Physica B 704 (2025) 417045

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Physica B: Condensed Matter

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Effect of 15% Fe doping on the structural, optical, electrical, and

thermoelectric properties of ZnO thin films
Neslihan Üzar a,b,*
a
Department of Physics, Science Faculty, Istanbul University, Vezneciler, 34134, Istanbul, Turkey
b
Nano Material Characterization and Device Design Research Laboratory, Department of Physics, Science Faculty, Istanbul University, Vezneciler, 34134, Istanbul,
Turkey

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

Keywords: In this study, zinc oxide (ZnO) thin films with 15 % iron (Fe) doping (Zn0.85Fe0.15O) were synthesized on glass
High concentration Fe-Doped ZnO and p-type silicon (Si) substrates via sol-gel dip coating and spraying methods. Structural characterization was
Thermoelectric properties performed using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray
Electrical properties
diffraction (XRD), all of which confirmed the formation of pure Fe-doped ZnO nanoparticles with a hexagonal
Sol–gel processes
PL measurement
ZnO polycrystalline structure. The optical transmittance in the visible spectrum was approximately 90 %, and the
Thin films band gap energy, determined using the Tauc method, was 3.23 eV. The refractive index of the sample decreased
from 1.8 to 1.5 as the wavelength increased in the visible spectrum. Photoluminescence (PL) analysis revealed a
band gap energy of 3.27 eV, with emissions at 2.45 eV and 1.81 eV. These last two emissions were attributed to
transitions from the conduction band to zinc vacancies and oxygen interstitial defect levels, respectively. The
electrical properties of the 15 % Fe-doped ZnO thin film on the Si substrate with gold (Au) contacts were
evaluated using current-voltage (I-V), Cheung, and Norde methods. The measurements yielded an ideality factor
between 3.78 and 5.7, a barrier height ranging from 0.57 eV to 0.66 eV, and series resistance values between
19.3 kΩ and 49.1 kΩ. Notably, as temperature increased, the Seebeck coefficient and electrical conductivity
improved, while thermal conductivity decreased. The thermoelectric material achieved maximum efficiency of
0.004 at 550 K, with a Seebeck coefficient of around − 2000 μV/K.

1. Introduction Thermoelectric materials convert a temperature difference into elec­

tricity and, conversely, generate a temperature difference when an
Energy is an integral part of modern life and essential for societal electric current is applied [6]. Their performance is quantified by a term
progress. Therefore, issues such as energy efficiency and renewable 2
known as the “figure of merit”, denoted as ZT = S καT. In this equation, S
energy sources are important at both individual and global levels. To represents the Seebeck coefficient, α denotes electrical conductivity, T is
achieve this, high-performance and cost-effective materials are the temperature, and κ stands for thermal conductivity. Since these
required. Consequently, intense research has focused on materials that parameters are tightly interconnected, increasing the ZT value is chal­
can be effectively used in electronic devices and in the energy sector. lenging. ZnO’s low electrical conductivity, due to its limited carrier
ZnO is one of the most promising materials in this context. ZnO has a concentration, and its high thermal conductivity make it unsuitable for
direct band gap of 3.37 eV and an exciton binding energy of 60 meV at commercial thermoelectric applications. However, by incorporating el­
room temperature. Furthermore, ZnO possesses high chemical stability, ements like Al, Ni, Ga, and Sb into ZnO, electrical conductivity can be
optical transmittance in the visible spectrum, and is composed of non- enhanced while simultaneously reducing thermal conductivity [7,8].
toxic and abundant elements [1]. These advantageous properties make Iron is a promising candidate for doping ZnO due to the presence of
ZnO suitable for a wide range of applications, including photodiodes, unpaired 3d electrons, its transition metal nature, the narrowing of the
gas sensors, transparent electrodes, and solar cells [2–5]. The increasing band gap through s-p interactions, and the similarity in ionic radii (with
production of waste heat from consumption and thermal energy from Fe3+ having an ionic radius of approximately 64 p.m., and zinc (Zn)
the sun has recently sparked greater interest in thermoelectric materials. having an ionic radius of about 74 p.m.) [9]. In the literature, Fe-doped

* Department of Physics, Science Faculty, Istanbul University, Vezneciler, 34134, Istanbul, Turkey
E-mail address: neslihanuzar@[Link].

[Link]
Received 3 November 2024; Received in revised form 11 February 2025; Accepted 17 February 2025
Available online 18 February 2025
0921-4526/© 2025 Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
N. Üzar Physica B: Condensed Matter 704 (2025) 417045

