ISSN 2070-2051, Protection of Metals and Physical Chemistry of Surfaces, 2021, Vol. 57, No. 3, pp. 488–499.

© Pleiades Publishing, Ltd., 2021.

NANOSCALE AND NANOSTRUCTURED

MATERIALS AND COATINGS

The Optical and Structural Properties of Undoped ZnO

and Co-doped ZnO:Alx:Cdy x = 1 at %, y = 1, 2, 3, 5 at %
Thin Films, and Their Electrical Characteristics as Photodiode
Nihat Demirbileka, Fahrettin Yakuphanoğlua, and Mehmet Kayab, *
a Department of Physics, Faculty of Science, Firat University, Elazig, Turkey
b
Tekirdağ Namık Kemal University, Çorlu Vacational School,
Machinery and Metal Technologies Department, Çorlu/Tekirdağ, Turkey
*e-mail: mehmetkaya75@hotmail.com
Received August 27, 2020; revised January 11, 2021; accepted January 12, 2021

Abstract—ZnO semiconductor thin films with and without Al/Cd additives were produced with sol–gel spin
coating technique. Also, photodiodes with and without Al/Cd additives were prepared using the same
method. The structural properties of thin films produced were examined with SEM and XRD. Optical prop-
erties were tested using UV spectrophotometer, and band gap energies of the films were analyzed using absor-
bance values obtained. It was observed that the films had hexagonal wurtzite crystal structure, and their band
gap energies reduce with increasing amount of Cd added. The electrical characterizations of photodiodes
were analyzed with phototransient current (I-t, C-t), current-voltage (I-V), capacitance-voltage (C-V) and
conductance-voltage (G/w-V) measurements. The barrier height and ideality factor parameters of the diodes
were calculated using thermoionic emission model. The photodiodes exhibited photosensitive behavior, and
it was seen that reverse bias current raised due to raising the light intensity. The results demonstrated that the
produced diodes can be used as photodiodes or photosensors in optoelectronic implementation.

Keywords: Co-doped ZnO, sol–gel, photodiode, optical properties

DOI: 10.1134/S2070205121030096

1. INTRODUCTION large surfaces and easy adjustment of additive concen-

Recently, a lot of researches have been done for the
production of nanostructured materials and their
applications in different fields. One of the most
important reasons of these studies is that their electri-
cal and optical properties can be checked by grain size
[1, 2]. This allows the nanostructured material to be
used for different applications depending on the grain
size and structure. For this reason, it is preferred to use
nanostructured materials especially in the construc-
tion of electronic circuit elements to be used for differ-
ent electronic circuit applications [3]. ZnO has a high
electrical conductivity and a direct-pass forbidden
energy range of approximate 3.37 eV at room tempera-
ture [4, 5]. The materials formed by combination of
II-VI group elements in the periodic table are semi-
conductors and have a high exciton binding energy
(60meV). ZnO semiconductor thin films are suitable
materials for electronic and optical devices. In addi-
tion, zinc oxide is non-toxic, widely available and
inexpensive. ZnO thin films are coated with a few dis-
similar techniques like chemical vapor deposition
(CVD) [6], chemical spray pyrolysis (CSP) [6, 7],
pulsed laser deposition (PLD), sputtering and sol–gel
[8]. Sol–gel method is widely used because of its cost-
effectiveness, simplicity of coating, application to
tration compared to other methods. Aluminum (Al)
[9, 10], gallium (Ga) [11] and indium (In) [12] are
mostly used as additive materials to produce semicon-
ductor thin films. There are also lots of studies on ZnO
thin films, which are doped with tin (Sn) [13], lithium
(Li) [14], magnesium (Mg) [15], zirconium (Zr) [16],
erbium (Er), manganese (Mn) [17], cadmium (Cd)
[18] and copper (Cu) [19]. Semiconductors with large
band (Broadband), which are permeable in the
appearing zone of the electromagnetic spectrum, have
a significant effect in the production of electronic and
optoelectronic devices [20]. The most important
advantages of transparent conductive and semicon-
ductor oxides are that they are chemically stable and
can be easily coated on different substrates [21]. In this
study, sol–gel method, which is easier and more eco-
nomical than other methods, was used to prepare
solution of the samples. ZnO semiconductor thin
films (on glass substrate) with and without Al/Cd
additives were produced with spin coating technique.
Also, photodiodes (on n-type Si substrate) with and
without Al/Cd additives were prepared using the same
technique. The impression of Cd added on the struc-
tural, optical and electrical properties of thin films and
photodiodes were analyzed.

