Materials Science in Semiconductor Processing 102 (2019) 104592

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Materials Science in Semiconductor Processing

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Spectroscopic characterization of CVD grown zinc oxide nanowires T

a a b,*
Rabina Bhujel , Sadhna Rai , Bibhu P. Swain (Ph.D)
a
Nano-processing Laboratory, Centre for Materials Science and Nanotechnology, Sikkim Manipal Institute of Technology, Majitar, Rangpo, 737136, India
b
Department of Physics, National Institute Technology Manipur, Langol, Imphal, 795004, Manipur, India

A R T I C LE I N FO A B S T R A C T

Keywords: Zinc oxide nanowires (ZnO-NWs) were deposited by oxidizing Zn powder and characterized by Field Emission
ZnO-NWs Scanning Electron Microscopy (FESEM), photoluminescence, X-ray diffraction (XRD) and X-ray photoelectron
FESEM spectroscopy (XPS) techniques to evaluate its structural, vibrational, optical and chemical composition prop-
XRD erties. The FESEM result shows that the length of the ZnO-NWs increases from 2.6 to 5.0 μm respectively, for
XPS
increasing the O2 flow rate from 40 to 120 sccm with a fixed diameter of 175 nm. The crystallite size and lattice
Phonon lifetime
strain of ZnO-NWs are 26.96 nm and 0.00174 to 0.00408 respectively with increasing of O2 flow rate. The
deconvoluted photoluminescence spectra indicated four major visible emission band at 394.64, 420.96, 465.29,
and 501.43 nm. The phonon lifetime of A1(TO) and E1(TO) decreased with increasing of O2 flow rate. Moreover,
the composition of Zn and O are 43 and 57 at. % respectively in the ZnO-NWs for the 100 sccm O2 flow rate.

1. Introduction microstructural, phonon modes, photoluminescence, and chemical

composition and core orbital spectra of ZnO-NWs with various O2 flow
Zinc oxide nanowires (ZnO-NWs) are one the most extensively rates. In this paper, we are mainly aimed at (a) to investigate the
studied nanostructured semiconductor material with the direct bandgap morphology, structural properties and lattice strain of ZnO-NWs, (b) to
energy of 3.37eV. In the past few decades, ZnO-NWs have attracted the investigate various phonon modes, phonon lifetime and chemical net-
tremendous interest of the researchers due to its widespread applica- work of the ZnO-NWs with different O2 flow rate, (c) to investigate the
tions in the field of photovoltaic devices [1], gas sensors [2], optoe- emission spectra of ZnO NWs with different O2 flow rate, and (d) detail
lectronics devices [3], UV-lasers [4], photodetectors [5] and photo- investigation of electronic structure of O(1s) and Zn(1s) core orbital at
catalysts [6]. Moreover, ZnO-NWs is also an active candidate material 100 sccm O2 flow rate. A comparative analysis has also been made
for the sensing of various gases such as NO2, CH3, CH2OH, NH3, H2S, between different ZnO-NWs with varying O2 flow rates from 40 to 120
O2and H2 at higher temperatures [7]. Xiang et al. synthesized p-type sccm at 850 °C.
ZnO-NWs using phosphorous pentaoxide as the dopant source and O2/
N2 mixture as a carrier gas via CVD technique and observed intense PL 2. Experimental details
spectra at 3.352eVat 850 °C [8]. Sakarni et al. synthesized ZnO-NWs
with varying O2 flow rate from 90 to 130 sccm at a high temperature of The ZnO-NWs were prepared on a p-type silicon substrate by the
960 °C and observed the length and diameter of ZnO-NWs varied from vapor-liquid-solid growth mechanism using a CVD reactor. At first, the
1.51 to 2.5 μm and 50–105 nm respectively [9]. Subannajui et al. pro- RCA cleaning procedure was performed to clean the Si substrate and
vided a detailed study of ZnO-NWs synthesized via vapor phase de- then Agnes were deposited by following the electroless deposition
position technique and demonstrated that change in O2 concentration method. The concentration of AgNO3 was fixed at 10 mM.After that, Zn
controlled the growth rate inside the CVD system [10]. Though various metal powder is taken in a ceramic boat and the Si substrate plated with
synthesis methods have been employed to the synthesis of ZnO-NWs AgNPs were then loaded in the reactor chamber. The Ag plated Si (100)
such as chemical vapor deposition (CVD), template-assisted growth substrate was placed on the downstream to the source with a distance of
[11], hydrothermal process [12], sputter deposition [13], carbothermal 4 cm. The temperature of the furnace was maintained in a growth
process [14], etc. with different O2 flow rates, the detail investigates the temperature of 850 °C and a base pressure of 10−5 Torr. The growth
microstructure, phonon modes and the defects present in ZnO-NWs duration was fixed in 2 h. The flow rates of O2 were varied from 40 to
have not been studied yet. Therefore, it is important to investigate the 120 sccm to study the effect of flow rates on the structure and bonding