ZnO materials have mostly been studied for their ferromagnetic prop­ which are generated by increasing dopant atoms can increase
erties and use as electrodes in supercapacitors [10–12]. In previous non-radiative recombination, thereby reducing the performance of
studies in which the author participated, the structural, electrical, op­ light-emitting devices. Additionally, these high doping-induced levels in
tical, and optoelectronic properties of pure ZnO and 6 % Fe-doped ZnO the band gap can contribute to a redshift in the photoluminescence (PL)
materials were investigated [13]. However, only two studies explored peak. The difference in ionic radii between Fe and Zn induces lattice
the thermoelectric properties of Fe-doped ZnO [9,14]. One of these disorder and strain, which becomes more pronounced at Fe concentra­
studies investigated the thermoelectric properties of ZnO with Fe doping tions above 15 %. This leads to degradation of the crystalline structure,
at various ratios (0%–0.5 %), which were formed into pellets using which may transition toward an amorphous phase. Such distortions,
hydrothermal synthesis and microwave sintering techniques. The along with the presence of interstitial atoms at higher doping levels,
highest ZT value found as 0.91 at approximately 800 K for the cause an increase in the lattice volume, thereby expanding the average
Zn0.997Fe0.003O sample [9]. In another study, FeO1.5-doped ZnO was crystal size. This weakens the material’s structural integrity and may
investigated using wet chemistry gel combustion followed by SPS sin­ reduce its performance in applications such as sensors and optoelec­
tering, where the Fe doping was in the form of FeO. According to this tronics. In summary, Fe doping levels exceeding 15 % in ZnO result in
study, while the electrical conductivity did not show a significant in­ significant degradation of its physical properties due to increased
crease, the thermal conductivity of the FeO1.5-doped ZnO was notably structural disruptions and defect formation. Therefore, doping ZnO with
reduced due to point defects from Fe substitution on Zn sites and the more than 15 % Fe is detrimental, making 15 % the critical threshold for
formation of a secondary phase (ZnFe2O4) in the crystal structure [14]. achieving optimal performance. For all these reasons, the high doping
This study aims to investigate the effects of high Fe doping concen­ rate was considered as 15 % in this study. According to previous ther­
tration in ZnO thin films (15 % Fe-doped ZnO), prepared on glass and Si moelectric studies on Fe-doped ZnO samples, high concentration
substrates via sol-gel dip coating and spraying methods, on structural, Fe-doped ZnO materials in the form of thin films have not been previ­
electrical, optical, and thermoelectric properties of ZnO. Doped ZnO can ously investigated. Structural characterizations were performed using
be synthesized using various methods, including chemical vapor depo­ SEM, XRD, and EDS. Optical properties were assessed through UV–Vis
sition [15], molecular beam epitaxy [16], RF magnetron sputtering optical transmittance and PL analyses. Thermoelectric properties were
[17], thermal evaporation [18], and sol-gel [19]. In this study, the determined by measuring the Seebeck coefficient, electrical conductiv­
sol-gel method is preferred due to its low cost and simple fabrication ity, and thermal conductivity from 300 K to 600 K, and by calculating
processes. The literature has shown that Fe doping levels in ZnO the ZT values based on these measurements. In this paper, pure ZnO was
generally do not exceed 20 % [20,21]. These studies have indicated that not synthesized, and the results were compared to those obtained for
doping ZnO with more than 15 % Fe can negatively impact the mate­ pure ZnO in previous studies in which the author was involved [8,22]. In
rial’s properties and promote the formation of secondary phases, such as these studies, the ZT value for pure ZnO, prepared under nearly identical
Fe2O3 [21]. The incorporation of transition metals, such as iron, into conditions, was found to be on the order of 10− 6 at 550 K, although it
ZnO often encounters the issue of limited solubility within the oxide increased with temperature [8,22]. Moreover, it has been noted that
matrix. This solubility can be influenced by factors such as the synthesis Fe-doped ZnO, with 15 % Fe doping, has not been studied as an inter­
temperature and dopant concentration. Additionally, the charge state of layer in the MIS (metal-interlayer-semiconductor) structure using
the dopants plays a critical role in determining the solubility limit. Due different methods such as Norde, Cheung, and I-V methods. Therefore,
to the limited solubility of iron, when the doping level exceeds 15 %, Fe this study aims to address these gaps in the literature.
atoms may fail to properly incorporate into the ZnO crystal structure.
Instead, they tend to form secondary phases such as FeO, Fe2O3, or 2. Experimental
ZnFe2O4, leading to phase separation and deterioration of the material’s
physical properties. This phenomenon can particularly cause in the loss 2.1. Synthesis of Fe-doped ZnO solution
of ferromagnetic properties in Fe-doped ZnO materials, replacing them
with antiferromagnetic or diamagnetic interactions. In addition to the Zinc acetate dihydrate (Zn(CH3CO2)2.2H2O) and iron (II) sulfate
formation of secondary phases, excessive Fe incorporation leads to the heptahydrate (FeSO4 .7H2O) were used as the primary precursors to
creation of various defects within the structure. Due to the production produce Fe-doped ZnO solution via the sol-gel method. The mole ratios
conditions and the differences in the ionic radii of Fe and Zn, point of iron and zinc in the solution were 15 % and 85 %, respectively,
defects such as zinc interstitials, oxygen interstitials, zinc vacancies, and resulting in a Zn0.85Fe0.15O composition. A 0.3 M solution was prepared
oxygen vacancies may predominate, depending on the specific condi­ by dissolving 1.4 g of zinc acetate dihydrate in 25 mL of ethylene glycol
tions. ZnO is known to be an n-type semiconductor, with electrons as the monomethyl ether (C3H8O2) as the solvent. This mixture was stirred at
majority carriers. Since Fe ions substitute Zn2+ in the host matrix as 800 rpm with a magnetic stirrer for a specific duration at 70 ◦ C. Sub­
Fe3+, zinc vacancies which are shallow acceptor-type defect levels can sequently, 0.32 g of FeSO4.7H2O was added to the solution. After stirring
be generated to maintain charge compensation. When the Fe doping the solution for approximately 30 min, ethanolamine (C2H7NO), used as
amount is significantly increased, the probability of formation of oxygen catalyst, was added to solution to ensure a uniform and transparent
interstitials, which are deep-acceptor type defects within the structure, solution. In this study, the molar ratio of the catalyst to Zn was assumed
increases. Hence such defects are a source of holes. High doping con­ to be “1”to ensure complete reaction.
centrations increase the density of acceptor-type defects, creating The prepared solution was then applied as thin films on glass and p-
recombination centers for carriers, which can reduce carrier concen­ type Si substrates. Prior to the coating process, the substrates were
tration. This, in turn, can decrease both electrical and thermoelectric cleaned to remove any contaminants.
efficiency. Additionally, any kind of defects in a material typically
reduce electrical conductivity because they scatter charge carriers, 2.2. Substrate cleaning
reducing their mobility. As the number of defects increases with
increasing doping concentration, more scattering occurs, and the car­ Initially, glass and p-type Si substrates were boiled in technical
riers’ velocity is further impeded. Fe concentrations exceeding 15 % can acetone for 15 min at approximately 60 ◦ C. The glass substrates were
result in Fe ions with varying charge states, potentially hindering then sequentially dipped in ethanol and a solution of hydrochloric acid
effective charge transport and making it more challenging to control (HCl) mixed with nitric acid (HNO3) in a ratio of 3:1 for a specified
carrier concentration. This can also increase the material’s ideality duration. Meanwhile, the silicon substrates were simmered in a mixture
factor and resistance, negatively affecting its electrical conductivity. consisting of 1 unit of ammonia (NH3), 1 unit of hydrogen peroxide
From an optical perspective, deep-type defect states within the band gap (H2O2), and 4 units of distilled water at 150 ◦ C for 15–20 min. After this

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N. Üzar Physica B: Condensed Matter 704 (2025) 417045

