Materials Science in Semiconductor Processing 121 (2021) 105334

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Materials Science in Semiconductor Processing

journal homepage: http://www.elsevier.com/locate/mssp

Synthesis and characterization of bismite nano-island thin films for

optoelectronic applications
Aus A. Najim
Nanotechnology and Advanced Materials Research Center, University of Technology, Baghdad, Iraq

A R T I C L E I N F O A B S T R A C T

Keywords: Ultra-smooth thin films of bismite Bi2O3 synthesized by physical vapor deposition (PVD) have been inspected for
Nano-islands their morphological, topographical, structural, and optical properties. Morphology and topography of the syn­
Bi2O3 thin films thesized thin films were investigated by (SEM) and (AFM) and reveal a homogeneous nano-island structure with
Ultra-smooth thin films
average grain size of 70 nm whereas the surface has a root mean square (RMS) roughness of 2.68 nm. The
Single-oscillator model
structural properties were investigated by (XRD) show the films having polycrystalline monoclinic structure of
bismuth oxide. The optical properties were studied by spectrophotometer and reveal the films having narrow
bandgap of 1.95 eV, the nonlinear optical constants were investigated by Wemple-DiDomenico model, the
calculated values of the single-oscillator energy and the dispersion energy were found to be 4.01 eV and 23.26
eV; respectively, the third-order nonlinear susceptibility was found to be 7.72 × 10− 12 esu. These characteristics
show the films are good candidate for nonlinear optoelectronics and various potential applications.

1. Introduction reactive pulsed laser deposition [22], reactive RF sputtering [23],

Nowadays; ultra-smooth nanostructured thin films have attracted
interests due to their notable characteristics and play a fundamental role
in the efficiency of the produced devices [1]. Metal oxide semiconductor
thin films (MOSTFs) have been used in various applications such as
transparent conductive films (TCF) [2], organic light-emitting diode
(OLED) [3], visible photo electrochemical water splitting photo­
electrodes based on organic semiconductor thin film (OSTF) [4], nano­
photonic devices [5], organic-inorganic perovskite thin films for
efficient planar heterojunction solar cells [6,7], flexible transparent
conductive materials [8], and recently it has been used for surface
interaction measurements [9]. Bismuth oxide is considered as one of the
most important materials in metal oxide semiconductor devices
manufacturing due to its fabulous physical and chemical characteristics
with a broad bandgap. Bi2O3 exists in six possible polymorphic forms
with high degrees of stability where α-Bi2O3 and δ-Bi2O3 forms are stable
while β-Bi2O3, γ-Bi2O3, ε-Bi2O3 and ω-Bi2O3 forms are metastable
[10–12]. Bi2O3 thin films have a wide range of applications such as
transparent electronics [13], solar cells [14], supercapacitors [15], ul­
traviolet (UV) photodetectors [16] and sunlight-driven photocatalysts
[17]. Bismuth oxide thin films have been prepared by various techniques
such as atomic layer deposition (ALD) [18], electrodeposition [19],
photochemical synthesis technique [20], physical evaporation [21],
thermal- and plasma-enhanced atomic layer deposition [24].
In this work, ultra-smooth nanostructured thin films of bismite Bi2O3
have been prepared by physical vapor deposition (PVD) technique then,
investigate their morphological, structural, and optical properties then
after evaluating the produced film to be used in potential advanced
optoelectronic applications.
2. Experimental
Pure Bi2O3 thin films were deposited on glass substrates by physical
vapor deposition technique (PVD), this technique provides a smooth and
well crystalline thin film [21]. The used technique is based on thermal
evaporation of bulk Bi2O3 powder provided by (Sigma-Aldrich, USA)
with 99.9% purity using Pt heating source, the vacuum chamber was
evacuated to a pressure of 1 × 10− 3 Pa, target to substrate distance was
15 cm and the substrate temperature was maintained at 400 ◦ C, the
growth rate was keep at 1 Å/s. The thickness of the prepared thin film
was measured using light interference and found to be 124 nm, there­
after the film was characterized by Shimadzu XRD-6000 diffractometer,
Tescan VEGA3 SB SEM scanning electron microscope, Angstrom
AA3000 SPM scanning probe microscope, and Metertech SP-8001
UV–Vis spectrophotometer to study the structural, morphological,
topographical, and optical properties respectively.

