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M. Soylu, M. Coskun
PII: S0925-8388(18)30080-X
DOI: 10.1016/j.jallcom.2018.01.079
Reference: JALCOM 44543
Please cite this article as: M. Soylu, M. Coskun, Controlling the properties of ZnO thin films by varying
precursor concentration, Journal of Alloys and Compounds (2018), doi: 10.1016/j.jallcom.2018.01.079.
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M. Soylu*, M. Coskun
Department of Physics, Faculty of Sciences and Arts, Bingol University, Bingol, Turkey
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Abstract
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This paper reports the synthesis of zinc oxide (ZnO) nanofibers, changing the molar
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concentration (M) of zinc acetate dihydrate (ZnAc) using 2-methoxyethanol and
monoethanolamine. X-ray diffraction pattern reveal that ZnO thin films indicate good
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crystallinity at high precursor concentration. Atomic force microscopy (AFM) images show
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the formation of ZnO nanofibers. The optical properties changing with increasing
concentration are understood from the recorded transmittance, absorbance and reflectance
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measurements. The band-gap narrowing (from 3.28 eV to 3.22 eV) of n-type ZnO thin films
heterojunction structure exhibits low rectifying ratio (RR). The current-voltage (I-V)
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characteristics show that the conductivity increases as the molar concentration of precursor
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decreases from 0.5 to 0.2 M. An optimum value of molar percentage for precursor
*Corresponding author: Department of Physics, Faculty of Sciences and Arts, Bingol University,
Bingol, Turkey e-mail address: soylum74@yahoo.com ; msoylu@bingol.edu.tr (M. Soylu)
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1. Introduction
Currently, there is strong interest in thin films of crystalline zinc oxide (ZnO) that
offers scientifically and technically, opportunities for the device applications. ZnO thin films
are known to be superior to many metal oxides because of its unique properties such as high
exciton binding energy (60 meV), piezoelectric, efficient emission at room temperature, wide-
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bandgap, and much higher electron mobility of 60-100 cm2V/s [1]. Nano-structure ZnO has
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been extensively worked in solar cells [2,3], photocatalysis [4,5], photonic crystals [6],
biological fluorescence imaging [7], sensors [8], piezoelectric nanogenerators [9], light
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emitting diodes (LED) [10] and photodiodes [11]. ZnO structure characterized by bonding of
Zn2+ and O2- shows n-type electrical conductivity, attributing the effect of oxygen vacancies
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(or interstitial Zn (Zni)). ZnO can be synthesized simply by many method because of the
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relatively easy oxidation of Zn.
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Over the past years, different methods have been reported for synthesis of ZnO
nanostructres, including chemical vapor deposition (CVD) [12], sol-gel [13], thermal
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evaporation [14], sputtering [15], allowing the modification of the surface structure and
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tailoring of the nanostructure. So-gel spin coating technique possesses advantages compared
to other method without requiring any vacuum and the sophisticated equipment set-up for the
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growth of the ZnO thin films as well as composition modification, control of the
stoichiometry, homoeneous and smooth thin films, possibility to produce the layer on large
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area. In most reports, the modification of ZnO thin films was realized by doping with various
metals, post-growth annealing treatment, tuning the Zn:O ratio and gas (oxygen, nitrogen,
argon) flow rate during the growth. In addition, the concentration of the precursor solution is
one of the controlling factors on sensitization of ZnO thin films [16,17]. Guzmán-Carrillo et
al. [18] synthesized ZnO nanostructures by modified polyol method. They concluded that
there was a relation between the molar concentration of zinc acetate Zn(Ac)2 and morphology,
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varying the molar concentration of the precursor salt, in the range 0.6-1.0 M. The effect of
precursor concentration on high-quality ZnO thin films should be further discussed, since the
film property (crystal quality, transparency, electrical conductivity, etc.) deteriorates after a
In the present work, we deposited thin films of ZnO on glass and Si substrates by
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using sol-gel method that is a wet-chemical technique. We presented the results of an
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experimental programme to investigate the characteristics of ZnO prepared as function of the
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2. Experimental Details
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To obtain ZnO thin films, all of materials were commercially supplied. Zinc acetate
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dihydrate (ZAD) (Zn(CH3COO)2.2H2O) is a zinc salt. 2-methoxyethanol (C3H8O2) is a
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a stabilizer. Experimental steps were performed to obtain sol-gel compositions [19]. Fig. 1
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shows flow chart of synthesis procedure for ZnO thin films. The precursor concentrations
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were tuned to be 0.2 M, 0.3 M and 0.5 M. The resultant sol was aged in a closed sample
preparation bottle at room temperature for 18 h. Molarity-dependent some parameters for the
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preparation conditions of ZnO nanostructures are given in Table 1. Before the deposition
process, in order to remove the unwanted contaminations, and thus to improve the quality of
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the films, soda-lime glasses (SLG) were carefully cleaned in ultrasonic bath with acetone,
methanol and deionized water (DI water), respectively. p- type Si substrates were chemically
cleaned. Finally, samples were cleaned with DI water and dried in pure nitrogen atmosphere.