cleaning process, the Si substrates were immersed in hydrofluoric acid room temperature. The band gap energy of the doped semiconductor
(HF) for approximately 10 s to get rid of the oxide layer from the sample material was calculated via the Tauc method, based on optical trans­
surface. Between each cleaning step, and after all processes were mittance data. The PL technique was employed to identify defects in the
completed, the substrates were stored in deionized water for period of structure introduced during the sol-gel method and Fe doping, as well as
time. to gather information about the band gap energy. The photo­
luminescence measurements were performed using a 450 W ozone-free
2.3. Preparation of thin film xenon lamp and a 55 mW HeCd laser with a 325 nm wavelength as
excitation sources. The excitation light was filtered and directed through
The Zn0.85Fe0.15O solution was coated on glass substrates using the a double-grating monochromator from Jobin Yvon-Horiba. This was
dip-coating method for optical (UV–Vis optical transmittance and PL done before the light entered the sample chamber. After interacting with
analyses) and structural measurements, and on p-type Si substrates the sample, the emitted light was dispersed. It was then detected by a
using spraying method for electrical and thermoelectric measurements. single-grating monochromator, also from Jobin Yvon-Horiba. The
The dip-coating method was chosen for structural and optical analyses emitted light was captured either by a photomultiplier tube (PMT) for
due to its ability to produce uniform and homogeneous films, which are broad spectral analysis or by a high-sensitivity, liquid nitrogen-cooled
crucial for precise optical characterization and structural integrity. Since InGaAs photodiode for precise detection of near-infrared emissions.
both top and bottom contacts are required for the electrical measure­ The required top and bottom contacts for electrical and thermo­
ments of the MIS structure (Au/Fe-doped ZnO/Si/Au), as shown in Fig. 1 electric measurements of the Zn0.85Fe0.15O/p-type Si diode were fabri­
(b), the dip-coating method, which involves double-sided coating, is not cated using the thermal evaporation method with Au metal, employing
suitable for this application. Therefore, the spraying method, which the NANOVAK NVTH-350 system. The upper contacts were designed as
allows single-sided coating of the interlayer to preserve the integrity of 1 mm diameter dots. Fig. 1(a) and (b) present the top view and sche­
the MIS structure, was preferred for the electrical measurements. matic representation of the Au/Zn0.85Fe0.15O/p-type Si/Au structure,
Thermoelectric and electrical measurements were conducted on the respectively. Electrical measurements were performed with a Keithley
same sample. 2400 multimeter. To evaluate the thermoelectric properties, a temper­
For structural characterization, the sample underwent 15 layers of ature gradient was created across the sample by heating one end with a
coating, while 6 layers were applied for all other analyses, including heater and cooling the other end with ice. The temperature difference
optical, electrical, and thermoelectric measurements. In the dip-coating along the thin films was monitored using a K-type thermocouple. The
process, each layer was deposited by immersing the substrate into the schematic diagram of the experimental setup for thermoelectric mea­
solution at a speed of 2 mm/s for 30 s. After immersion, the sample was surements is shown in Fig. 1 (c).
removed from the solution and allowed to drain for 2 min to eliminate
excess solution. Subsequently, the sample was dried for 2 min at 3. Results and discussions
approximately 200 ◦ C in a heater attached to the dip coater. This pro­
cedure ensured proper deposition of each layer on the substrate. The XRD analysis is a key technique used in structural characterization to
spraying method was used to deposit the material on the Si substrate at determine whether a material is crystalline or amorphous.
200 ◦ C. The solution was sprayed from a distance of 25 cm with a flow The XRD spectrum shows that the sample has a crystalline structure,
rate of 3 mL/min. A waiting time of 2 min was applied between each but this structure is disrupted due to the high concentration of Fe doping
layer. After deposition, all thin films underwent a 30-min annealing (Fig. 2) and it starts to shift towards an amorphous structure. But,
process in a box oven at 300 ◦ C to promote crystallization. although not all XRD peaks belonging to ZnO are visible, the XRD peaks
representing the planes indicated by the Miller indices are clearly visible
in Fig. 2. The sample possesses a hexagonal ZnO polycrystalline struc­
2.4. Characterization of Zn0.85Fe0.15O film
ture, matching PDF Card No. 79–0205. Compared to pure ZnO produced
under the same conditions (Ref. [13]), the XRD peaks shift to higher
In this study, structural properties of Zn0.85Fe0.15O film were char­
angles. This shift in the 15 % Fe-doped ZnO may suggest that Fe is
acterized using SEM, EDS, and XRD analyses. XRD measurement was
present in the compound as Fe3+ [23]. The radius of the Fe3+ ion (64 p.
conducted with an APD 2000 PRO XRD device, with a precision of 1◦ ,
m.) is smaller than that of the Zn2+ ion (74 p.m.); therefore, when Fe3+ is
over a range of 30◦ –80◦ . The surface morphology and particle size of the
introduced as an impurity into the crystal lattice, it can compress the
film were analyzed using SEM. The chemical compositions of the film
lattice. This compression reduces the values of lattice parameters and
and their relative proportions were characterized by EDS. Both SEM and
causes the XRD peaks to shift to higher angles [23]. Dopants with
EDS analyses were carried out with the Thermo Scientific Apreo 2 S
various ionic radii elements can alter lattice parameters, inducing
LoVac device, with SEM measurements taken at a magnification of
stresses within the crystal. At high concentrations, these dopants may
250,000x.
also cause the material to become amorphous, introducing defects and
For optical characterization, non-contact techniques including PL
displacements in the crystal structure. As the dopant concentration in­
and optical transmittance measurements were used. Optical trans­
creases, these defects become more noticeable, possibly leading to a loss
mittance was measured with a PERKIN ELMER UV–Vis spectrometer,
of the crystal’s regular arrangement [24]. The strongest peak of
covering a wavelength range of 200–1100 nm, in an air environment at

Fig. 1. (a) The top view, (b) schematic representation of the Au/Zn0.85Fe0.15O/p-type Si/Au structure and (c) schematic diagram of the experimental setup for
thermoelectric measurements.

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N. Üzar Physica B: Condensed Matter 704 (2025) 417045

crystal size. Microstrain (ε), defined in Eq. (4), quantifies the average
lattice strain within a material’s crystal structure [30]. It represents the
relative deviation of lattice parameters from their ideal values, caused
by defects, dislocations, or other distortions.
β
ε= (4)
4 tan θ
The obtained results for the parameters D, a, c, β, d, δ, and ε using the
Debye-Scherrer technique for the (002) plane are presented in Table 1.
The Williamson–Hall method is a widely used method in materials
science for analyzing both crystallite size and microstrain in crystalline
materials. According to this method, the broadening of diffraction peaks
in XRD spectrum arises from two primary factors: crystallite size
(Scherrer component, βc ) and microstrain (βε ) [31]. The relationship
between these factors is expressed by Eq. (5):
βhkl = βc + βε , (5)

where βhkl is the extended full width at half maximum. Smaller crys­
tallites lead to increased peak broadening due to the limitations imposed
by their finite size [32]. Additionally, microstrain, which refers to in­
ternal structural deformations within the crystal, further contributes to
Fig. 2. XRD spectrum of Zn0.85Fe0.15O sample with Miller indices (hkl).
the broadening by introducing distortions that affect the diffraction
pattern [33]. Therefore, both crystallite size and microstrain are crucial
Fe-doped ZnO corresponds to the (002) plane, indicating that the sample
factors in determining the extent of peak broadening observed in X-ray
prefers to orient along this plane.
diffraction analysis. The W-H method employs several submodels to
The XRD spectrum analysis helps evaluate several physical param­
interpret diffraction peak broadening. Among these, the Uniform
eters in a crystal structure, such as crystallite size (D), the full width at
Deformation Model (UDM), the Uniform Stress Deformation Model
half maximum (FWHM), lattice constants (a, b, c), interplanar spacing
(USDM), and the Uniform Deformation Energy Density Model (UDEDM)
(d-spacing), and dislocation density (δ). These parameters can be
are the most notable. The UDM assumes that the strain within the
determined using methods like the Williamson-Hall (W-H), Stokes-
crystallite is uniformly distributed throughout the crystal [32]. This
Wilson, Debye-Scherrer, Halder-Wagner and Size-Strain Plot (SSP)
model is based on the idea that the strain affects peak broadening in a
[25]. In this study, the Debye-Scherrer and Williamson-Hall methods
homogeneous manner. According to the UDM, diffraction peak broad­
were used. The average crystallite size of the thin film was computed
ening results from uniform lattice distortions and can be described by:
with the Debye-Scherrer equation given in Eq. (1). It is important to note
that this value is an estimate. Kλ
βhkl = + 4ε sin θ, (6)
D cos θ
Kλ
D= , (1)
β cos θ where ε represents the microstrain, which is assumed to be constant
throughout the crystal. This assumption leads to a simple linear rela­
where D is the average crystallite size, λ denotes the wavelength of the X- tionship between β cos θ and 4 sin θ. Accordingly, the value at which the
ray with a value of 0.154 nm, β represents the FWHM of the diffraction linear curve intersects the y-axis in the graph of β cos θ (on the y-axis)
peaks, θ refers to the Bragg angle, and K is the Scherrer constant. The versus 4 sin θ (on the x-axis) provides the average crystal size, while the
value of K depends on some factors such as the crystallites’ shape, dis­ slope indicates the microstrain. The USDM extends the UDM by ac­
tribution, and the diffraction line indices. Typically, K ranges from 0.62 counting for non-uniform stress distribution within the crystal. Unlike
to 2.08 [26,27]. In this study, K was set to 0.94. In this work, by applying the UDM, which assumes uniform strain, the USDM incorporates the
a fitting method to the XRD peaks shown in Fig. 2 using the Origin effects of internal stresses that vary across the crystal [32,34]. In other
program and selecting the single peak fit mode, the FWHM and Bragg words, this model is particularly useful for describing situations where
angle values for each peak were determined approximately. Since the stress is unevenly distributed, resulting in more complex peak broad­
structure in this study is identified as wurtzite ZnO, the lattice param­ ening behavior. According to the USDM, the microstrain can be
eters (a, b, and c) were calculated using Eq. (2) [28]. In a hexagonal formulated as shown in Eq. (7).
crystal structure, it is known that a = b. ( )
( ) Kλ 4σ sin θ
βhkl cos θ = + (7)
1 4 h2 + hk + k2 l2 D Yhkl
= + 2, (2)
d2hkl 3 a2 c
Yhkl given in Eq. (7) can be defined as follows for hexagonal crystal
structures.
where h, k, and l symbolize the Miller indices of crystal plane, and d-
[ ( ) 2 ]2
spacing (dhkl) is calculated using the formula dhkl = 2 sin λ
θ , which is (h+2k)2
derived from Bragg’s law. Dislocation density in a crystallite refers to the h + 3 + alc
2

