere
(9) are shown by the continuous line, and the experimental with size. The values calculated in the present study using
results are shown by solid circles [37] and triangles [38]. Equation (9) are shown by the continuous line, and the exper-
imental results are shown by solid circles [39] and triangles
[40].
4.3

ZnS nanowire
4.2
3.20

4.1 3.15 ZnSe nanowire

Eg(L)eV

3.10
4.0
3.05

3.00
Eg(L)eV

3.9
2.95

3.8 2.90

2.85
3.7
2 4 6 8 10 12 2.80
L(nm) 2.75

Figure 8. Variation of energy band gap of ZnS nanowire with 2 4 6 8 10 12

L(nm)
size. The values calculated in the present study using Equation
(10) are shown by the continuous line, and the experimental
results are shown by solid circles [34]. Figure 11. Variation of energy band gap of ZnSe nanowire with
size. The values calculated in the present study using Equation
(10) are shown by the continuous line, and the experimental
4.00
results are shown by solid circles [34].
3.95

ZnS Nanofilm substantial increase in the value of Eg (D). Moreover,

3.90
the predicted results are in agreement with the exist-
ing experimental data for the entire range of the CdSe
Eg(h)eV

3.85
nanosphere. Our model is also supported by the quan-
3.80 tum confinement theory, which suggests that the holes
in the valence band and the electrons in the conduc-
3.75 tion band are confined by the potential barriers of
the surface or potential well of quantum box. Because
3.70
2 4 6 8 10 12
of the confinement of the electrons and holes, the
h(nm) band gap energy increases between the valence band
and the conduction band with decreasing the particle
Figure 9. Variation of energy band gap of ZnS nanofilm with size. Figure 2 presents the energy band gap of CdSe
size. The values calculated in the present study using Equation nanowire calculated by Equation (10), along with the
(11) are shown by the continuous line.
experimental data [33,34] which support the model pre-
dictions. As revealed from Figure 2, the energy band
results show that the band gap energy Eg (D) increases gap increases with the decrease in particle size. The
with the decreasing particle size. It is observed that energy band gap increases sharply with the reduction
when the particle size is less than 6 nm, there is a of size 4 nm onwards. Our results are very close to
 JOURNAL OF TAIBAH UNIVERSITY FOR SCIENCE 5

experimental verdicts [37,38,34]. This supports the cor-

2.8
rectness of the formulation used. We have used Equa-
ZnTe tions (9) and (10) to calculate the band gap of ZnSe
2.7
nanomaterial semiconductor in different shapes and
sizes. The computed values are reported in Figures 10
Eg(D/L/h)eV

2.6 and 11. Our model predictions are close to the exper-
imental findings [34,39–40]. Throughout the full size
2.5 range for ZnSe nanosphere, there is a good agreement
with the experiment. Figure 11 exhibits the size depen-
2.4
dence of band gap expansion of ZnSe nanowire. The
results obtained are compared with the experimental
2 4 6 8 10 12 14 16 18 data [34]. As shown in figure, the band gap expan-
D/L/h(nm) sion firstly rises slowly then increases rapidly with the
decreasing the size. Graphical depiction of the increase
Figure 12. Variation of energy band gap of ZnTe nanosphere,
in band energy with shape and size confirms that at
nanowire and nanofilm with size top to bottom respectively. The
values calculated in the present study using Equations (9)–(11) nanoscale not only the size but also shape plays a signif-
are shown by the continuous line, and the experimental results icant part. Volume to surface area ratio varies with shape
are shown by solid delta [41] and square [34]. and size which alters the number of surface atoms
at nanoscale and consequently the cohesive energy.
Hence, the band gap energy changes at nanoscale. This
results obtained by Li et al. [33,34] as shown in Figure 2. can be explained quantum mechanically as the particle
Equation (11) is used to calculate the size-dependent size reaches the nanoscale, the number of overlapping
energy band gap of CdSe, CdTe, ZnS, ZnSe and ZnTe of orbitals or energy level decreases and the thickness of
semiconductors nanofilms. The computed results are band becomes thinner. This will cause a rise in energy
reported in Figures 3, 6, 9 and 12. It is observed that the band gap between the valence band and the conduc-
energy band gap of nanofilms increases with decrease tion band. This describes the higher energy band gap in
in size. The trend of increasing the energy band gap with SCNs than their corresponding bulk counterpart.
decreasing size is same as that of spherical nanosolids
and nanowires. It is observed from Figure 12 that the
effect of size decreases as we go from spherical to
4. Conclusion
nanowire and nanofilm. This trend is expected since the In brief, a simple model is formulated to calculate the
surface to volume ratio increases with decreasing size. It band gap energy of semiconductor nanomaterials in
should be mentioned here that the experimental results different sizes and shapes, viz., spherical nanosphere,
are not available for the CdSe, CdTe, ZnS, ZnSe and ZnTe nanowires and nanofilms. It is reported from the theory
nanofilms. We are reporting our model projection in the that energy band gap increases as particle size of the
absence of the experimental data. Our prediction may semiconductor nanomaterials decreases. Furthermore,
be of the current interest to the researches engaged our model prediction of the energy band gap is reason-
in the experimental research. Since cohesive energy ably consistent with the available experimental data.
decreases by Equation (3) with the decreasing of parti- We are confident that this theory will show an impor-
cle size of nanofilms, which leads to increase the band tant role where experimental data are not available so
gap energy launched by Equation (11). The size depen- far.
dence of band gap energy of CdTe nanosphere using
Equation (9) is shown in Figure 4. It is seen that the
Acknowledgements
band gap energy of CdTe nanosphere increases on
decreasing the particle size. The results reported are The authors are thankful to the referee for their valuable com-
ments that have been useful in revising the manuscript.
compared with the available experimental observations
[35,36]. There is a good accord between our proposed
model and the experiments. The size dependence of Disclosure statement
band gap energy of CdTe nanowire using Equation (10) No potential conflict of interest was reported by the authors.
is plotted in Figure 5. We compared our predictions
with the experimental data reported by Li et al. [34].
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