*
Corresponding author.
E-mail addresses: [email protected], [email protected] (B.P. Swain).

https://doi.org/10.1016/j.mssp.2019.104592
Received 22 March 2019; Received in revised form 19 June 2019; Accepted 24 June 2019
1369-8001/ © 2019 Elsevier Ltd. All rights reserved.
R. Bhujel, et al. Materials Science in Semiconductor Processing 102 (2019) 104592

Fig. 1. SEM images of ZnO-NWs with 40–100 sccmO2 flow rates.

of as-synthesized ZnO-NWs. After the deposition, the furnace was AgNPs behaves as the seeding layer for the growth of ZnO-NWs on Si
cooled down gradually with the rate of 3 °C/min. The morphology of substrate. Hence, the diameters of ZnO-NWs are solely dependent upon
ZnO-NWs was studied using field emission scanning electron micro- the size of AgNPs and the length of ZnO-NWs is very sensitive towards
scope (FESEM: JEOL-JEM-3000F). The chemical networks and optical the O2 flow rate in the growth system. It may be due to O2 as reactant
properties of ZnO-NWs were analyzed by XPS and Photoluminescence gas to enhance the rate of reaction between Zn and O2.
spectroscopy. Photoluminescence studies were conducted with a
PerkinElmer LS-45 fluorescence spectrometer with a Xe discharge lamp 3.2. X-ray diffraction
operating at room temperature. Structural characterization was done
with the help of XRD using (Rigaku Saturn 724+ Cu (Kα)Single crystal Fig. 2(a) shows the crystal planes of ZnO-NWs from XRD at a dif-
X-ray diffractometer) and Raman spectroscopy was done using ferent O2 flow rate from 40 to 120 sccm. The 2θ diffraction patterns at
(Labram-1Dilor-JobinYvon-Spexmake). Furthermore, the chemical 31.74, 34.52, 36.27, 38.87, 43.14, 47.57, 54.44, 56.56, and 62.85°
composition and bonding networks of the as-synthesized ZnO-NWs corresponds to (100), (002), (101), (102), (110), (103), (112) and (004)
were characterized with the help of XPS spectroscopy using (VG ESCA- respectively. Furthermore, the XRD diffraction patterns of ZnO-NWs
LABMK II system equipped with an Mg KαX-ray (1253.6 eV) source. indicated that it has a perfect hexagonal wurtzite structure with lattice
constants of a = 0.326 nm and c = 0.521 nm in accordance with the
3. Results and discussion values in the standard card (JCPDS number 36–1451 for ZnO). The
planes of Zn appears at 2θ = 38.8° and 43.1° corresponding to (100)
3.1. FESEM and (101) planes respectively. The Zn component decreased mono-
tonically with increasing O2 flow rate. The highly intense peak at
Fig. 1 shows the FESEM images of ZnO-NWs grown at the O2 flow 36.27ocorresponding to (101) plane is used to calculate the crystallite
rates of 40, 60, 80 and 100 sccm. The SEM images show the deposition size of ZnO-NWs by using the Debye Scherrer formula i.e.
of highly dense and randomly oriented arrays of ZnO-NWs on the p-type 0.9λ
Si substrate. By increasing the O2 flow rate from 40 to 100 sccm the D=
βCosθ (1)
length of ZnO-NWs varies from 2.6 to 5.0 μm while the diameter is fixed
at~175 nm. The growth mechanism is the VLS technique in this case as where D is the crystallite size of ZnO-NWs, ?? is the X-ray wavelength

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R. Bhujel, et al. Materials Science in Semiconductor Processing 102 (2019) 104592

Fig. 2. (a) Different XRD planes of ZnO-NWs with 40–100 sccm O2 flow rate. (b)βcosθ vs 4 Sin θ plot to evaluate lattice strains from Williamson- Hall formula.