number of dislocations present in the crystal structure. Dislocations are Yhkl = ( )2 ( )4 ( )( ) ,

2
defects caused by misalignments or irregularities in the atomic (h+2k)2 (h+2k)2
s11 h2 + 3
+ s33 al
c
+ (2s13 + s44 ) h2 + 3
al
c
arrangement and have a significant impact on the mechanical properties
of materials. The dislocation density in a crystallite can be expressed (8)
mathematically as follows [29]
where s11 , s13 , s33 , and s44 represent the elastic compliances of ZnO [32,
1
δ= . (3) 34]. By applying a linear fit to the data shown in the graph of βhkl cos θ
D2
on the y-axis versus 4 Ysin θ
on the x-axis, the crystallite size and strain
As can be seen from Eq. (3), dislocation density is directly related to hkl

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N. Üzar Physica B: Condensed Matter 704 (2025) 417045

Table 1
Some crystal parameters and values related to XRD analysis depending on the Debye-Scherrer model.
( ) ( )
Sample β (o) a=b (Å) c (Å) d-spacing (Å) D (nm) δ nm− 2 ε 10− 3

Zn0.85Fe0.15O 0.285 3.29 5.16 2.58 30 0.0011 3.974

values can be derived from the y-intercept and slope of the fitted line,
respectively. The final model, the UDEDM, is an extension of the UDM
that incorporates the concept of deformation energy density. This model
considers not only the strain but also the energy associated with the
deformation within the crystal lattice. The UDEDM is particularly useful
for analyzing materials where deformation energy plays a significant
role in peak broadening. According to the UDEDM, βhkl cos θ can be
written as Eq. (9).
( ( )1/2 )
Kλ 2u
βhkl cos θ = + 4σ sin θ (9)
D Yhkl

In an elastic system where Hooke’s law is valid, the energy density can
( )
be defined as u = ε2 Yhkl /2. According to this model, the graph of
( )1/2
βhkl cos θ (on the y-axis) versus 4σ sin θ Y2u
hkl
(on the x axis) is

considered. When a linear fit is applied to this graph, the slope provides
the value of u, while the y-intercept gives the average crystal size D [32,
34]. The results obtained from the XRD peak analysis using the W–H Fig. 3. SEM image of the surface morphology of the synthesized Zn0.85Fe0.15O
method are presented in Table 2. at 250,000× magnification. The nanoparticles exhibit a nearly plate-like
The average crystallite size determined using the Williamson-Hall morphology with a uniform size distribution. Small surface irregularities are
method is smaller than that obtained from the Debye-Scherrer also observed, which may influence the material’s physical and/or chemi­
method, while microstrain is higher. The Debye-Scherrer method typi­ cal properties.
cally provides more consistent and straightforward results, whereas the
Williamson-Hall analysis takes both crystallite size and microstrain into thin film in the visible spectrum is around 90 % (Fig. 5 (a)). The band
account, offering a more detailed understanding of XRD peak broad­ gap energy of the semiconductor material, produced as the thin film
ening. Consequently, the two methods can yield similar but distinct with nanoparticles on its surface, is found to be around 3.23 eV (Fig. 5
results. In this study, the relationship between the results from the (b)). The bandgap energy was determined using the Tauc method, as
Debye-Scherrer and Williamson-Hall methods was found to be consis­ shown in Eq. (10) [36].
tent with the findings in the study on Fe-doped ZnO in Ref. [35]. ( )1/2
The surface morphology and grain size of the thin film were exam­ (αhν) = B hν − Eg , (10)
ined using SEM analysis. The SEM image of the 15 % Fe-doped ZnO is
shown in Fig. 3. In the study referenced in Ref. [13], pure ZnO and 6 % where α, h, ν, B, and Eg symbolize the absorption coefficient, Planck
Fe-doped ZnO were produced. Pure ZnO exhibited an irregular nanodot constant, frequency, a material-specific constant, and band gap energy,
shape, while Fe doping led to more regular structures, with respectively. The band gap energy is determined by finding the value
nanoplate-like formations observed [13]. As the amount of Fe in ZnO where the linear curve intersects the x-axis in the (ahv)2 (on the y-axis)
increases, the number of nanoplate-like particles also increases signifi­ versus photon energy (hv, on the x-axis) graph, as obtained using this
cantly. This suggests that Fe promotes the formation of nanoplate method. It is observed that the band gap energy of the 15 % Fe-doped
structures. According to Fig. 3, the average width of these nanoplates ZnO sample narrows compared to the band gap energy of pure ZnO
varies between 15 and 95 nm. and 6 % Fe-doped ZnO, as determined by the Tauc method in Ref. [13].
The chemical components of the sample and their distribution on the This narrowing may be attributed to an increase in defects within the
sample surface are shown in the EDS spectrum (Fig. 4(a)) and EDS structure and the deterioration of the crystal caused by excessive doping.
mapping (Fig. 4(b)), respectively. Using the Swanepoel method [37,38], both the refractive index and the
The EDS spectrum in Fig. 4(a) indicates that a pure Fe-doped ZnO thickness of the sample were determined. For all optical, electrical, and
material is obtained. Fig. 4 (b) exhibits that the O, Fe, and Zn elements optoelectronic measurements, the material has a 6-layer coating. As
are uniformly distributed on the surface of the thin film. shown in Fig. 5(c), the refractive index decreases as the wavelength of
In the second part of the study, the optical properties of the the incident light on the sample increases. The inset graph in Fig. 5(c)
Zn0.85Fe0.15O sample were investigated through optical transmittance displays the wavelength-dependent refractive index values in the visible
and PL analyses. The optical transmittance graph, along with the spectrum. It is observed that the refractive index of the sample is
refractive index and band gap energy graphs derived from the optical approximately 1.8 at 400 nm and around 1.5 at 700 nm. These results
transmittance data, are shown in Fig. 5. are consistent with the literature. Robina Ashraf and colleagues reported
It is found that the optical transmittance of the 15 % Fe-doped ZnO that the refractive index of pure ZnO ranged from 1.78 to 1.48 across