488
 THE OPTICAL AND STRUCTURAL PROPER
2. EXPERIMENTAL
In this study, pure ZnO and co-doped ZnO:Alx:Cdy
(x = 1 at %, y = 1, 2, 3, 5 at %) thin films, and also pure
n-Si/ZnO and co-doped n-Si/ZnO:Alx:Cdy (x = 1 at %,
y = 1, 2, 3, 5 at %) photodiodes were prepared via a sol-
gel method and a spin-coating technique. To prepare the
samples, zinc acetate dihydrate (Zn (CH3COO)2⋅2H2O)
as a essence of zinc, aluminum nitrate nonahydrate
(Al(NO3)3⋅9H2O) and cadmium acetate [Cd(CH3COO)2⋅
2H2O] as additive materials, 2-methoxyethanol
(DME) [C3H8O2] as a dissolvent, and monoethanol-
amine (MEA) [C2H7NO] as a stabilizer were used
respectively. The content of solutions of ZnO with and
without additive was prepared as 0.5 M, and heated at
60°C for 1 h in bottles with a magnetic stirrer in order
to get homogeneous solution, and then was aged for
20–24 h.
Glass substrates with 2 × 1 cm2 size and 2 mm
thickness were cleaned by using acetone, ethanol, dis-
tilled water and then dried with nitrogen gas to prepare
thin films. The solutions of ZnO with and without
additive Al/Cd were poured on glass substrates, and
spined at 1500 rpm for 15 s. Later, the films were
heated at 250°C for 10 min and then this procedure
was repeated 5 times in order to increase the thickness
of films. To obtain photodiodes, n-type Si substrates
with 1 × 1 cm2 size were cleaned by using RCA method
and dried with nitrogen gas. Then, the solution was
poured on the cleaned substrates, the films were spined
at 3000 rpm for 30 s. and heated at 250°C for 10 min.
This procedure was repeated 3 times in order to increase
the thickness of the films. Finally all thin films and
diodes were annealed at 450°C in the furnace for 1 hr
and then cooled at room temperature [21].
The structure properties and morphology of thin
films were investigated by images obtained using scan-
ning electron microscope (SEM). XRD patterns were
obtained with X-ray diffractometer in the 2θ range
between 10° and 90° at room temperature. The trans-
mittance and absorption spectra of the films were
evaluated in the wavelength range of 200–1000 nm
through UV–VIS–NIR spectrophotometer and the
optical band gap energies of thin films were computed.
The current–voltage, the capacitance–voltage, the
conductance-voltage and the photoresponse charac-
teristics of the fabricated diodes were examined using
KEITHLEY 4200 semiconductor characterization
system.
3. RESULTS AND DISCUSSION
3.1. Surface Morphology and XRD Analysis
Scanning electron microscope (SEM) images of
pure ZnO and co-doped ZnO:Alx:Cdy thin films were
taken to obtain information about their surface mor-
phology, in Figs. 1a–1e. SEM images of thin films
show us that the pure ZnO and co-doped ZnO struc-
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
489
tures are homogeneously coated on the glass substrate,
there are no agglomeration and gaps on the surface.
Particles are nearly in identical dimension and covered
very appropriate on the surface, it is seen that the
grains are held together better, and also have nanofiber
structures.
Similar structure and morphology were shown by
Yakuphanoglu et al. [22] for pure ZnO and Cd doped
ZnO thin films synthesized similar as samples fabri-
cated in this study. Also, morphological structures of
Al-doped ZnO and Al, Na co-doped ZnO thin films,
which were produced using sol–gel method and spin
coating technique, were investigated by Wang et al.
[23]. It is stated that the surfaces of the thin films pro-
duced by them are homogeneous, like the surfaces of
the samples fabricated in this study.
X-Ray diffraction patterns of pure and co-doped
ZnO specimens synthesized through sol–gel method
on glass substrates are given in Figs. 2a–2e. It is seen
that all the pure and co-doped ZnO nanoparticles fab-
ricated are in crystal structure. When the diffraction
patterns were examined, it was determined that the
films were in the hexagonal wurtzite crystal structure
in the zincite (ZnO) phase. In addition to, it is deter-
mined that the characteristic peaks belonging to the
ZnO phase (34, 22°, 2θ) correspond to the plane
(002). Also, similar diffraction peak (002) was again
observed for the co-doped samples (ZnO:Al 1%, Cd
1%; ZnO:Al 1%, Cd 2%; ZnO:Al 1%, Cd 3%; Al 1%,
Cd 5%). When the diffraction patterns of cadmium-
doped AZO (AZO—Al-doped zinc oxide) thin films
were examined, it was observed that the peak density
in the plane (002) decreased with increasing Cd con-
tribution in general. The densities of the peaks can
change due to the accumulation of excess cadmium
atoms in the ZnO matrix and disrupting in the struc-
ture. As cadmium concentration increases, Cd atoms
occupy the intermediate regions in the lattice. This
causes an increase in mesh defects in the crystal [22].
In addition, with addition of Cd, a small amount of
secondary phases can occur in the structure. In XRD
patterns of cadmium-doped AZO films, the absence
of peaks of other phases indicates that Cd ions enter
the crystalline structure and replace it with O–2 ions. It
is also seen that the films grow along c-axis. Similarly,
different proportions of Cd doped ZnO thin films,
Cd(1 and 3 at %) doped by Yakuphanoglu et al. [22],
Al 1 at % and Cd (2, 4, 6, 8 at %) codoped by Duan et
al. [24], Cd (0.15, 0.25, 0.35 and 0.45 at %) doped by
Jule et al. [25], and Cd (5, 10, 20, 30 at %) doped by Li
et al. [26]. They reported that all prepared thin films
have hexagonal wurtzite structure and grown perpen-
dicular to c-axis of the crystal structure in desired per-
fection. Wang et al. [23] investigated the structure of
Al-doped ZnO and Al, Na co-doped ZnO thin films
produced using the same method. They observed that
the structure of the enlarged ZnO films was hexago-
nal. In an other research, Xu et al. [27] studied crystal
structure of pure ZnO, Al-doped ZnO and Al, K co-
Vol. 57 No. 3 2021
490 DEMIRBILEK et al.