ZnO gel was deposited on the glass and p- type substrates and rotated at 800 rpm for 35 s.
After ZnO coating, the samples were subjected to heat treatment at 480 °C for 1 h. Al
(aluminum) was thermally evaporated on the back side of p-Si substrates (for ohmic contact),
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and then on the ZnO thin films through a molybdenum mask. Thus, the resulting Al/ZnO/p-Si
device structures were obtained. The structural characteristics of the ZnO thin films were
analysed by X-ray diffraction (XRD, Rigaku) using Cu Kα radiation. The surface morphology
of the thin films was evaluated by atomic force microscopy (AFM) measurements. From these
measurements, the average film thickness was estimated to be about 115±0.5 nm. Optical
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characterization was carried out by using UV-vis spectroscopy (Shimadzu UV-VISNIR 3600
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spectrophotometer). The information about molecular vibrations was provided by Raman
spectroscopy. Keithley 2400 voltage source was used for the current-voltage (I-V)
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characterization of ZnO/p-Si heterojunctions.
Fig. 2 shows X-ray diffraction (XRD) pattern of ZnO thin films (deposited on the
Refinement of X-ray diffraction pattern was used to determine the crystal structure
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parameters. XRD spectra indicated the presence of almost all characteristic peaks of ZnO thin
films, which correspond to diffraction planes at (100), (002), (101), (102), (110), (103), (200),
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(112), (201), (004) and (202), respectively. ZnO thin films obtained using pulsed laser
deposition (PLD) technique exhibit only one peak corresponding to (002) plane in the 2θ
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range of 20-60 degree [20]. ZnO has wurtzite structure of a hexagonal pattern with space
group P63/mc. The peaks show very well match with data in Joint Committee on Powder
Diffraction Standard (JCPDS) card No. 36-1451. Dominant peaks are seen at Bragg’s angle
(2θ) of 27° to 33°. Shift in diffractions peaks is observed for different conditions of the
precursor concentration, showing that no structural deformation caused in the lattice of ZnO
upon molarity. XRD peaks on ZnO thin film prepared with precursor solution of 0.5 M were
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more intense and narrow, indicating good crystallinity of the films. However, ZnO thin film
with precursor solution of 0.2 M exhibited higher crystallinity when compared to other
sample (precursor solution of 0.3 M). It is seen from Table 2 that the full width at half
increases for 0.5 M. The peak intensity is high for solution concentration of 0.5 M, showing
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the influence of precursor molarity on surface texture (orientation) of the ZnO films. The
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content of the component elements has an effect on the type of deformation texture. Texture-
dependent properties affect the magnetic properties, elasticity, stress and elongation. The
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texture coefficient (TC(hkl)) of the plane is specified by the preferred orientation of surface and
estimated by [21],
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I ( hkl ) / I 0 ( hkl )
TC( hkl ) = (1)
N −1
∑I ( hkl ) / I 0 ( hkl )
M
n
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where I(hkl) is the measured relative intensity of the plane (hkl), N represents the number of
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diffraction peaks, Io(hkl) is the standard intensity of the plane (hkl) taken from the JCPDS
data. Depending on the molar concentration, the texture coefficients for ZnO films are
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tabulated in Table 2. If the texture coefficient is equal to 1, the crystal orientation is randomly
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oriented [22]. Dominant peaks for all samples indicate that the surface of the thin films is
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textured along (100) plane. TC value of (100) peak calculated for 0.5 M is high when
compared to other samples. While the molarity is increased from 0.2 M to 0.3 M, the TC
value of (002) peak increases from 2.55 to 2.60, and then it remains constant with increase in
molarity up to 0.5 M. Even if the increase in the texture coefficient causes an increase in grain
boundary mismatch, it introduces additional porosity in thin films. The increased porosity has
a potential for permeation of gas molecules in the mechanism of gas sensing [23]. Reduction
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in texture coefficient of (100) plane can produce the saturated bonds across the plane, creating
the interfacial satates which act as energy levels for junctions. The texture analysis provides
the information about the factors affecting gas adsorption and desorption.