E-mail address: aus772005ma@yahoo.com.

https://doi.org/10.1016/j.mssp.2020.105334
Received 2 April 2020; Received in revised form 9 July 2020; Accepted 11 July 2020
Available online 7 August 2020
1369-8001/© 2020 Elsevier Ltd. All rights reserved.
A.A. Najim Materials Science in Semiconductor Processing 121 (2021) 105334

Fig. 1. a) SEM micrograph b) AFM micrograph c) grain size distribution and d) XRD pattern of the prepared film [inset: Crystal structure view towards (100) plane].

island structure with no cracks and pinholes, AFM micrograph (see

Table 1
Fig. 1b) reveals the film has an ultra-smooth surface with a root mean
The calculated values of texture coefficient.
square RMS roughness of 2.68 nm and confirms the existence of nano-
Miller index (hkl) Texture coefficient TC(hkl) islands with an average size of 70 nm (see Fig. 1c), these findings are
(100) 4.43456 similar to the work reported in Refs. [25–27]. The structural charac­
(020) 0.49413 teristics were analyzed by X-ray diffractometer (Shimadzu XRD6000)
(112) 0.01285
with CuKα radiation, Fig. 1d shows the XRD pattern and reveals the film
(112) 0.00775
has a polycrystalline monoclinic structure of α-Bi2O3, the diffraction
(040) 0.01267
angles 16.92◦ , 22.26◦ , 27.06◦ , 37.41◦ and 44.48◦ correspond to the
reflection planes (100), (020), (112), (112) and (040) respectively
3. Results and discussion (PDF#72–0398). Moreover, it is possible to distinguish the preferred
orientation of the prepared thin film by calculating texture coefficient
3.1. Morphology, topography, and structure analysis TC(hkl) for the (hkl) planes using the following equation [13]:
[ ]− 1
I(hkl) 1 ∑ I(hkl)
Morphology and topography of the synthesized Bi2O3 thin film were TC(hkl) = (1)
analyzed using Tescan VEGA3SB scanning electron microscopy (SEM) Io (hkl) n Io (hkl)
and Angstrom AA3000 atomic force microscopy (AFM), Fig. 1a shows
where I(hkl) and IO(hkl) are the intensities of lattice planes for the
the SEM micrograph of Bi2O3 thin film and reveals homogeneous nano-

Fig. 2. Absorption and extinction coefficients of bismite Bi2O3 nano-island thin film.