(a) 10 μm (b) 15 μm

(c) 15 μm (d) 15 μm

(e) 10 μm

Fig. 1. SEM images of pure ZnO (a), Al 1% Cd 1% ZnO (b), Al 1% Cd 2% ZnO (c), Al 1% Cd 3% ZnO (d) and Al 1% Cd 5%
ZnO (e).

doped ZnO thin films produced using the sol–gel
method and spin coating technique. It is observed in
their study that the structure of all films was coated
perpendicular to c-axis of the crystal structure in
desired perfection. The results obtained are also in
agreement with the studies in the literature [22–27].
3.2. Optical Properties
Optical properties of synthesized pure ZnO and co-
doped ZnO thin films were investigated. Absorbance,
transmittance and band gap energy graphs of speci-
mens are given in Figs. 3a–3c. As shown in Fig. 3a,
ZnO thin films with added Al and Cd show absorption
limit lower than 400 nm. It was observed that absorp-
tion limit gradually decreased with addition of Al and
Cd. It is understood that the samples with lower addi-
tive are better for conductivity. The optical transmit-
tance curves of pure and co-doped thin films are seen in
Fig. 3b. It is observed that pure ZnO and co-doped
ZnO thin films with added Al and Cd are quite trans-
parent in wavelength range from 400 to 500 nm. In Fig.
3b, transmittances of thin films increase dramatically
for Cd1% and Cd 2%, but decrease for Cd 3% and Cd
5%. Their transmittance values vary between 83 and
90%, which are seen in Table 2. Also, band gap ener-
gies of the samples are given in Table 2. The band gap
energies were computed from basic absorption edge of
the thin films. The variation in the band gap energy is
owing to the shift in the band edge. The band gap
energy is calculated via Equation (1) [25].
(αhv )1/ n  = A(hv − E g ). (1)

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 57 No. 3 2021

 THE OPTICAL AND STRUCTURAL PROPER 491

12 000

10 000 (002) From down (a) to up (e)

(a) Pure ZnO
8000 (b) Al 1%, Cd 1%-ZnO

Intensity
(c) Al 1%, Cd 2%-ZnO
6000 (d) Al 1%, Cd 3%-ZnO
(e) Al 1%, Cd 4%-ZnO
4000

2000

0
20 30 40 50 60 70 80 90
2θ

Fig. 2. XRD patterns of pure ZnO (a), ZnO (Al 1%, Cd 1%) (b), ZnO (Al 1%, Cd 2%) (c), ZnO (Al 1%, Cd 3%) (d) and ZnO
(Al 1%, Cd 5%) (e).