crystallinity. FWHM that is inversely proportional to the average crystallite size makes it
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possible to find the crystal size for ZnO using Scherrer equation. The average crystallite size
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(D) is given as follows [24]:
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0.94λ
D= (2)
β cosθ
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where λ is the incident x-ray wavelength with the value of 1.54 A°. β is the FWHM. The value
0.94 is the correlation factor. θ is the Bragg angle. D values are given in Table 3. The
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crystallite size increases with increasing solution molarity, but it decreases with increase in
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molarity further. The literature on similar variation is available [16,25]. The solution molarity
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has an effect on the crystallite size of the films. Furthermore, the grain size is influenced by
the preparation conditions, i.e., growth rate, the aging time of solution and the nucleation refer
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to the grain size. Dislocation density (δ) in the unity of lines/m2 and strain values (ε) along c-
1
δ= (3)
D2
β cosθ
ε= (4)
4
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Dislocation density is evaluated considering the peak of (002). The values are given in Table
3. Both the dislocation density (δ) and strain (ε) values decrease as the precursor
concentration increases. The parameters also include an increase for 0.5 M. The dislocation
density for our samples was found in the order of 1013. The value is low when compared with
6.395x1014 value determined for spray deposited nanocrystalline ZnO thin films by Alkhayatt
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and Hussian [26].
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The lattice parameters ’’a’’ and “c” for the wurtzite structure are determined from the
reciprocal of the spacing (dhkl) between (hkl) planes. Lattice constant (a) is calculated using
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the following relation [27]:
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λ h2 + k 2 + l 2
a= (5)
∑ I (hkl ) / I 0 (hkl )
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2 1
N
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1
=
(
4 h 2 + hk + k 2
+
)l2
(6)
2
a2 c2
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d hkl 3
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where dhkl is interplanar spacing for planes with Miller indices (hkl). The determined lattice
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parameters for the peak (002) are listed in Table 3. Standard values for ZnO polycrystalline
powder were found to be a = 3.249 Å, c = 5.201 Å [28,29]. The value of c/a ratio is 1.60 for
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ZnO with precursor concentration of 0.5 M. This is in good agreement with the value found
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for zinc oxide thin films prepared by thermal oxidation [30]. The c/a ratio is examined for the
effects on the lattice parameters due to the precursor concentration in ZnO. The c/a ratio is
approaching the standard value of about 1.63, as the precursor concentration increases.
for ZnO thin films deposited on the glass substrates is shown in Fig. 3a-d. The results
confirmed the presence of Zn and O elements. As seen from Fig. 3(d), the content of Zn
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increases with increasing molar concentration. Fig. 4a-c shows AFM micrograph of ZnO thin
films (0.2 M, 0.3 M and 0.5 M, respectively). AFM results show the existence of nano-fiber
structure. Figures exhibit different morphological images. The surface with nano-particles is
indicates the machined surface state. The surface parameters include the arithmetic average of
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absolute values (Ra), root mean squared (Rq), average distance between the highest peak and
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lowest valley in each sampling length (Rz) and maximum peak height (Rp). The roughness
appears to change with molar concentration. The lowest value of surface roughness was
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obtained for the sample prepared at molar concentration of 0.5 M.