Table 2
The results of the Williamson-Hall analysis of Zn0.85Fe0.15O thin film.
Sample UDM USDM UDEDM

D (nm) ε (10− 3) D (nm) ε (10− 3) σ (MPa) D (nm) ε (10− 3) u (KJm− 3)

Zn0.85Fe0.15O 29.30 6.03 24.13 8.25 119 21.29 8.48 51.8

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N. Üzar Physica B: Condensed Matter 704 (2025) 417045

Fig. 4. (a) EDS spectrum and (b) EDS mapping of the produced 15 % Fe-doped ZnO thin film.

Fig. 5. The graph of (a) optical transmittance, (b) band gap energy, and (c) refractive index of 15 % Fe-doped ZnO sample.

300–900 nm [39]. In a study by Goktas et al., it was found that as the Fe as the Fe source in the solution. The result of PL measurement, another
doping ratio in ZnO increased, the refractive index in the visible region optical characterization method taken at room temperature, is presented
decreased. For 9 % Fe doping, the refractive index was approximately in Fig. 6. This method provides insights into both the defects present in
1.7 [40]. According to the Swanepoel method, the estimated thickness of the structure and the band gap energy. To make a more detailed optical
the produced thin film is 945 nm. In Ref. [13], the thickness of the pure analysis, Gaussian curve fitting was applied to the PL spectrum, allowing
ZnO thin film with a 6-layer coating was calculated to be 390 nm, while the identification of the emission peaks. The fitted spectrum shows three
the 6 % Fe-doped ZnO coating had a thickness of approximately 500 nm. main peaks at approximately 379 nm, 506 nm, and 685 nm. The peak at
The increase in Fe ratio in the compound led to a thicker film, which may 379 nm corresponds to 3.27 eV (UV emission), which may represent the
be due to the higher concentration of iron (II) sulfate heptahydrate used band gap energy of the prepared semiconductor material. This value is

6
N. Üzar Physica B: Condensed Matter 704 (2025) 417045

interatomic forces, and cause displacements in atomic positions. Addi­

tionally, the size mismatch between the host ions and the doping ions
acts as a barrier to thermal conductivity. At high concentrations, these
excess defect levels will significantly shorten the average free path of
phonons, reducing thermal conductivity. The decrease in thermal con­
ductivity, in turn, leads to an improvement in thermoelectric perfor­
mance. However, for electrical conductivity and Seebeck coefficient to
improve, an optimal level of doping must be achieved. Excessively high
doping levels may negatively affect carrier mobility and thermoelectric
efficiency.
After determining the optical properties of the Zn0.85Fe0.15O sample,
electrical analysis was performed. Using the data from this analysis, key
electrical parameters of the produced film, such as the ideality factor,
series resistance, and barrier height, were calculated using the therm­
ionic emission, Cheung, and Norde models. The I-V characteristics of the
Au/Zn0.85Fe0.15O/p-type Si MIS structure were thoroughly examined
using these three models. In this study, Fe-doped ZnO with a thickness of
approximately 945 nm was used as the interlayer material. The I-V
Fig. 6. PL spectrum of Zn0.85Fe0.15O thin film coated on glass substrate. characteristics of sample under the Au contacts are shown in Fig. 7(a)
and (b) using linear and semi-logarithmic scales, respectively. Fig. 7 (a)
in close agreement with the estimated band gap energy obtained by the appears to be a combination of the I-V behavior of a semiconductor
Tauc method. The visible emission at 506 nm (2.45 eV) can be attributed associated with a p-n junction and a metal that follows Ohm’s law. As
to the transition between the conduction band and defect levels caused ZnO is a semiconductor, excessive Fe doping may impart metallic
by zinc vacancies [41,42]. It is known that zinc vacancies in ZnO, an behavior to the material. On the other hand, Fig. 7 (b) clearly shows that
n-type semiconductor, create acceptor-type defect levels just above the the structure remains in semiconductor form and continues to exhibit
valence band. This defect level typically appears around 0.9–1.2 eV diode-like properties.
above the valence band [43]. The orange emission at 685 nm (1.81 eV) Thermionic emission refers to the release of electrons when thermal
may be related to transitions between the conduction band and defect energy is sufficient to surpass the material’s work function. In other
levels caused by oxygen interstitials [44]. When comparing these results words, this model explains how electrons are released as the tempera­
with those from Ref. [13], it is evident that the band gap energy de­ ture increases, particularly in metals or semiconductors. It also describes
creases with 15 % Fe doping, compared to pure ZnO and 6 % Fe-doped how the flow of electrons occurs and how this emission affects the
ZnO. This may be attributed to the more pronounced formation of donor current [45]. The thermionic emission model is characterized with Eq.
levels created by Fe atoms. Increasing the doping ratio also provides (11) [46].
more opportunities for the formation of various defects in the forbidden [ ( ) ]
qV
band gap. I = I0 exp − 1 , (11)
nkT
The peaks related to defects in the PL spectrum provide significant
insights into the thermoelectric properties of ZnO as well as its electrical where the symbols V, n, k, T, q, and I0 denote the applied voltage, ide­
and optical properties. These defect-related emissions are crucial for ality factor, Boltzmann constant, temperature, electric charge, and
understanding how various types of defects, such as zinc vacancies and saturation current (leakage current), respectively. Typically, the satu­
oxygen interstitials, influence the material’s electrical and thermal ration current I0 is defined as:
conductivities, as well as its Seebeck coefficient. The peaks observed in ( )
the PL spectrum between 450 nm and 900 nm, as shown in Fig. 6, are qϕb
I0 = AA* T 2 exp − . (12)
known as deep-level emissions. These peaks in the visible range are kT
attributed to point defects, and notably, the visible peak at 685 nm is
Here, A indicates the contact area, A* is identified as the Richardson
stronger than the UV peak at 379 nm, indicating that a high concen­
constant for ZnO, valued at 32 Acm− 2 K− 2, and ϕb represents the
tration of defects is present in the 15 % Fe-doped ZnO thin film. When Fe
Schottky diode’s barrier height [46]. The leakage current and ideality
ions substitute for Zn, they are expected to be in the +2 oxidation state.
factor for the MIS structure were derived from the linear portion of the
However, the presence of Fe3+ ions in the structure requires charge
forward bias region shown in Fig. 7(b). By applying a linear fit to this
compensation, which is achieved through the creation of zinc vacancies.
graph, the intersection point with the y-axis (logarithmic I(A)) gives the
The peak observed at 506 nm belongs to zinc vacancies and forms
saturation current, while the slope represents the ideality factor. The
shallow acceptor-type defects within the structure. In fact, the presence
barrier height is calculated using Eq. (12). According to the thermionic
of zinc vacancies in the PL spectrum proves that Fe is present in the host
emission model, the average leakage current is approximately 7.0 ×
material as Fe3+. Since thin film production is carried out under air at­
10− 6 A. Additionally, the barrier height and ideality factor of the sample
mosphere, excess oxygen or excessive doping leads to strain within the
are determined to be 0.57 eV and 3.78, respectively.
lattice, resulting in the formation of oxygen interstitials. Oxygen in­
Another method used to investigate the electrical properties of
terstitials create deep acceptor-type trap states. These defects, being
semiconductor materials, such as the ideality factor, barrier height, and
carriers of holes, lead to carrier recombination in n-type semiconductor
series resistance (Rs), is the Cheung method. The ideality factor and
ZnO, causing carrier traps that limit conductivity. This reduction in
series resistance are calculated using the formula in Eq. (13) [47].
carrier concentration subsequently enhances the resistivity and the
Seebeck coefficient. It is known that the Seebeck coefficient and elec­ dV nkT
= + IRs (13)
trical conductivity change inversely proportional to each other. How­ d(ln I) q
ever, the most pronounced effect of these defects on thermoelectric
properties is their ability to decrease thermal conductivity. These When a linear fit is applied to the graph dV/ d ln(I) (on the y-axis) versus
atomic-scale defects act as scattering centers for phonons. Point defects I (on the x-axis), the slope provides Rs as per Eq. (13), while the y-axis
disrupt phonon propagation because they alter the atomic mass, affect intersection point provides nkT/q, which can also be used to calculate
the value of n (Fig. 8 (a)) [47]. The barrier height can be determined