Where, α is absorbtion coefficient, A is constant
based on probability of transition and n is an index that
completes optical absorption process. Thus, the graph
of ( αhv ) against hv was drawn using these parame-
1/n
ters. To calculate band gap energy, the tangent was
drawn to the curve on the graph in Fig. 3c, and the
point where the tangent crosses the x-axis was taken
into account. That is, the value of ( αhv ) is 0 on the
1/n
end of tangent crosses x-axis, and so Eg is equal to hv.
In the Eq. (1), n is taken as 1/2 for materials with direct
band transitions while it is taken as 2 for materials with
indirect band transitions.
Considering the band gap energy values given in
the Table 1, it was observed that 3.25 eV for pure ZnO
and the values decreased from 3.23 to 3.14 eV for co-
doped samples. Similarly, the optical band gap energy
values were determined as 3.275, 3.257, 3.248, 3.223
and 3.160 eV for Cd 0%, Cd 2%, Cd 4%, Cd 6% and
Cd 8% doped ZnO thin films [24], 3.15, 3.05, 2.89,
2.79 and 2.76 eV for Cd 0%, Cd 0.15%, Cd 0.25%, Cd
0.35% and Cd 0.45% doped ZnO thin films [25], 3.27,
3.23, 3.21, 3.17 and 3.16 for Cd 0%, Cd 5%, Cd 10%,
Cd 20% and Cd 30% doped ZnO thin films [26],
respectively. The obtained optical band gap energy
values of thin films in present work are between 3.25
and 3.14 eV, and they decrease reasonably with
increasing Cd additive. All these results show us high
rate of Cd dopant does not effect the optical band gap
energy of ZnO seriously, but low rate of Cd dopant
decreases the optical band gap energy of ZnO severely.
Yakuphanoglu et al. [22] fabricated pure ZnO and Cd
(1 and 3%) doped ZnO thin films by sol–gel and spin
coating. They pointed that optical transmittance var-
ied from 68 to 82%, and optical absorption was seen in
wavelength range 380–410 nm for all of pure ZnO and
Cd doped ZnO specimens. In addition to, they calcu-
lated Eg values of ZnO, CZO (Cd 1%) and CZO (Cd
3%) thin films as 3.24, 3.22 and 3.18 eV, respectively.
The optical transmittance values are lower than those
of Al/Cd doped thin films fabricated in this study.
Also, optical band gap energies of samples fabricated
by Yakuphanoglu et al. [22] are higher according to the
results obtained in this study. Their samples contain
only Cd additive, but the samples fabricated in this
study contain both Al and Cd additives. It is under-
stood that Al improves optical transmittance and con-
ductivity of the samples.
In a study by Xu et al. [27], similar thin films were
synthesized using the same method, and optical band
gap energies of synthesized sample were investigated.
It is seen that Eg values for pure ZnO thin film is 3.280 eV,

Table 1. Effect of additive on transmittance and band gap of ZnO

Sample name Transmittance, % Band gap, eV
Pure ZnO 95 3.25
Al 1% and Cd 1% co-doped ZnO 90 3.23
Al 1% and Cd 2% co-doped ZnO 87 3.18
Al 1% and Cd 3% co-doped ZnO 85 3.21
Al 1% and Cd 5% co-doped ZnO 83 3.14

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 57 No. 3 2021

492 DEMIRBILEK et al.

(a) (b)
3.5 100
ZnO 90
3.0
Al 1% Cd 1% 80

Transmittance, %
2.5 Al 1% Cd 2% 70
Absorbance

2.0 Al 1% Cd 3% 60
Al 1% Cd 5% 50
1.5
40 ZnO
1.0
30 Al 1% Cd 1%
0.5 20 Al 1% Cd 2%
0 10 Al 1% Cd 3%
0 Al 1% Cd 5%
–0.5
200 300 400 500 600 700 800 900 1000 200 300 400 500 600 700 800 900 1000
Wavelengh, nm Wavelengh, nm
(c)
2.0
ZnO
Al 1% Cd 1%
Al 1% Cd 2%
(αhv)2, arbitrary unit

1.5 Al 1% Cd 3%
Al 1% Cd 5%

1.0

0.5

0
3.0 3.1 3.2 3.3 3.4 3.5
hv, eV

Fig. 3. (a) Absorbance curve of pure and co-doped ZnO thin films (b) Transmittance curve of pure and co-doped ZnO thin films
(c) energy band gap of pure and co-doped ZnO thin films.

for ZnO thin film with Al 1% doped is 3.295 eV, and Eg
decreased from 3.300 to 3.289 eV with increasing addi-
tived K for ZnO thin films co-doped with Al 1% and K
(1 to 10%). In their study and our study, it is seen that
the additive materials decreased the values Eg. Also, it
was determined by different researches [22, 27] that
band gap energies of ZnO thin films decreased with
increasing additive materials. Wang et al. [23]
explained that transmittance values of co-doped ZnO
thin films added with Al and Na were above 85%, and
Eg values decreased from 3.94 to 3.83 eV, with increas-
ing Na percent. Caglar et al. [28] obtained that optical
transmittance was about 80%, and band gap energies
were 3.280, 3.285, 3.280 and 3.276 eV, respectively for
pure ZnO and ZnO thin films added with Cu (1, 3,
5%), which were produced the same method. The
transmittance values shown above studies are lower
while Eg values are higher than those of our samples.
From this, it is concluded that the films having better
conductivity properties can be obtained by adding
small amount of Al and Cd to ZnO. The results in this
study are compatible with results obtained by Gozeh
et al. [29]. The transmittance values were approxi-
mately 83–94% for Cd (0.1 wt %) and La (0.1–4 wt %)
co-doped ZnO samples, which produced by Gozeh
et al. [29] using the same method. Also, Eg values were
decreased from 3.25 to 3.14 eV, with increasing La
doped.
3.3. Electrical Characteristics of Photodiodes
In this study, the current-voltage characteristics of
n-Si/ZnO, and co-doped n-Si/ ZnO : Alx : Cdy (x =
1%, y = 1, 2, 3, 5%) photodiodes were analyzed under
dark and different light intensities. I–V characteristics
of photodiodes are shown in Fig. 4. As seen in Fig. 4,
current increases in direct proportion with light inten-
sity. These results show us the diodes prepared are
light sensitive photodiodes. To understand the electri-
cal characteristics of diode-based devices, I–V mea-
surements are very important [30]. The electrical
parameters of photodiodes such as barrier height, ide-
ality factor and reverse bias leakage current were
acquired through I–V measurements.