Fig. 5a shows the transmittance spectra for ZnO thin films as a function of solution
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molarity. There is sharp absorption edge at about 300 nm. The average transparency is over
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80%. The absorption band is blueshifted with decreasing precursor concentration, showing a
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variation in the optical bandgap in the visible region. The transparency depends on the
wavelength of the incident exciting beam. It decreases with increasing molarity in the infrared
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region. The transparency is also related to the Zn/O stoichiometric ratio. The transparency
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improves as the stoichiometric ratio (Zn/O) approaches 1 [31]. In the present study, the
transparency increases in the visible region, as both the precursor concentration and
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stoichiometric ratio (Zn/O atomic ratios changing from 2.28 to 1.93) decrease. With the
further decrease in concentration, the transparency continues to increase, but, Zn/O atomic
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ratio not. The spectrum of ZnO thin films has characteristic absorption bands at 581 nm and
663 nm, indicating the electron transitions. Peaks that appear to be weak are characteristic p-d
Fig. 5b shows the reflectance characteristics of ZnO thin films as a function of the
concentration affects the absorption characteristics of ZnO thin films. There is a strong
absorption to excite electrons from the valence band to the conduction band. While the
molarity is increased from 0.2 M to 0.5 M, the absorbance increases in UV-region. The
absorption shows a significant increase at wavelengths <400 nm, showing the intrinsic band
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gap absorption (free carrier absorption) of ZnO thin films [34]. Quantum size effect induces
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shifting of absorption spectra [18,35,36].
The analysis of the optical absorption measurement is carried out to obtain the optical
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band gap of the films. The optical band gap is calculated by the following relation [37]:
αhν = B(hν − E g ) n
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where B is a constant coefficient, α absorption coefficient, Eg the optical band gap , hν is the
photon energy and. n that is an index determines the character of optical absorption. It is equal
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to 1/2 for allowed direct, 3/2 for forbidden direct, 2 for allowed indirect, and 3 for forbidden
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indirect transition. The plot of (αhν)2 vs. hν gives the best fit by Tauc plot method, showing a
discontinuity (Fig. 5d). Thus, the optical energy gap of ZnO thin films has the allowed direct
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transition. The optical absorption coefficient ( α ≥104 cm−1) displays direct band to band
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transitions. The resulting optical band gaps are given in Table 3. The effect of molar
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concentration on the Eg is seen as more effective. The Eg values were determined to be 3.28,
3.25, and 3.22 eV for 0.2 M, 0.3M and 0.5 M, respectively. It is reported in the literature that
the direct band gap value of ZnO thin films extends from 2.20 eV up to 3.30 eV [38-40]. The
direct band gap value of ZnO thin films differs according to the synthesis method used in the
synthesis of ZnO thin films, i.e. sol-gel, metalorganic vapour phase epitaxy (MOCVD), DC
reactive magnetron co-sputtering from metallic Zn, and spray pyrolysis method. The Eg
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values are also affected by the amount of charge carriers in ZnO films and the random
distribution of crystallites inside nanocrystalline ZnO film layers. The decrease in energy at
higher precursor concentration is thought to be caused by localized states. The states may
arise from some defects and oxygen vacancies, taking into account structural disorders [41].
However, it is recognized that there is a decrease in the band gap energy as a result of the
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increase in the crystalline size with increase in precursor concentrations. The optical band gap
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and the crystallite size of ZnO are expected to be related to each other, as they change as a
function of molarity [42]. The variation of optical band gap with crystallite size is expressed
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as follows [43]:
πa
E g = E g (∞ ) + Eb b
2
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(8)
R
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where Eg(∞) is bulk band gap, Eb is the exciton binding energy (approximately 60 meV for
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ZnO), ab is exciton Bohr radius and R is nano-crystallite radius (= D/2). Optical band gaps
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calculated for 0.2 M, 0.3 M and 0.5 M are 3.20 eV, 3.203 eV and 3.24 eV, respectively. The
theoretical band gaps as well as the experimental are confirmed by the change of the
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crystallite size.