(1.54 nm), β is the FWHM of the most intense XRD peak and θ is the ZnO-NWs [17]. The asymmetric A1(LO) and E1(LO) modes are obtained
value of diffraction angle. The crystallite size of ZnO-NWs is 26.96 nm 578 cm−1 correspondings to the oxygen defects present in the ZnO-NWs
as calculated by using equation (1). The strain present the ZnO-NWs [18]. A SO phonon peak is observed at around 485 cm−1 in between the
was further calculated by applying the Williamson-Hall formula ‫׃‬ E2 (high) and A1(LO) peak corresponding to the nanowire dimensions
K and characteristics of phonon confinement in ZnO-NWs, which shows
βCosθ = + 4εSinθ
(2) an enormous increase in the intensity for higher O2 flow rates. The main
D
observation in Fig. 3 (a) are as follows, (i) E2H-2L shows the peak po-
where ε is the slope of the fitted straight line as shown in Fig. 2(b) and K sition shifts to higher wavenumber, (ii) the two shoulder peaks of
is shape factor (0.9). The lattice strain of ZnO-NWs varied from 0.00408 E2(High), A1(TO) and E1(TO) peak position remains constant, and (iii)
to 0.00174 with the positive slope, corresponding to the presence of A1(LO) and E1(LO) peak show red shift with increasing in the O2 flow
tensile strain in the ZnO-NWs thin films. Lupan et al. previously re- rate from 40 to 120 sccm. E1(TO) peak attribute mainly due to the
ported similar XRD results for the ZnO-NWs deposited by CVD tech- presence of dislocations or defects in ZnO-NWs thin films. The shifting
nique at 650 °C [15]. The increase in tensile strain is may be due to the of E2H-2L peak towards higher wavenumber corresponds to the in-
formation of greater sized crystals also due to the increasing ZnONWs creasing number of Zn-O bonds in ZnO-News with an increase in the O2
length at higher O2 flow rates. flow rate. Even more, the redshift of A1(LO) and E1(LO) phonon modes
is due to the fact that at higher O2 flow rate more number of Zn-O bods
3.3. Raman spectroscopy are formed and also the oxygen vacancy present in ZnO-NWs are filled
to some extent. For detail phonon analysis, each the Raman spectra of
The zone center optical phonons for ZnO-NWs with C64 V space group ZnO-NWs from 250 to 625 cm−1 were deconvoluted into six Lorentzian
are peaks. Fig. 3(b) shows deconvolution of Raman spectra of ZnO-NWs of
Γopt = 1A1 + 2B1 + 1E1 + 2E2 (3) 120 O2 flow rate. The peak position of A1(TO), E1(TO), E2(High), SO,
A1(LO) and E1(LO) are observed at 331.2, 384.7, 436.7, 483.9, 522.5
where A1, E1, and E2 are Raman active modes and B1 refers to the and 565.9 cm−1 respectively. The full width at half maxima (FWHM) of
Raman inert mode. A1 and E1 are considered as the polar modes hence A1(TO), E1(TO), E2(High), SO, A1(LO) and E1(LO) are 41.41, 54.08,
are split into the transverse optic (TO) and longitudinal optic (LO) 18.93, 32.82,26.87, and 36.56 respectively. The FWHM of Raman shifts
phonons. The E2 mode corresponds to the non-polar phonon vibration, indicates the defect distribution and it is inversely related to the hole
which generates two peaks for E2 (high) and E2 (low) mode phonons. lifetime of ZnO-NWs.
Fig. 3 (a) shows the room temperature Raman spectra of ZnO-NWs with Fig. 4(a) shows the Raman peak position and FWHM of A1(TO) and
the O2 flow rates varying from 40 to 120 sccm. The Raman signature at E1(TO) at O2 flow rates of 40-120 sccm. The Raman peak position of
333 and 383 cm−1 correspond to A1(TO) and E1(TO) phonons respec- A1(TO) and E1(TO) shifted from 329.38 to 331.18 cm−1 and increasing
tively [16]. The narrow and intense band observed at 438 cm−1 is as- 385.25 to 384.7 cm−1, indicating the change of interparticle interaction
signed for the E2 (high) mode which describes the crystal quality of the

Fig. 3. (a)Raman spectra of ZnO-NWs, and (b) deconvolution of Raman spectra into six Gaussian peaks for ZnO-NWs with O2 flow rate from 40 to 120 sccm.