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 57 No. 3 2021

 THE OPTICAL AND STRUCTURAL PROPER 493

10–2 ZnO 10–2 Cd 1%

10–3 10–3

I, A 10–4 10–4

I, A
10–5 10–5

10–6 Dark
10–6 Dark
20 mW/cm2
20 mW/cm2 40 mW/cm2
40 mW/cm2
60 mW/cm2 60 mW/cm2
10–7 10–7 80 mW/cm2
80 mW/cm2
100 mW/cm2 100 mW/cm2
–3 –2 –1 0 1 2 3 –3 –2 –1 0 1 2 3
Voltage, V Voltage, V
10–1 Cd 2% 10–1 Cd 3%

10–2 10–2

10–3 10–3
10–4
10–4
I, A

I, A

10–5
10–5
10 –6 Dark Dark
20 mW/cm2 –6 20 mW/cm2
40 mW/cm2
10 40 mW/cm2
60 mW/cm2
10–7 60 mW/cm2
80 mW/cm2
80 mW/cm2 100 mW/cm2
100 mW/cm2 10–7
10–8
–3 –2 –1 0 1 2 3 –3 –2 –1 0 1 2 3
Voltage, V Voltage, V
10–1 Cd 5%

10–2

10–3
I, A

10–4

10–5
Dark
20 mW/cm2
40 mW/cm2
10–6 60 mW/cm2
80 mW/cm2
100 mW/cm2
10–7
–3 –2 –1 0 1 2 3
Voltage, V

Fig. 4. I–V characteristics of the pure ZnO and co-doped ZnO with Al 1% and concentrations of Cd 1%, Cd 2%, Cd 3%, Cd 5%
for different light intensity conditions.

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 57 No. 3 2021

494 DEMIRBILEK et al.

2.0 × 10–3 5.0 × 10–9 10 kHz 20 mW/cm2

Cd 1% 20 mW/cm2
10 kHz 40 mW/cm2
40 mW/cm2 10 kHz 60 mW/cm2
60 mW/cm2 10 kHz 80 mW/cm2

1.5 × 10–3
80 mW/cm2
100 mW/cm2
4.0 × 10–9 10 kHz 100 mW/cm2

Cd 1%
I(A)

3.0 × 10–9

C(F)
1.0 × 10–3

2.0 × 10–9
5.0 × 10–4
1.0 × 10–9
0

0 5 10 15 20 25 30 35 40 0 5 10 15 20 25 30 35 40
Time, sn Time, sn
8.0 × 10–3 20 mW/cm2 6.0 × 10–9 10 kHz 20 mW/cm2
40 mW/cm2 10 kHz 40 mW/cm2
60 mW/cm2 10 kHz 60 mW/cm2
80 mW/cm2
100 mW/cm2
5.0 × 10–9 10 kHz 80 mW/cm2
–3 10 kHz 100 mW/cm2
6.0 × 10
I(A)

Cd 2% C(F) 4.0 × 10–9

Cd 2%
4.0 × 10–3 –9
3.0 × 10

2.0 × 10–3 2.0 × 10–9

0 1.0 × 10–9

5 10 15 20 25 30 35 40 0 5 10 15 20 25 30 35 40
Time, sn Time, sn

Fig. 5. Transient photocapacitance and current transient measurements of co-doped ZnO with Al 1% and concentrations of
Cd 1%, Cd 2%.

The electrical characteristics of photodiodes can be
analyzed by thermoionic emission model shown in
equation 2.
I = I 0 exp [q (V − IRs ) nkT ] ,
where n is ideality factor, q is electronic charge, Rs is
series resistance, k is Boltzmann constant, V is applied
voltage, T is temperature and I 0 is reverse saturation
current given in Eq. (3).
High value of ideal factor indicates that oxide layer,
series resistance, interface states and inhomogeneities
of Schottky barrier height occur between film layer
and silicon [31]. Generally, ideality factors of photodi-
(2) odes fabricated using the same method are higher than 1.
For example; ideality factor was determined as 3.4 for
co-doped Cd(0.1) wt %–La (0.1 wt) ZnO, and barrier
height was determined as 0.49 eV [29]. It is seen that
band gap energy and barrier height decrease when n-
Si/ZnO is fabricated as co-doped with different ele-