7
N. Üzar Physica B: Condensed Matter 704 (2025) 417045

Fig. 7. I-V characteristics of the Au/Zn0.85Fe0.15O/p-type Si MIS structure measured under forward and reverse bias conditions. The graph is presented in two forms:
(a) linear scale, where the relationship between current and voltage is shown for both positive and negative bias, and (b) semi-logarithmic scale, which highlights the
exponential behavior of the current at higher voltages and allows for better visualization of the current in the reverse bias region.

Fig. 8. (a) dV/ d ln(I) versus I graph, (b) H(I)-I graph to calculate the electrical parameters using the Cheung method.

using Eq. (14). The point where the linear region of the graph, with H(I)
on the y-axis and I on the x-axis, intersects the vertical axis provides the
barrier height, while the slope indicates the series resistance (Fig. 8 (b))
[47]. Thus, the series resistance can be determined in two different ways
using this method.
( ) [ ]
nkT I
H(I) = V − ln = nϕb + IRs (14)
q AA* T2
The series resistance obtained from the dV/dln(I)-I graph is 49.1 kΩ,
while from the H(I)-I graph, it is found to be 47.2 kΩ. As shown, the two
results are quite close, confirming the consistency of this method. Ac­
cording to the Cheung model, the barrier height and ideality factor of the
sample are obtained approximately 0.62 eV and 5.4, respectively.
Apart from these methods, series resistance and barrier height of
Schottky contacts can also be calculated using the Norde method. The
Norde method defines a function, F(V), as presented in Eq. (15) [48].
( )
V kT I
F(V) = − ln (15)
γ q AA* T2

In this study, γ, a dimensionless integer greater than the ideality factor,

is taken to be 5. Fig. 9 shows the graph of F(V) as a function of V at room
temperature. The minimum of the graph of F(V) versus V is used to Fig. 9. The graph of F(V) versus V used in the Norde method.

8
N. Üzar Physica B: Condensed Matter 704 (2025) 417045

determine the barrier height ϕb as fallows. Controlling the temperature and atmospheric conditions during the
synthesis process can be one of the ways to optimize the defect levels and
V0
ϕb = F(V0 ) + , (16) interface states. At the same time, the drying temperature of the film can
γ
be increased and its duration can be extended during film coating.
where F(V0 ) refers to the minimum value observed in the graph of F(V) However, the most effective method to reduce the effect of defects and
versus V, and V0 is the bias voltage at which this minimum occurs. The interface states can be to provide recrystallization by applying long-term
series resistance Rs of the MIS structure can be determined using the annealing process at high temperature in an environment different from
Norde model with the following formula [48]. the atmosphere, such as under Ar gas. In heat treatments performed at
( ) high temperatures, defects can be reduced and the crystal structure of
kT the material can be improved, thus increasing the mobility of the car­
Rs = (γ − n) (17)
qI riers and decreasing the ideality factor. In addition, other methods could
be preferred instead of the spraying method to achieve a more homo­
Using the Norde method, the calculated values for barrier height and
geneous coating. In short, it is clear that in future studies, doping levels
series resistance are 0.66 eV and 19.3 kΩ, respectively. The results ob­
and process parameters should be carefully selected in order to enhance
tained from these three methods of electrical characterization are
the electrical properties of ZnO and therefore its thermoelectric
summarized in Table 3 for easy comparisons.
properties.
The ideality factor, which is significantly larger than 1, can be
Thermoelectric materials are promising candidates for sustainable
attributed to the deterioration of the crystal structure in the Fe-doped
energy solutions, as they can convert waste heat into useable energy and
ZnO material, as indicated by the XRD results [46]. Since the obtained
provide cooling without mechanical parts or refrigerants [52]. Ongoing
values of ideality factor are average values derived from multiple con­
research is focused on improving their efficiency and reducing costs.
tacts, this situation can be attributed to the inhomogeneity of the barrier
There are four key parameters for determining the performance of
height and the interface states [49]. Additionally, factors such as the
thermoelectric materials: Seebeck coefficient, electrical conductivity,
interfacial native oxide layer, series resistance, and other contributing
thermal conductivity, and the figure of merit (ZT). The ZT value, which
elements may also play a role in this phenomenon [50]. Another
indicates the thermoelectric performance of a material, is closely related
important parameter in determining electrical characteristics is series
to these three other parameters. The Seebeck coefficient measures the
resistance, and different results are obtained using the Norde and
voltage generated due to the temperature difference in the sample. To
Cheung methods. The primary reason for this discrepancy may be the
determine whether a material functions as a thermoelectric material,
different voltage ranges employed in the two methods [51]. The ϕb
one end (or surface) of the material is heated while the other end (sur­
calculated using the I-V method is smaller than those obtained from the
face) is cooled, creating a temperature gradient. In this study, a
Cheung and Norde methods. This variation in results can be attributed to
film-shaped sample was used, where the left end was heated with a
the different calculation methods and regions used across all methods. In
heater and the right end was cooled with ice. The voltage created across
the I-V method, the barrier height is calculated using data from the
the material due to this temperature difference was measured with a
linear region of the I-V curve. In contrast, the Norde method uses data
voltmeter. The temperature difference between the two ends was
from the entire I-V characteristic curve, while the Cheung method cal­
monitored using a K-type thermocouple. The Seebeck coefficient is given
culates the barrier height from the nonlinear region of the I-V curve
by Eq. (18), which relates the temperature and voltage difference [53].
[50]. To sum up, the high ideality factor observed in the electrical
measurements of 15 % Fe-doped ZnO, determined using three methods, ΔV
S= , (18)
may largely be due to the effects of defects or interface states in the ΔT
material. The integration of Fe doping into the ZnO crystal structure may
promote the formation of defects such as oxygen vacancies, zinc in­ where ΔV and ΔT are the voltage and temperature difference between
terstitials, zinc vacancies, and oxygen interstitials. In addition, the dis­ the cold and hot terminals of thermoelectric sample, respectively. The
tortions in the ZnO crystal structure with Fe doping may lead to the unit of S is typically μV/K or V/K. The Seebeck coefficient results for
formation of more interface states on the surface of the material. These Zn0.85Fe0.15O across the temperature ranges from 300 K to 600 K are
states prevent the movement of carriers, leading to a decrease in elec­
trical conductivity and a high ideality factor. Therefore, it is important
to minimize the defect density and interface states in the material. One
way to reduce defects is to optimize the doping process and synthesis
conditions. To explain in more detail; reducing the dopant concentration
is one of them. Reducing the doping level can reduce the defect density
in the material. Very high doping levels can lead to the accumulation of
defects, which can have negative effects on electrical conductivity.
Optimizing the Fe concentration can reduce the number of interface
states and defects. In addition, by changing the used solvent in the so­
lution, the source materials can be dissolved better. In addition, the pH
of the prepared solution can be optimized. It is believed that the basic
nature of ZnO solutions allows the formation of more orderly structures.