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Fig. 5. Photoluminescence spectra of ZnO-NWs and inserted deconvolution of

PL spectra into four Gaussian peaks with different O2 flow rate.

NWs with different O2 flow rate. The phonon lifetime(τph) of ZnO-NWs

were estimated inversely related to the FWHM of Raman spectra con-
sidering from Heisenberg uncertainty principle
1/ τ = (FWHM)/ℏ (4)
where ђ is the Plank’s constant. The phonon lifetime of A1(TO), E1(TO),
E1(High), SO, A1(LO) and E1(LO) are varied from 2.16 × 10−13 to
1.28 × 10−13s, 2.77 × 10−13 to 0.98 × 10−13s, 3.19 × 10−13 to
0.98 × 10−13s, 7.44 × 10−13to 1.62 × 10−13s and 2.37 × 10−13 to
Fig. 4. (a) Raman peak position and FWHM of A1(TO) and E1(TO), (b)Raman 1.45 × 10−13s respectively. All phonon lifetime is increasing with in-
peak position and FWHM of A1(LO) and E1(LO), and (c) Intensity ratios of creasing of O2 flow rate. The increasing of phonon life of A1(LO) in ZnO
A1(TO)/E1(TO) and A1(LO)/E1(LO) peaks with O2 flow rates of 40-120 sccm.
NWs with increasing O2 flow rate is not clear.

in the ZnO NWs. The FWHM of A1(TO) and E1(TO) increasing from 24.5 3.4. Photoluminescence
to 41.4 cm−1and19.1 to 54.1 cm−1 respectively. This due to increasing
FWHM of A1(TO) and E1(TO) corresponds to the crystal defects arising Fig. 5 shows the room temperature photoluminescence spectra of
from either Zinc or oxygen vacancy. The length of ZnO-NWs increases ZnO-NWs synthesized at the O2 flow rates varied from 40 to 120 sccm.
with increasing the O2 flow rates. This further leads to an increase in The PL spectra detect the presence of two prominent bands at around
the structural defects within the ZnO-NWs. Fig. 4(b) shows the Raman 394 (3.14 eV) and 465 nm (2.6 eV) for ZnO-NWs synthesized at the O2
peak position shifting of both A1(LO) and E1(LO) peak towards the red flow rate of 120 sccm [19] which is further deconvoluted into four
region from 547.54 to 522.51 cm−1, for higher flow rates of O2 showing bands at around 393, 418, 465 and 514 nm. The band gap of ZnONWs is
an increase in the phonon confinement effect and decrease in the 3.14 eV as obtained by the PL spectra which is slightly less than the
structural constraint of the ZnO-NWs film as a result of the increased band gap of ZnO crystal i.e. (3.37eV). This could be due to the presence
length of ZnO-NWs. The FWHM of A1(LO) and E1(LO) decreases from of more number of dangling bonds in ZnONWs than that of ZnO crys-
41.54 to 26.87 cm−1 with increasing the O2 flow rates, corresponding tals. Moreover when the O2 flow rate increased the length and diameter
to the randomness of the nanowire dimensions. Fig. 4(c) shows the of ZnONWs increases so as the dangling bonds. Which results in the
intensity ratios of A1(TO)/E1(TO) with different O2 flow rate. The decrease of the band gap in ZnONWs as compared to the ZnO crystals.
A1(TO)/E1(TO) decreases from 2.02 to 0.42 with increasing the O2 flow Li et at. studied the effect of increasing dangling bonds on the band gap
rate which corresponds to the increasing structural anisotropy and ionic of SiC-NWs [20–22]. The emission spectra at 393 nm (P1) corresponds
behavior of ZnO-NWs. to the near-band-edge emission of ZnO-NWs which arises due to the
Table 1 shows the phonon lifetime of different phonon in the ZnO recombination of electron-hole pairs in between the valence and

Table 1
PhononLifetime Estimated from FWHM of Raman spectra.
O2flow rate τA1(TO) τE1(TO) τE2(High) ( × 10−13s) τSO ( × 10−13s) τA1(LO) τE1(LO)
( × 10−13s) ( × 10−13s) ( × 10−13s) ( × 10−13s)

40 sccm 2.16 2.77 3.19 7.44 0.86 2.37

60 sccm 1.94 1.56 2.91 6.45 0.94 1.90
80 sccm 1.54 1.16 2.75 4.21 1.31 1.52
100 sccm 1.51 1.05 2.76 2.29 1.73 1.42
120 sccm 1.28 0.98 2.80 1.62 1.97 1.45