2
A.A. Najim
Fig. 3. Bandgap of bismite Bi2O3 nano-island thin film.
Fig. 4. Plot of (n2-1)− 1
versus the square of photon energy for Bi2O3 nano-
island thin film.
prepared Bi2O3 thin film and the standard powder diffraction for the
corresponding (hkl) plane, while n is the total number of (hkl)
reflections.
The values of texture coefficient for the (hkl) planes are tabulated in
Table 1 and clearly seen the highest TC(hkl) value correspond to reflec­
tion plane (100), this means the preferred orientation is (100) and the
film has a higher degree of orientation along a-axis, this finding is
coincident with previous work [13].
3.2. Optical properties
The optical properties were investigated using UV–Vis–NIR spec­
trophotometer (Metertech SP-8001), Fig. 2 shows the absorption and
extinction coefficients of Bi2O3 thin film which are evaluated using the
following equations [28,29]:
A pared thin film show a homogeneous nano-island of the polycrystalline
α = 2.303
d
αλ
k=
4π
where α, A, d, k, and λ are absorption coefficient, absorbance, film
thickness, extinction coefficient, and wavelength; respectively, Fig. 2a
shows the absorption coefficient as a function of wavelength, it is clearly
seen the values of the absorption coefficient are greater than 104 cm− 1,
this indicates the film has a direct bandgap nature. Fig. 2b shows the
Materials Science in Semiconductor Processing 121 (2021) 105334
extinction coefficient and exhibits high values comparable to those re­
ported in Ref. [30–32].
The bandgap of Bi2O3 thin film was calculated using the following
equation [33]:
(αhv)2 = D(hv − Eg) (4)
where h, v, D, and Eg are Planck’s constant, photon frequency, propor­
tionality constant, and optical bandgap; respectively, Fig. 3 shows the
bandgap of the prepared Bi2O3 thin film and found to be 1.95 eV, this
value fairly agrees with the findings reported in Ref. [23,34].
The nonlinear optical constants were investigated using Wemple-
DiDomenico model [35].
Eo Ed
n2 − 1 = (5)
Eo2 − E2
where n, Eo, Ed, and E are the refractive index, single-oscillator energy,
dispersion energy, and photon energy respectively; Fig. 4 show the plot
of (n2-1)− 1 versus the square of photon energy and a fitting straight line
where the intercept represents Eo/Ed whereas the slope represents 1/
EoEd, the single-oscillator energy Eo is found to be 4.01 eV, Eo is also
considered as the average energy gap ~2 Eg as reported by Tanaka [36]
while the dispersion energy Ed is found to be 23.26 eV, these values are
coincident with the calculated values for α-Bi2O3 reported by Shannon
et al. [37].
Furthermore, based on Wemple-DiDomenico model, the static
refractive index n(0) at null photon energy (hν →0) in addition to the
lattice dielectric constant at zero-frequency ε = n2 (0) are calculated
using the following equation [38].
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅
Ed
n(0) = 1 + (6)
Eo
The calculated values of n(0) and ε were found to be 2.6 and 6.8
respectively; these values are comparable to those reported by Shannon
et al. [37].
The nonlinear optical parameters play an important role thin films
performance when the optical material is illuminated by an intensive
light, the third-order nonlinear susceptibility χ(3) can be estimated at the
zero-frequency region by the following equation [39]:
( )4
1.7 × 10− 10 [ 2 ]4 − 15 Ed
χ (3) = no − 1 = 6.817 × 10 (7)
(4π)4 Eo
The calculated value of χ(3) was found to be 7.72 × 10− 12 esu, this
value is higher by a factor of (18.4 and 2.2) than the third-order
nonlinear susceptibility for both bulk Bi2O3 and Bi2O3 nanoparticles
reported by Baolong et al. [40], the raise of third-order nonlinear sus­
ceptibility value might be due to the quantum size effect of nano-island,
this characteristic might be more significant for the development and
design of new nonlinear optical materials and devices [41].
4. Conclusions
In conclusion, an ultra-smooth thin film of bismite Bi2O3 was pre­
pared by physical vapor deposition (PVD) on a glass substrate, the