concentrations is shown in Fig. 6. Near-band emission (NBE) of all the samples reveals under
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the excitation wavelength of λ=370 nm. PL measurement shows a broad peak centered at
about 402 nm for 0.2 M. The peak maximum shows a slight shift when varying the precursor
concentration. The peak intensity is higher at molar concentration of 0.5 M, showing a partial
mechanism. It is considered that the lowest non-radiative defect density is in the ZnO sample
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with a concentration of 0.5 M. The red-shift emission of the PL can be attributed to layers
containing large densities of defects i.e., lattice distortions, electron–phonon interactions, and
localized charge carriers [44,45]. PL measurements can be used to determine the band gap.
The approximated band gap of 3.08 eV is low when compared to that determined from the
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The non-destructive Raman method allows the analysis of the interaction of phonons
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(vibration modes) with the carrier electrons, phase orientation, low frequency transitions, and
transport properties. Fig. 7 shows the Raman spectra of ZnO thin films at room temperature.
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λincidence is 532 nm. According to the backscattering geometry, Raman scattering was recorded
in the range of 200 to 2500 cm−1 as a function of the precursor concentration. All of samples
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give peaks, indicating phonon dispersion branches in ZnO. While the position of the peak
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exhibits a weak dependence on the molar concentration, the highest peak intensity is seen in
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the ZnO sample with the concentration of 0.5 M. Because ZnO has the hexagonal wurtzite
crystal structure, scattering is in the direction of the c-axis [46]. So, it is expected that
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scattering by the allowed E2 and A1 (longitudinal optical, LO) and E2 phonon modes in
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Raman scattering will occur in paralel (HH) and crossed (VH) polarization, respectively. One
cannot observe the E1 (LO) mode due to the forbidden nature of the transition (Raman
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selection rule). A broad peak at 564 cm-1 corresponds to the A1high (LO) phonon mode of ZnO,
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indicating the lattice vibrations of Zn atoms. The peak at 1109 cm-1 is related to the 2 A1high
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(LO) phonon mode, defining the wurtzite phase of ZnO and vibration of the oxygen atoms.
The FWHM at 564 cm-1 was found to be 64.43 cm-1, 82.56 cm-1, 78.42 cm-1 for the ZnO
samples with concentrations of 0.5 M, 0.3 M and 0.2 M, respectively. In this case, FWHM
results confirmed the crystalline quality of the ZnO thin film with a concentration of 0.5 M as
related to the localized states in the band gap is explained as Urbach-Martienssen tails and
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α = α 0 exp
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(9)
Eu
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where α 0 is a constant, Eu is the Urbach energy. Fig. 8 shows the plots of ln(α) as a function
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of photon energy (hν). The plot is formed to establish a reciprocal gradient of the linear
portion for determining Urbach energy. Urbach tail is attributed to the effect of possible
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defects such as impurity, the disorderness of the film, and the density of state. Urbach energy
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values are given in Table 3. The lowest value of Urbach energy was obtained for the sample
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degradation of the film quality. The molarity of the solution can cause strain that changes the
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interatomic spacing of ZnO thin films. The disorderness of the film, which is related with the
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Urbach energy, is locally depending on stress due to the interatomic distance. The exciton
coefficient associated with the refractive index, is combined with Urbach tailing [48]:
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E − E1
C
k = k0 exp (10)
Eu
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where ko is a constant, Eu is the Urbach band energy and E1 is energy value showing the onset
of absorption. Absorption and extinction coefficients (k) show similar character. The plots of
extinction coefficient (k) vs. wavelength are shown in Fig. 9. The extinction coefficient varies
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depending on the molarity, indicating normal dispersion behaviour. The relationship between
the complex refractive index (n) and the exciton coefficient (k) is as follows:
n* (λ ) = n(λ ) + ik (λ ) (11)
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R=
(n − 1)2 + k 2 (12)
(n + 1)2 + k 2
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1+ R 4R
n= + − k2 (13)
1− R (1 − R )2
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The refractive index dispersion is evaluated by using Wemple and DiDomenico’s single
oscillator model [49]. The refractive index at a certain frequency is given as follows [49]:
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Ed E0
n2 = 1 + (14)
E − (hν )
2 2
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0
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where E0 is the oscillator energy. Ed is the dispersion energy and related to the band-to-band
optical transition intensity. Fig. 10 shows the variation of 1/(n2-1) vs. (hν)2 of the ZnO thin
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films. The Ed and E0 are estimated from the fitting straight line. Results are given in Table 3.