Table 3
Electrical parameter values calculated using different methods.
Sample I-V method Cheung method Norde method

n ϕb n Rs Rs ϕb Rs ϕb
(eV) (kΩ) (kΩ) (eV) (kΩ) (eV)
(dV/ (H
dln (I)-I)
(I))
Fig. 10. Seebeck coefficient of 15 % Fe-doped ZnO thin film depending on
Zn0.85Fe0.15O 3.78 0.57 5.4 49.1 47.2 0.62 19.3 0.66
temperature.

9
N. Üzar Physica B: Condensed Matter 704 (2025) 417045

shown in Fig. 10. The measurements showed a significant decrease in (mK). It indicates how quickly heat can be transferred through the
both the Seebeck coefficient and thermoelectric performance at 600 K; material [55]. Thermal conductivity is a critical factor in the perfor­
therefore, all thermoelectric measurements were terminated at this mance of thermoelectric materials. For thermoelectric applications, high
temperature. electrical conductivity combined with low thermal conductivity is ideal,
The negative Seebeck coefficients obtained as a function of temper­ as it maximizes the figure of merit (ZT). A material with low thermal
ature indicate that the doped material is an n-type semiconductor. At conductivity can maintain a temperature gradient more effectively, thus
300 K, the Seebeck coefficient is around − 128 μV/K, and it increases to improving the efficiency of thermoelectric generators. In semi­
around − 2000 μV/K at 550 K. These results show exceptionally high conductors, while phonon movement largely dictates thermal conduc­
Seebeck values. However, at 600 K, the Seebeck coefficient of tivity, the contribution of carriers to this property is typically less
Zn0.85Fe0.15O begins to decrease. Notably, these Seebeck coefficients are significant. Additionally, factors such as crystal structure, defects, va­
significantly higher than those observed for pure ZnO produced in cancies, and the arrangement of atoms or molecules in the material also
similar studies [8,22]. influence thermal conductivity [56–58]. The calculation of thermal
The electrical properties of 15 % Fe-doped ZnO thin film on Si sub­ conductivity was performed across the 300–600 K temperature range
strate were obtained by measuring the resistance value at various tem­ using the formula κ = AΔTQL
. Here, Q represents the heat transferred from
perature values. From these resistance values, the electrical conductivity the hot end to the cold end of the material, L denotes the length sepa­
l
was calculated as a function of temperature using the formula α = RA . rating these two ends, A is the cross-sectional area of the thermoelectric
Here, R defines the resistance, l and A denote the length and area of the thin film, and ΔT is the temperature gradient.
thin film, respectively. The change in electrical conductivity of the At low temperatures, thermal conductivity generally increases as
produced semiconductor material depending on temperature is shown phonon movement becomes more ordered with fewer scattering events.
in Fig. 11. At low temperatures, the electrical conductivity of semi­ At high temperatures, increased phonon scattering typically reduces
conductors is typically low due to reduced carrier concentration and thermal conductivity. Furthermore, at elevated temperatures, the
limited thermal energy, which restricts the availability of charge car­ interaction between phonons and carriers can complicate the behavior
riers. As the temperature increases, the carrier concentration also in­ of thermal conductivity. Nanostructured materials have the potential to
creases, leading to a rise in electrical conductivity. On the other hand, improve the Seebeck coefficient by lowering thermal conductivity,
electrical conductivity may continue to increase due to higher carrier while maintaining or even improving electrical conductivity [59]. The
concentration and band gap narrowing, but very high temperatures can obtained results are satisfactorily consistent with these explanations.
also introduce significant phonon scattering, which may limit carrier The thermal conductivity of thin film decreases from 13 W/mK to 6
mobility and affect conductivity. As seen in Fig. 11, although electrical W/mK with increasing temperature (Fig. 12).
conductivity increases with temperature, the values remain relatively Finally, after determining the electrical conductivity, thermal con­
low. ductivity, and Seebeck coefficient as functions of temperature, the ZT
The calculations show that electrical conductivity increases with values, which depend on these three parameters, were calculated. The
temperature in the range of 300 K–600 K. Specifically, the conductivity sample exhibits the highest performance at 550 K, achieving a ZT value
of the 15 % Fe-doped ZnO thin film rises from 0.1 S/m to around 30 S/m of approximately 0.004. Beyond this temperature, the ZT value de­
as the temperature increases. This behavior follows the natural mecha­ creases, reaching 0.00024 at 600 K. ZT values are shown in Fig. 13 on
nism of semiconductors: at low temperatures, conductivity is primarily both semi-logarithmic and linear scales.
governed by extrinsic carriers, while at high temperatures, intrinsic In previous studies involving the author, the ZT value for pure ZnO,
carriers dominate [54]. As the material is n-type, at lower temperatures, prepared under nearly identical conditions, was in the order of 10− 6 at
the conductivity is mainly contributed by carriers in the donor levels. As 550 K [8,22]. These results indicate that Fe doping enhances the ther­
the temperature increases, however, deep-level defects and carriers from moelectric performance of ZnO, primarily by increasing the Seebeck
the valence band also begin to contribute to the overall conductivity. coefficient and reducing thermal conductivity. To the best of our
Thermal conductivity (κ) is another key parameter that measures a knowledge, no studies in the literature have specifically explored the
material’s ability to conduct heat, typically expressed in units of W/ low-cost and simple production of Fe-doped ZnO thin films as

Fig. 11. Electrical conductivity of the produced sample in the temperature

range of 300 K–600 K. Fig. 12. Thermal conductivity of the sample at different temperature values.