morphological, topographical, and structural characteristics of the pre­
(2) monoclinic structure of α-Bi2O3, the linear and nonlinear optical con­
stants were investigated and show the film has a narrow bandgap, as
well as high nonlinear optical constants. These characteristics mean this
(3)
film has potential as a nonlinear optical material.
CRediT authorship contribution statement
Aus A. Najim: Conceptualization, Data curation, Investigation,
Methodology, Software, Validation, Visualization, Formal analysis,
3
A.A. Najim
Writing - original draft, Writing - review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The author gratefully acknowledges the Nanotechnology and
Advanced Materials Research Centre (NAMRC), University of Technol­
ogy, Baghdad, Iraq for preparing, performing experiments, and con­
ducting all tests.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.mssp.2020.105334.
References
[1] P. Melpignano, et al., E-beam deposited ultra-smooth silver thin film on glass with
different nucleation layers: an optimization study for OLED micro-cavity
application, Org. Electron. 11 (6) (2010) 1111–1119.
[2] Pengpeng Xiong, et al., Transparent electrodes based on ultrathin/ultra smooth Cu
films produced through atomic layer deposition as new ITO-free organic light-
emitting devices, Org. Electron. 58 (2018) 18–24.
[3] Xinwen Zhang, et al., Efficient non-doped blue phosphorescent organic light-
emitting devices by incorporating Ag-island nanostructures, Org. Electron. 58
(2018) 25–32.
[4] Lei Wang, et al., Improved stability and performance of visible
photoelectrochemical water splitting on solution-processed organic semiconductor
thin films by ultrathin metal oxide passivation, Chem. Mater. 30 (2) (2018)
324–335.
[5] Deen Gu, et al., Ultrasmooth and thermally stable silver-based thin films with
subnanometer roughness by aluminum doping, ACS Nano 8 (10) (2014)
10343–10351.
[6] Wei Zhang, et al., Ultrasmooth organic–inorganic perovskite thin-film formation
and crystallization for efficient planar heterojunction solar cells, Nat. Commun. 6
(1) (2015) 1–10.
[7] Ross A. Kerner, et al., Ultrasmooth metal halide perovskite thin films via sol–gel
processing, J. Mater. Chem. 4 (21) (2016) 8308–8315.
[8] Xiao Dai, et al., Ultra-smooth glassy graphene thin films for flexible transparent
circuits, Sci. Adv. 2 (11) (2016), e1601574.
[9] Howard A. Dobbs, et al., Ultra-smooth, chemically functional silica surfaces for
surface interaction measurements and optical/interferometry-based techniques,
Adv. Eng. Mater. 20 (2) (2018) 1700630.
[10] Aus A. Najim, Synthesis and characterizations of (δ-Bi2O3)0.93(TiO2)0.07 thin films
grown by PLD technique for optoelectronics, Mater. Sci. Semicond. Process. 71
(2017) 378–381.
[11] Deng Hong-Yan, Hao Wei-Chang, Xu Huai-Zhe, A transition phase in the
transformation from α-, β-and∊-to δ-bismuth oxide, Chin. Phys. Lett. 28 (5) (2011),
056101.
[12] A.F. Gualtieri, S. Immovilli, M. Prudenziati, Powder X-ray diffraction data for the
new polymorphic compound ω-Bi2O3, Powder Diffr. 12 (2) (1997) 90–92.
[13] Kadhim R. Gbashi, et al., Structural, morphological, and optical properties of
nanocrystalline (Bi2O3)1− x:(TiO2)x thin films for transparent electronics,
Plasmonics 14 (3) (2019) 623–630.
[14] Aus A. Najim, et al., Synthesis of efficient and effective γ-MnO2/α-Bi2O3/a-Si solar
cell by vacuum thermal evaporation technique, Plasmonics 13 (3) (2018) 891–895.
Materials Science in Semiconductor Processing 121 (2021) 105334
[15] Deyu Qu, et al., An asymmetric supercapacitor with highly dispersed nano-Bi2O3
and active carbon electrodes, J. Power Sources 269 (2014) 129–135.
[16] Kibret A. Messalea, et al., Bi 2 O 3 monolayers from elemental liquid bismuth,
Nanoscale 10 (33) (2018) 15615–15623.
[17] Abdo Hezam, et al., Synthesis of heterostructured Bi2O3–CeO2–ZnO photocatalyst
with enhanced sunlight photocatalytic activity, Ceram. Int. 43 (6) (2017)
5292–5301.
[18] Q. Qiao, et al., Experimental investigations of the bismuth oxide film grown by
atomic layer deposition using triphenyl bismuth, Thin Solid Films 622 (2017)