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It is seen that the oscillator energy is decreased and approached to value of E0 = 2Eg for 0.3 M
as the molar concentration increases. The dispersion energy value (4.056 eV) for 0.5 M is the
lowest level of the prepared ZnO samples, while the dispersion energy value for 0.3 M is
6.338 eV. This indicates that the dispersion energy depends on the precursor concentration. A
similar investigation was made by Dhas et al. [50] for cobalt oxide (Co3O4) films. They found
a relation for optical band gap energy (E0 = 1.5Eg). The dispersion energy (Ed) is an important
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tool to study the strength of interband optical transitions which change with solution
concentration. Also, the Ed/E0 ratio from the relation n0=(1+Ed/E0)1/2 allows to find the value
The total power loss (the volume and surface energy) transmitted through the
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by a low dissipation factor (tan δ ). The factor tan δ is defined as the following ratio [51]:
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ε2
tan δ = (15)
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ε1
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where ε is the complex dielectric constant with the real (ε1) and imaginary (ε2). The
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dissipation factor tanδ in a dissipative system is related to the loss-rate of power. Fig. 11
shows the variation of tanδ vs. λ. As can be seen in Fig. 10, the dissipation factor increases as
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function of molarity. The energy loss function plays important role in optoelectronic device
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applications. The volume and surface energy loss functions are written as follows [52]:
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1 ε
− Im * = 2 2 2 (16)
ε ε1 + ε 2
C EP
1 ε2
− Im * = (17)
ε + 1 (ε1 + 1) + ε 2
AC
2 2
Fig. 12a,b shows the plots of the volume and surface energy loss vs. hν . The surface energy
loss is lower compared to the volume energy loss. Both parameters vary as a function of
molarity.
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3.2. I–V Characteristics of ZnO/p-Si Heterojunction Diodes
bias and forward bias. The first system is in thermal equilibrium, indicating that Fermi energy
is constant across ZnO and p-Si. An ohmic contact between p-Si and Al electrode occurs. The
junction allows current flow in one direction (forward bias applying a positive voltage to p-Si)
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[53]. The barrier to electrons in the conduction band of ZnO (injection of electrons) is small
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compared to the holes (hole injection) in p-Si. In the case of forward bias of ~1 V, the barrier
to the injection of electrons disappears as a result of this process (second diagram in Fig. 13a).
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So, the carriers in the ZnO can diffuse to the p-Si, resulting in diffusion current. Fig. 13b
shows the current-voltage (I-V) measurements of Si heterojunctions with ZnO thin films
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prepared at various molar concentrations. It is seen that ZnO/p-Si heterojunction shows
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rectifying behavior. The rectification property comes from an asymmetric and nonlinear I-V
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curve. The observed rectification is caused by barrier between n-ZnO and p-Si. Metal-
semiconductor Schottky barrier is considered negligibly small. The rectification ratio (RR) is
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also voltage dependent. The current increases sharply from 17.9 µA at 0.54 V to 590 µA at 2
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V, as the bias voltage in forward direction goes beyond 0.54 V. However, the current
increases slowly under negative bias in reverse direction and reaches to 17.8 µA at -2 V. So, it
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is evident that the rectifying effect is observed throughout the positive bias voltage. The diode
RR, as-known I(+2 V)/I(-2 V), was found in the range 16.31–33.05 for the heterojunction
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structure. The RR increases with increasing molar concentration. The optimized molar
and the effect of interfacial asymmetry [54]. The high symmetry of the I-V plots in the
forward and reverse direction reduces the rectification efficiency. The findings indicate a
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probable way to control the rectifying property in transparent conduction oxide based Si
The forward bias current of ZnO/p-Si heterojunction diode increases, as the precursor
concentration increases. The leakage current increases slowly with increasing bias voltage in
negative direction. However, the higher leakage current is seen with increasing molar
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concentration. ZnO’s Fermi-energy shift is responsible for the increase in the leakage current.