10
N. Üzar Physica B: Condensed Matter 704 (2025) 417045

carefully selected to optimize thermoelectric performance. Generally,

films of intermediate thickness provide an ideal balance for achieving
the best thermoelectric performance. In this study, the film thickness is
945 nm. If the film thickness were lower, the Seebeck coefficient could
have been higher and the thermal conductivity could have been lower.
In this way, the thermoelectric performance could have been further
improved. In this study, the optimized thickness was not determined
because the films were prepared under the same conditions to compare
the obtained results related to some physical properties with those from
the studies referenced in Refs. [8,13,22]. The film thickness could have
been reduced by decreasing the number of coatings or the amount of
sprayed solution. However, the focus was more on investigating the type
and amount of the dopant material rather than the effect of thickness on
the thermoelectric properties. Therefore, no study was conducted
regarding the optimized thickness. Despite the film thickness being
sufficiently high, the low electrical conductivity is another reason why
the thermoelectric performance is not at the desired level. This could be
largely attributed to the acceptor-type defect states created by zinc va­
Fig. 13. ZT values of 15 % Fe-doped ZnO thin film consisting of nanoparticles cancies and oxygen interstitials observed in the PL spectrum, which act
as a function of temperature. as recombination centers and reduce the carrier concentration. Addi­
tionally, the scattering mechanisms induced by the increased defects at
thermoelectric materials using the sol-gel method. Therefore, the results high doping levels could have caused a reduction in electrical current.
obtained in this study are promising for advancing research in this area.
It is clear that Fe doping significantly improves the thermoelectric per­ 4. Conclusions
formance of ZnO. Despite the improvement in the thermoelectric per­
formance of Fe-doped ZnO compared to pure ZnO, the desired values (at This study successfully synthesized 15 % Fe-doped ZnO thin films
least ZT = 1) have still not been reached. One of the reasons for this using sol-gel dip coating and spraying methods on glass and silicon
could be the film thickness. Studies on thermoelectric power measure­ substrates. The main objective of this study was to investigate the op­
ments have shown that as the film thickness decreases, the Seebeck tical, electrical, structural, and thermoelectric properties of high con­
coefficient increases [60,61]. This increase is due to the reduction in centration Fe-doped ZnO. Structural characterization techniques,
carrier concentration and the enhancement of surface effects, which including SEM, EDS, and XRD, confirmed the formation of a pure Fe-
cause carriers to move less freely, leading to an increase in the Seebeck doped ZnO nanoparticles with a hexagonal ZnO polycrystalline struc­
coefficient. As the carriers become more confined, they generate a ture. The film exhibited high optical transmittance of approximately 90
higher potential difference. Moreover, the impact of surfaces on the % in the visible spectrum, with a band gap of 3.23 eV, determined using
carriers can lead to a greater energy difference between electrons. the Tauc method. The refractive index decreased from 1.8 to 1.5 as the
However, this increase in Seebeck coefficient corresponds to a decrease wavelength increased from 400 to 700 nm. Photoluminescence analysis
in electrical conductivity, as the carriers’ mobility is reduced due to revealed a band gap of 3.27 eV, with emission peaks attributed to
more frequent interactions with surfaces and boundaries. Additionally, electronic transitions involving zinc vacancies (2.45 eV) and oxygen
crystal defects and surface interactions may cause scattering of the interstitials (1.81 eV). The sol-gel synthesis method, combined with Fe
carriers, which further limits the electrical conductivity of the film. As doping, notably increased the probability of defect levels within the ZnO
the film thickness increases, the carriers’ mobility improves, and the structure. This modification has enabled the ZnO, which originally
Seebeck coefficient stabilizes, approaching the values observed in bulk emitted in the UV region, to also exhibit photoluminescence in the
materials. In bulk materials, the Seebeck coefficient is typically lower visible range. Electrical measurements, including those derived from the
because, as carrier concentration increases, the energy difference be­ Norde, Cheung, and thermionic emission methods, indicated ideality
tween carriers becomes less pronounced. With increasing film thickness, factors ranging from 3.78 to 5.7, barrier heights between 0.57 eV and
both the carrier concentration and the reduction of surface effects lead 0.66 eV, and series resistance values between 19.3 kΩ and 49.1 kΩ,
to an increase in electrical conductivity, as the carriers are able to move depending on the method used. Thermoelectric measurements showed
more freely. Regarding thermal conductivity, as the film thickness de­ that as temperature increased, both the Seebeck coefficient and elec­
creases, there is more interaction with surfaces, which can limit phonon trical conductivity improved, while thermal conductivity decreased. The
propagation. Phonons are scattered when they collide with surfaces, maximum thermoelectric efficiency reached 0.004 at 550 K, with a
leading to a decrease in thermal conductivity. This reduction becomes Seebeck coefficient of approximately − 2000 μV/K, highlighting the
significant when the film thickness falls below 100 nm, which is ad­ potential of Fe-doped ZnO thin films for thermoelectric applications. In
vantageous for thermoelectric performance, as lower thermal conduc­ addition, while it was observed in previous studies on the thermoelectric
tivity contributes to higher efficiency. However, as the film thickness properties of ZnO that the ZT value reached maximum values at high
increases, phonons can move more freely due to the reduced influence of temperatures [62], this study observes an enhancement in ZnO’s per­
surface effects, allowing them to propagate over longer distances within formance at lower temperatures with Fe doping.
the material, thus increasing thermal conductivity. As the film thickness
approaches bulk levels, thermal conductivity also increases. The ther­ Declaration of competing interest
moelectric performance (ZT) is determined by the combination of these
parameters. Therefore, each parameter exhibits different behavior in The authors declare that they have no known competing financial
various thickness regimes. As the film thickness decreases, the combi­ interests or personal relationships that could have appeared to influence
nation of low electrical conductivity, high Seebeck coefficient, and low the work reported in this paper.
thermal conductivity can enhance ZT. In contrast, as the film thickness
increases, the rise in electrical conductivity, along with the decrease in Acknowledgement
Seebeck coefficient and the increase in thermal conductivity, can reduce
ZT. In conclusion, film thickness is a critical parameter that must be This research received financial support from TÜBİTAK under grant

11
N. Üzar Physica B: Condensed Matter 704 (2025) 417045

number 121F465 in Turkey. The author would also like to express [24] M. Pal, U. Pal, J.M.G.Y. Jiménez, F. Pérez-Rodríguez, Effects of crystallization and
dopant concentration on the emission behavior of TiO2:Eu nanophosphors,
appreciation to Abdullah Ateş, head of the I.U. Strategy Department, and
Nanoscale Res. Lett. 7 (1) (2012) 1.
Associate Professor Cemil Akçay from the Faculty of Architecture at [25] [Link]
Istanbul University for their support. Furthermore, the author extends rsgnfj6l.
deep gratitude to Professor Barış Kınacı from the Photonics Application [26] J.I. Langford, A.J.C. Wilson, Scherrer after sixty years: a survey and some new
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and Research Center at Gazi University for his invaluable help with some [27] V. Uvarov, I. Popov, Metrological characterization of X-ray diffraction methods at
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Abdulaziz for his support. Materials, Mater. Charact. 85 (2013) 111.
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various type rare earth elements doped ZnO thin films, J. Mater. Sci. 29 (2018)
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