( )
qΦ b
 I 0 = AA*T 2 exp −
. (3)
nkT
In Eq. (3), A is diode contact area, A* is Richardson
constant which is equal to 112 A cm −2 K −2 for n-type
silicon, and Φ b is barrier height. Ideality factor and
barrier height of photodiodes were computed. The
lowest ideality factor and barrier height were obtained
as 4.5 and 0.44 eV respectively for co-doped
n-Si/ZnO:Alx:Cdy (x = 1%, y = 2%). This result shows
us the photodiode prepared demonstrates a non-ideal
behavior owing to the ideality factor is greater than n = 1.
ments, and so conductivity of the sample improves.
The photoresponse of diodes was measured under
dark and different light intensities. As shown in Fig. 4,
the reverse bias currents of photodiodes clearly
increase in direct proportion depending on light inten-
sity. This means that the diodes prepared are photore-
sponse and photoconductive, and they can be used in
different optoelectronic circuits.
The transient photocurrent computations are very
worthy for photoresponse analysis of diode. They were
performed and demonstrated in Figs. 5a, 5c. When the
light is turned on, the current suddenly increases and

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 57 No. 3 2021

 THE OPTICAL AND STRUCTURAL PROPER 495

1200 (a) (b)

ZnO ZnO
Cd 1% Cd 1%
1000 Cd 2% Cd 2%
Cd 3% 0.01 Cd 3%
Photoresponse

800 Cd 5% Cd 5%

logIph, A
600

400 1E–3

200

0 20 40 60 80 100 120 20 40 60 80 100

P, mW/cm2 logP, mW/cm2

Fig. 6. (a) Photoresponse vs. Power and (b) Plot of logIph versus logP for all diodes.

4.0 × 10–9
ZnO 10 kHz Cd 1% 10 kHz
8.0 × 10–10 50 kHz 50 kHz
100kHz 100kHz
200kHz 3.0 × 10–9 200kHz
300kHz 300kHz
–10 400kHz 400kHz
6.0 × 10
500kHz 500kHz
C(F)

C(F)

600kHz 2.0 × 10–9 600kHz

–10 700kHz 700kHz
4.0 × 10 800kHz 800kHz
900kHz 900kHz
1 MHz 1.0 × 10–9 1 MHz
–10
2.0 × 10
0
0
–2 –1 0 1 2 3 –1.0 –0.5 0 0.5 1.0 1.5 2.0
Voltage, V Voltage, V
10 kHz
Cd 2% 50 kHz
4.0 × 10–9 100kHz
200kHz
300kHz
3.0 × 10–9 400kHz
500kHz
600kHz
C(F)

2.0 × 10–9 700kHz

800kHz
900kHz
1.0 × 10–9 1 MHz

–1.0 × 10–9
–1.0 –0.5 0 0.5 1.0 1.5 2.0
Voltage, V

Fig. 7. The capacitance-voltage-frequency plots of pure ZnO and co-doped n-Si/ZnO:Alx:Cdy (x = 1%, y = 1, 2%) photodiodes.

rapidly reaches a constant value for different intensi- turned off. The Ion/Ioff values of the diodes under the
ties ranges (20, 40, 60, 80, and 100 mW/cm2), and then light intensity of 100 mW/cm2 were found as 92.12 and
the current reaches its first value when the light is 271.22 for Cd 1% and Cd 2%, respectively. This indi-

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 57 No. 3 2021

496 DEMIRBILEK et al.

8.0 × 10–3 10 kHz 1.2 × 10–2 Cd 1% 10 kHz

ZnO 50 kHz 50 kHz
100kHz 1.0 × 10–2 100kHz
6.0 × 10 –3 200kHz 200kHz
300kHz 300kHz
400kHz 8.0 × 10–3 400kHz
G(S)

G(S)
500kHz 500kHz
4.0 × 10–3 600kHz 6.0 × 10–3 600kHz
700kHz 700kHz
800kHz 4.0 × 10–3 800kHz
2.0 × 10–3 900kHz 900kHz
1 MНz 1 MНz
2.0 × 10–3
0 0
–2 –1 0 1 2 3 –2 –1 0 1 2
V(V) V(V)
1.2 × 10–2 Cd 2%
10 kHz
1.0 × 10–2 50 kHz
100kHz
200kHz
8.0 × 10–3 300kHz
G(S)

400kHz
6.0 × 10–3 500kHz
600kHz
4.0 × 10–3 700kHz
800kHz
900kHz
2.0 × 10–3 1 MНz
0
–2 –1 0 1 2
V(V)

Fig. 8. The conductance-voltage-frequency plots of pure ZnO and co-doped n-Si/ZnO:Alx:Cdy (x = 1%, y = 1, 2%) photodiodes.