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The leakage current includes the components of recombination-generation in the depletion
layer and tunneling-induced currents [55]. The combined effects of molar concentration may
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result in leakage current varying local density of recombination centers. The increase of
leakage current is an indication for the degradation of surface and interface properties,
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corresponding to the defect-induced conduction. However, the reverse leakage current is
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much larger in wide-gap Schottky barrier diodes (SBDs) [56].
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The thermionic emission (TE) theory provides the relationship between current density
q (V − JRs A) q (V − JRs A)
J = J 0 exp 1 − exp − (18)
nkT kT
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qφ
J 0 = A*T 2 exp − b (19)
kT
where φb is the barrier height. Well-known k, A, A*, n, q and T are defined in our previous
work [19]. The term, V - JRsA is a term based on the voltage drop across the heterojunction.
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Rs is the series resistance. The apparent barrier height ( φb , BH) and ideality factor (n) are
given as follows:
kT A*T 2
φb = ln (20)
q J 0
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q dV
n= d ln(J ) (21)
kT
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The y-axis intercept and the slope of the straight-line region (from the log I vs. V plot) allow
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to find the φb and n. The diode parameters were determined as function of molar
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concentration. It is seen that the barrier height and the ideality factor increase with increasing
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precursor concentration. In order to determine the diode parameters, taking into accounting
V0 kT I (V )
F (V ) = − (22)
γ q AA*T 2
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where γ is the integer (dimensionless) greater than n. Fig. 14 shows the plots of F(V) vs.
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V0 kT
Φ b = F (V0 ) + − (23)
γ q
kT (γ − n)
Rs = (24)
qI 0
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Results are listed in Table 3 and in accordance with the values determined from forward bias
lnI–V plots. The ideal factor, which is greater than 1, indicates the presence of mechanisms
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conduction in metal-insulator-semiconductor (MIS). Different current regimes become
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dominant, as the voltage increases (V≤0.5, 0.5≤V≤1.2 V or V ≤2). According to Schottky
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φ β E1 / 2
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J = A*T 2 exp − b exp s (25)
kT kT
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Considering Schottky effect, the current density is written as follows:
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β E1 / 2
J = J 0 PF (26)
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kT
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J0 is the low-field current density, and equal to A σ s F. The symbol F is external electric field.
β s and β PF are Schottky and Poole–Frenkel coefficients. Theoretical value is given as:
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1/ 2
q
β s = (27)
4πε 0ε
where, E is the electric field, ε the dielectric constant of the medium, ε 0 the permittivity of
free space. The relationship between the coefficients is given as 2 β s = β PF . The theoretical
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values of β S and β PF were found to be 1.10x10-5 and 2.21x10-5 eVm1/2V-1/2, respectively.
Fig. 15a shows semi-log plots of reverse current density (Jrev) vs. V1/2. From the slope of
straight line in the linear region, the values of β were found to be 3.08x10-5, 3.87x10-5 and
1.29x10-5 eVm1/2V-1/2, for the concentrations of 0.2 M, 0.3 M and 0.5 M, respectively. The
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solution concentration. This is attributed to the bulk limited conduction process and the non-
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uniform electric field [60]. Fig. 15b shows typical J–V characteristics ploted in log–log scale
under forward bias at room temperature. It is seen that there are two distinct linear regions,
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including different conduction mechanisms. The current obeys a power law exponent (in the
form of J∝Vm). The slope at low voltage region (V < 0.5 V) is ~ 1, denoting that the forward
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biased current is ohmic conduction. Whereas, at higher voltages (1.2 < V < 2.1 V) where the
exponential trap distribution is observed, indicating that the forward biased current is
controlled by drift of charge carriers under dominant trap distribution. In the ohmic region
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V
J = P0eµ (28)
d
C
where P0 is the density of thermally generated hole, d the thickness and µ is the hole mobility.