65–70.
[19] T.P. Gujar, et al., Electrosynthesis of Bi2O3 thin films and their use in
electrochemical supercapacitors, J. Power Sources 161 (2) (2006) 1479–1485.
[20] Dulce Perez-Mezcua, et al., Photochemical solution deposition of β-Bi 2 O 3 thin
films, J. Sol. Gel Sci. Technol. 81 (2) (2017) 355–361.
[21] Chin-Chung Yu, et al., Stabilization of the β-phase Bi2O3 (201) thin film by an
ultrathin Bi (001) seeding layer, Vacuum 169 (2019) 108918.
[22] B.L. Zhu, X.Z. Zhao, Study on structure and optical properties of Bi2O3 thin films
prepared by reactive pulsed laser deposition, Opt. Mater. 29 (2006) 2–3, 192-198.
[23] P. Lunca Popa, et al., Structural, morphological and optical properties of Bi2O3
thin films grown by reactive sputtering, Thin Solid Films 624 (2017) 41–48.
[24] Matthias J. Müller, et al., Growth of Bi2O3 films by thermal-and plasma-enhanced
atomic layer deposition monitored with real-time spectroscopic ellipsometry for
photocatalytic water splitting, ACS Appl. Nano Mater. 2 (10) (2019) 6277–6286.
[25] Qiang Hu, et al., A light-trapping structure based on Bi 2 O 3 nano-islands with
highly crystallized sputtered silicon for thin-film solar cells, Optic Express 19 (101)
(2011) A20–A27.
[26] Mahima Arya, et al., In-plane and out-of-plane plasmons in random silver
nanoisland films, Plasmonics 13 (2) (2018) 373–383.
[27] Ekaterina Babich, et al., Self-assembled silver–gold nanoisland films on glass for
SERS applications, Phys. Status Solidi Rapid Res. Lett. 12 (1) (2018) 1700226.
[28] Aus A. Najim, et al., Structural, topography, and optical properties of Ba-doped
Mn3O4 thin films for ammonia gas sensing application, Phys. Status Solidi 215 (24)
(2018) 1800379.
[29] Ammar T. Salih, et al., Study of structural phase transition in nanocrystalline
Cobalt Oxide thin films by pulsed laser deposition, Mater. Res. Express 6 (7)
(2019), 076415.
[30] S. Condurache-Bota, et al., Optical and electrical properties of thermally oxidized
bismuth thin films, Appl. Surf. Sci. 257 (24) (2011) 10545–10550.
[31] Mihaela Girtan, et al., Study of oxide/metal/oxide thin films for transparent
electronics and solar cells applications by spectroscopic ellipsometry, AIMS
Materials Science 4 (3) (2017) 594–613.
[32] V. Dolocan, F. Iova, Optical properties of Bi2O3 thin films, Phys. Status Solidi 64
(2) (1981) 755–759.
[33] A.T. Salih, A.A. Najim, A.D. Faisal, Influence of annealing temperature on the
structural, morphological, optical and electrical properties of Cu7S4 thin films
prepared by chemical bath deposition, J. Inorg. Organomet. Polym. 30 (2020)
2258–2265, https://doi.org/10.1007/s10904-019-01358-y.
[34] A. Iljinas, S. Burinskas, J. Dudonis, Synthesis of bismuth oxide thin films deposited
by reactive magnetron sputtering, Acta Phys. Pol., A 120 (1) (2011) 60–62.
[35] S.H. Wemple, M. DiDomenico Jr., Behavior of the electronic dielectric constant in
covalent and ionic materials, Phys. Rev. B 3 (4) (1971) 1338.
[36] Keiji Tanaka, Optical properties and photoinduced changes in amorphous As-S
films, Thin Solid Films 66 (3) (1980) 271–279.
[37] D. Shannon, Robert, et al., Refractive index and dispersion of fluorides and oxides,
J. Phys. Chem. Ref. Data 31 (4) (2002) 931–970.
[38] Ahmed Saeed Hassanien, K.A. Aly, A. Akl Alaa, Study of optical properties of
thermally evaporated ZnSe thin films annealed at different pulsed laser powers,
J. Alloys Compd. 685 (2016) 733–742.
[39] Ahmed Saeed Hassanien, A. Akl Alaa, Optical characterizations and refractive
index dispersion parameters of annealed TiO2 thin films synthesized by RF-
sputtering technique at different flow rates of the reactive oxygen gas, Phys. B
Condens. Matter 576 (2020) 411718.
[40] Baolong Yu, Congshan Zhu, Fuxi Gan, Optical nonlinearity of Bi2O3 nanoparticles
studied by Z-scan technique, J. Appl. Phys. 82 (9) (1997) 4532–4537.
[41] Huidan Zeng, et al., Large third-order optical nonlinearity of ZnO–Bi2O3–B2O3
glass–ceramic containing Bi2ZnB2O7 nanocrystals, J. Eur. Ceram. Soc. 34 (16)
(2014) 4383–4388.