cates that the diodes exhibit strong photoresponse
behavior. Amount of photogenerated charge carriers
increases when diode is illuminated, and current
occurs due to existence of free electrons. Current of
diode decreases when number of free electrons is
decreased. This proves that interface states have com-
pleted filling process.
Under various light intensities, capacitance–time
(C–t) graphs of photodiodes for 10 kHz frequency are
shown in Figs. 5b, 5d. As shown in the Figures, photo-
capacitance clearly increases in direct proportion
depending on light intensity. Photocapacitive and
photoconducting behavior of diodes produced indi-
cates that these diodes can be used as a photodetector
in optoelectronics applications.
We can analyze photoconduction mechanism of
diodes through following Eq. (4),
I ph = AP m.
In Eq. (4), Iph is photocurrent, P is illumination
intensity and A is a constant. It is indicated that pho-
toconducting mechanism of diodes shows a sublinear
behavior through plot of logIph versus logP in Fig. 6b.
The m values were obtained as 0.37, 0.64, 1.90 and 1.30
for Cd 1%, Cd 2%, Cd 3% and Cd 5%, respectively. If
m values are between 0.5 and 1, photoconducting
mechanism of diodes refers a sublinear behavior [32].
In this study, m values of photodiodes for co-doped n-
Si/ZnO:Alx:Cdy (x = 1%, y = 1, 2%) exhibit sublinear
behavior. Similarly, m value of Al/p-Si/n-ZnO/Al
photodiode produced using the same method was
determined as 0.81 [32].
3.4. Capacitance-voltage Characteristics of Photodiodes
The capacitance–voltage (C–V) and conduc-
tance–voltage (G–V) plots of n-Si/ZnO and co-
doped n-Si/ ZnO:Alx:Cdy (x = 1%, y = 1, 2%) photo-
diodes are shown in Figs. 7 and 8, respectively. As seen
clearly in Fig. 7, at negative voltage state, capacitance
(4) increases with decreasing frequency. However, at pos-
itive voltage state, capacitance does not change with
varying frequency, and it remains constant. In Fig. 8,
at positive voltage state, conductance does not vary
with different frequency, but at negative voltage state,
conductance increases with increasing frequency.

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 57 No. 3 2021

 THE OPTICAL AND STRUCTURAL PROPER 497

6.0 × 10–7 10 kHz 10 kHz

ZnO 50 kHz Cd 1% 50 kHz
1.0 × 10–6
100kHz 100kHz
200kHz 200kHz
300kHz 8.0 × 10–7 300kHz
4.0 × 10–7 400kHz 400kHz
Cadj(F)

Cadj(F)
500kHz 500kHz
600kHz 6.0 × 10–7 600kHz
700kHz 700kHz
2.0 × 10–7 800kHz 4.0 × 10–7 800kHz
900kHz 900kHz
1 MHz 1 MHz
2.0 × 10–7
0
0
–3 –2 –1 0 1 2 3 –3 –2 –1 0 1 2 3
V(V) V(V)
10 kHz
Cd 2% 50 kHz
1.0 × 10–7
100kHz
200kHz
8.0 × 10–8 300kHz
400kHz
6.0 × 10–8 500kHz
Cadj(F)

600kHz
700kHz
4.0 × 10–8 800kHz
900kHz
2.0 × 10–8 1 MHz

–2.0 × 10–8
–3 –2 –1 0 1 2 3
V(V)

Fig. 9. Adjusted capacitance plots of pure ZnO and co-doped n-Si/ ZnO:Alx:Cdy (x = 1%, y = 1, 2%) photodiodes.

The graphs of the capacitance–voltage and con- The graphs of adjusted capacitance and adjusted
ductance–voltage demonstrates a non-linear attitude. conductivity at different frequencies are shown in Figs. 9
This undesirable situation can be based upon series and 10. In Figs. 9, 10, some peaks are seen in graphs of
resistance and density of the interface states. In order Cadj–V and Gadj–V. These peaks demonstrate the pres-
to remove influence of space charge capacitance, ence of interface state density, space charge capaci-
interface states density and series resistance, we can tance states, and series resistance between the silicon
adjust the capacitance – voltage and the conduc- and film layer.
tance–voltage graphs via Eqs. (5), (6), (7) [32]. Hence, interface state density (Dit) of diodes can be

(G  )
computed through Eq. (8) [38];
+  ( ωCm ) C
2 2
m   m
Cadj = , (5) Gm  
a   +  ( ωCm )  
2 2

 Dit (N ss  ) = 2  ω max . (8)