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In the SCLC region where traps are active, the current density is represented by:
9 µεε 0 2
J= E (29)
8d
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If the free carrier density p is lower than the trapped carrier density pt, the current density is
J = qµp ( x) F ( x) (30)
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F is the electric field. The expression for J, in the presence of an exponential trap distribution
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with total trap density, Nt(E):
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Hb E
Nt ( E ) = exp − (31)
Et Et
2l + 1
l +1 l
l εε 0 V l +1
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J = q µN v
1−l
2l +1 (32)
l +1 l +1 Hb d
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where Hb is the density of trap, Nv is the effective density of state in the valence band
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(1.04x1019 cm-3 for p-type Si), Et is the characteristic trap energy, when the exponential trap
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distribution depends on the characteristic temperature via Et = kTc and l = Et/kT = Tc/T. The
slope of the J–V curve plotted in terms of log–log scale is T0/T+1. According to the trap
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modeling of SCLC phenomena, charge transport parameters are given in Table 4. The
mechanism, follows the differences of the characteristic trap energy [63]. The characteristic
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trap energy obtained for the precursor concentration of 0.2 M is close to the value of 20 meV
In this work, ZnO nanofiber films prepared at the various molar rates (0.2, 0.3 and 0.5
M) were deposited onto the glass and p-type Si (100) substrates by sol–gel spin coating
method. The effect of precursor solution molarity was investigated upon the structural, optical
and electrical properties in detail. The sol–gel synthesized ZnO thin films exhibit excellent
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crystalline structure in hexagonal (wurtzite) crystal form. XRD results reveal that all the
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structural parameters are dependent on the changing molarity. AFM images indicate that ZnO
films are formed from nanofibers. The optical energy gap values show a decrease with the
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increase in the precursor concentration. The application of ZnO nanofibers grown on p-type
Si reveals Schottky diode type behavior with low rectification ratio. The value of current
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increases as the molar concentration increases. J–V characteristics in Al/n-ZnO/p-Si
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heterojunction follow SCLC mechanism controlled by an exponential trap distribution.
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Results indicate that the molarity effect can be used to control the structural, optical and
Acknowledgments
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This work was financially supported by the Scientific Research Projects Commission of
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Zn at wt.% 64 65 68
O at wt.% 33 27 29
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ZnAc2 (g) 0.439 0.658 1.097
React. Time 6 6 6
(h)
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Stirring rate 800 800 800
(rpm)
ethylene 10 10 10
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glycol (ml)
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Film 175 167 182
thickness
(nm)
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films
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(nm)
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Dislocation 5.600 5.057 50.800
density (δ)
x1013
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lines/m2
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E0 (eV) 6.176 6.879 4.043
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Ed (eV) 4.265 6.338 4.056
M
Et (meV) 19 24 56
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Figure Caption
Fig. 3. (a-c) EDX results of ZnO thin films, (d) elements by corresponding atomic wt.% for
material.
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Fig. 4. AFM microphotographs in 40x40 µ m2 area of ZnO thin films for (a) 0.2 M, (b) 0.3 M
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and (c) 0.5 M, respectively.
Fig. 5. (a) Transmittance spectra of undoped ZnO thin films, (b) reflectance spectra (c)
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absorption spectra (d) plots of ( αhν )2 vs. hν as a function of the precursor concentration.
Fig. 10. The variation of 1/(n2-1) vs. (hν)2 for ZnO thin films.
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Fig. 12a,b. Volume energy loss (a) and surface energy loss (b) as functions of hυ for the
films.
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Fig. 13a,b. (a) The energy-band diagram in thermal equilibrium, (b) the I-V characteristics of
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ZnO/p-Si heterojunctions.
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Fig. 15a,b. (a) Semi-log plots of reverse current density (b) J–V characteristics ploted in log–
log scale.
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Fig. 3a-d.
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Fig. 6.
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Fig. 8.
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Fig. 10.
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Fig. 12a
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Fig. 13a.
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Highlights
► ZnO thin films were fabricated on glass substrates. ► Solution molarity affected main
optic parameters. ► The diode parameters of ZnO/p-Si were found to depend on molar rate.
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