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R. Bhujel, et al. Materials Science in Semiconductor Processing 102 (2019) 104592

Table 2
Details of deconvolution of ZnO NWs Photoluminescence with difference O2 flow rate.
O2flow rate (sccm) P1 (eV) P2(eV) P3(eV) P4(eV) FWHM1 (eV) FWHM2 (eV) FWHM3 (eV) FWHM4 (eV)

40 394.64 420.96 465.29 501.43 21.104 36.962 34.077 65.196

60 393.79 419.18 463.73 501.54 21.012 35.865 36.326 63.593
80 392.88 417.96 462.68 500.13 21.13 35.287 36.632 62.61
100 391.14 415.07 461.25 500.17 20.708 34.202 38.851 62.278
120 389.55 414.25 461.26 498.27 19.942 35.817 35.06 60.027

conduction band showing good crystallinity of ZnO-NWs. The emission spectrum shows the presence of auger peaks for Zn at 474.85, 500.55,
spectra at 418 nm (P2) corresponds to the zinc vacancy related defect 583.69, 664.54eV are corresponding to L2M45M45, L2M45M45, L1M23M23,
states, and peak at 465 nm (P3) corresponds to the oxygen defect due to and L1M23M23 respectively. The Auger peak of OKLL and CKLL are ob-
the transition of an electron from the conduction band of ZnO-NWs to served at976.7 eV and 1234.3eV respectively. The estimated atomic
Oins [23]. However, the peak of emission spectra at 514 nm (P4) is percentage for oxygen and Zinc are further calculated by using the
observed due to the electronic transition occurring between the closely formula,
spaced impurities levels as created by the oxygen vacancy [24]. The Ai
details of photoluminescence deconvolution spectra in Table 2, with the Si
Atomic %=
difference O2 flow rate. A
∑ Si
i (5)

3.5. X-ray photoelectron spectroscopy where Ai is the area under the curve and Si is the sensitivity factor.
Therefore, the composition of zinc and oxygen comes out to be 57 and
Fig. 6(a) shows the broad spectrum XPS scan of ZnO-NWs at an O2 43 at.% respectively at the O2 flow rate of 100 sccm.
flow rate of 100 sccm to examine the chemical compositions and Fig. 6(b) shows the core orbital XPS spectra of O(1s) region for ZnO-
bonding networks present on it. The spectrum shows the presence of NWs with the O2 flow rate of 100 sccm. The peak accounts for the
zinc and oxygen atoms with a very small carbon peak, which confirms presence of three shoulders like structures at different binding energies
the good purity of as-synthesized ZnO-NWs. The core orbital spectra for hence it is deconvoluted into three peaks by doing the Gaussian fitting.
Zn(3d), Zn(3p), Zn(3s), C(1s), O(1s), Zn(2p)3/2, Zn(2p)1/2and Zn(2s) The peak with the binding energy of 524.8eV and FWHM of 5.74 eV
are observed at ~14.1, ~89, ~140, ~284, 530.3, 1021.2, 1044.4 and corresponds to the presence of the outer oxide layer of surface Zinc
~1200 eV respectively [25]. A doublet signal is observed for Zn(2p) atoms. The peak energy at 529.0eV with FWHM 5.27 eV is associated
orbital at 1021.2 and 1044.4 eV corresponding to the Zn(2p)3/2 and Zn with the internal bonding between the Zn and Oxygen atom. The peak
(2p)1/2core levels. The Ag(3d) core orbital is observed at the binding energy associated with 535.0eV having FWHM of 4.83 eV corresponds
energy of 337.22 eV from the catalyst. The binding energy difference of to the surface O-O-Zn- bonding region of the nanowires.
~23 eV between the two 2p signals reveals the presence of +2 oxi- Fig. 6(c) shows the core orbital spectra for Zn (2p)3/2 region at the
dation state of Zn atom in the ZnO wurtzite structure. Even more, the binding energy range of 1010–1050 eV. The presence of shoulders

Fig. 6. (a) XPS spectra of ZnO-NWs, (b) Deconvulation O(1s) XPS spectra, and (c) deconvulation of Zn(2p3/2) XPS spectra for ZnO-NWs of 100 sccmO2 flow rate.

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