( )
2 2
+ ( ωCm )  a
2 qA  Gm   1 − Cm 
  m2
G     Cox    +     
Gadj = , (6)   ω max   Cox 
a   +  ( ωCm )
2 2
In Eq. (8), ω is angular frequency, Cox is capaci-
tance of insulator layer,  m  
G
a = Gm − (Gm2 ( ωCm ) )Rs .
2
(7) is maximum mea-
 ω max
In the equations above, ω is angular frequency, Cadj sured conductance, Cm is measured capacitance and A
adjusted capacitance, Gadj adjusted conductivity, Cm is area of diode.
measured capacity, Gm measured conductivity and a is The graphs of Dit with varying frequency for co-
adjustable parameter depending on Rs, Gm and Cm. doped n-Si/ ZnO:Alx:Cdy (x = 1%, y = 1, 2%) photo-

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 57 No. 3 2021

498 DEMIRBILEK et al.

3.0 × 10–2
ZnO 10 kHz 6.0 × 10–2 Cd 1% 10 kHz
–2 50 kHz 4.0 × 10–2 50 kHz
2.0 × 10
100kHz 100kHz
200kHz 2.0 × 10–2 200kHz
1.0 × 10–2 300kHz 0 300kHz
Gadj(S)

Gadj(S)
400kHz –2.0 × 10–2 400kHz
0 500kHz 500kHz
600kHz –4.0 × 10–2 600kHz
–1.0 × 10–2 700kHz –6.0 × 10–2 700kHz
800kHz –8.0 × 10–2 800kHz
900kHz 900kHz
–2.0 × 10–2 –1.0 × 10–1
1 MHz 1 MHz
–1.2 × 10–1
–3.0 × 10–2
–3 –2 –1 0 1 2 3 –3 –2 –1 0 1 2 3
V(V) V(V)
3.0 × 10–2 Cd 2% 10 kHz
50 kHz
3.0 × 10–2
100kHz
1.0 × 10–2 200kHz
0 300kHz
–1.0 × 10–2 400kHz
Gadj(S)

500kHz
–2.0 × 10–2 600kHz
–3.0 × 10–2 700kHz
800kHz
–4.0 × 10–2 900kHz
–5.0 × 10–2 1 MHz
–6.0 × 10–2
–3 –2 –1 0 1 2 3
V(V)

Fig. 10. Adjusted conductance plots of pure ZnO and co-doped n-Si/ ZnO:Alx:Cdy (x = 1%, y = 1, 2%) photodiodes.

Cd 1% Cd 2%
1.5 × 1014 6.0 × 1013
–2

Dit, eV–1 cm–2

cm

1.0 × 1014 4.0 × 1013

–1
Dit, eV

5.0 × 1013 2.0 × 1013

0 0

0 400.0 k 800.0 k 0 400.0 k 800.0 k 1.0 M

200.0 k 600.0 k 1.0 M 200.0 k 600.0 k
Frequency, Hz Frequency, Hz

Fig. 11. The graphs of Dit versus frequency of co-doped n-Si/ ZnO:Alx:Cdy (x = 1%, y = 1, 2%) photodiodes.

diodes are shown in Fig. 11. As it is clearly seen in Fig. 11, doped with different elements [31, 32]. It is seen that
the interface states density inreases at low freqency, Dit value of n-Si/ZnO:Al 1%:Cd 2%/Al diode is lower
and it attains a constant value by decreasing at high than that of n-Si/ZnO:Al 1%:Cd 1%/Al diode. This
freqencies. Similar results were shown for p-Si/ZnO result demonstrates that intensity quality of interface

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 57 No. 3 2021

 THE OPTICAL AND STRUCTURAL PROPER
states of co-doped n-Si/ZnO:Al 1%:Cd 2% diode is
more better than that of co-doped n-Si/ZnO:Al
1%:Cd 1% diode, and conductivity of co-doped
n-Si/ZnO:Al 1%:Cd 2% diode is better when used as
photodiode.
4. CONCLUSIONS
In this work, morphological, structural and optical
properties of pure ZnO and Al/Cd co-doped ZnO thin
films, and electrical characteristics of n-type Si photo-
diodes produced using sol–gel method and spin coat-
ing technique were investigated. SEM images pointed
that the coating on the glass substrate were homoge-
neously, nanofiber structures were occurred, and the
grains were held together on the surface of the films.
The crystal structure of thin films was determined as
hexagonal wurtzite structure with X-ray diffraction
studies. The band gap energy values of films synthe-
sized decreased with increasing Cd content. It was
determined that the synthesized diodes were light sen-
sitive with the values of Ion/Ioff. In terms of ideality fac-
tor and barrier height, co-doped n-Si/ZnO:Al 1%:Cd
2% photodiodes are better than the others. Moreover,
this photodiode is better than others in terms of inter-
face states density. This result indicates that co-doped
n-Si/ZnO:Al 1%:Cd 2% photodiode is better conduc-
tive. The acquired results suggest that co-doped
ZnO/n-Si photodiodes can be used in the optoelec-
tronic devices such as photosensors and photodetec-
tors.
FUNDING
This study was supported by Firat University, for PhD
thesis (Project no. FF16.24). Author thanks to Firat Uni-
versity.
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