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A study of the effect of 2.5 MeV ⁴ He ²⁺ ion irradiation on the optical, electrical, morphological and structural properties of ZnO thin films is presented. Polycrystalline zinc oxide thin films were deposited on soda lime glass substrates using the spray pyrolysis technique. During the process, the substrates’ surfaces were kept at 400, 450 and 500°C. The samples were analyzed by different techniques and the optical results showed a red shift in the energy band gap after irradiation. It was also confirmed that the wurtzite-type hexagonal structure of the ZnO films remained after irradiation, the crystallite size increased and the lattice parameters decreased due to He ²⁺ irradiation. SEM micrographs revealed that ion irradiation favors the nucleation and the formation of grains in the films. Micrographs showed nanometric particles with spherical and flake-like forms, which depend on the deposition temperature. A decrement in the average particle size of the samples deposited at 400 and 450°C was observed after irradiation; meanwhile, an increase in the particle size was detected in the film deposited at 500°C. The resistivity values increased with He ²⁺ ion irradiation.
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Mater. Res. Express 9(2022)116403 https://doi.org/10.1088/2053-1591/aca240
PAPER
Effect of
4
He
2+
ion irradiation on the optical, electrical,
morphological, and structural properties of ZnO thin lms
Alejandra López-Suárez
, Dwight Acosta and Carlos Magaña
Instituto de Física, Universidad Nacional Autónoma de México, 04510, Ciudad de México, Mexico
Author to whom any correspondence should be addressed.
E-mail: chipi72@gmail.com
Keywords: ZnO, thin lms, SEM, optical band gap, XRD, resistivity, ion irradiation
Abstract
A study of the effect of 2.5 MeV
4
He
2+
ion irradiation on the optical, electrical, morphological and
structural properties of ZnO thin lms is presented. Polycrystalline zinc oxide thin lms were
deposited on soda lime glass substrates using the spray pyrolysis technique. During the process, the
substratessurfaces were kept at 400, 450 and 500 °C. The samples were analyzed by different
techniques and the optical results showed a red shift in the energy band gap after irradiation. It was
also conrmed that the wurtzite-type hexagonal structure of the ZnO lms remained after irradiation,
the crystallite size increased and the lattice parameters decreased due to He
2+
irradiation. SEM
micrographs revealed that ion irradiation favors the nucleation and the formation of grains in the
lms. Micrographs showed nanometric particles with spherical and ake-like forms, which depend
on the deposition temperature. A decrement in the average particle size of the samples deposited at
400 and 450 °C was observed after irradiation; meanwhile, an increase in the particle size was detected
in the lm deposited at 500 °C. The resistivity values increased with He
2+
ion irradiation.
1. Introduction
Zinc oxide (ZnO)is an II-VI semiconductor with a band gap of 3.3 eV and excitonic energy of 60 meV, abundant
in nature, low cost, and low toxicity. These properties have made it a highly appreciated material for research and
applications, especially in optoelectronics and photocatalysis.
ZnO can absorb UV light; however, if the goal is to increase the photocatalytic activity, it is required to
enhance the ability of the semiconductor to absorb light between 400 and 700 nm. To achieve this, the
decrement of its band gap is mandatory. Some research [1,2]have carried out to reduce the band gap by doping
ZnO with transition metals since this procedure does not modify the crystalline structure of the semiconductor;
however, some other physical properties are changed. In this sense, alternatives have been sought to modify the
band gap without substantially changing the materials properties.
Ion implantation is a technique capable of tailoring the physical properties of materials since there is
sufcient control over the experimental conditions, such as the type of ion, its energy, the uence, and the
implantation angle of the projectile; which can modify the defects produced in the structure of the material, the
depth of the doping region, the number of defects produced in the material and the possibility of implanting at
the surface when a low energy accelerator is not available, respectively. Changing these setup conditions makes it
possible to modify well-dened areas of the material, as small or large as required. It is also feasible to alter the
materials surface or an internal region by changing the ion energy, its angle of implantation, or both. This is the
main reason why ion irradiation has become an important technique to modify the physical properties of
materials and several groups have studied the irradiation of different semiconductors, such as silicon, silicon
carbide, germanium, gallium arsenide and in particular ZnO [3,4], by using different ions at different energies
and uences. For instance, Tomic, et al [5]worked with silicon and showed evidence that a 23 MeV I beam can
anneal the pre-existing damage of the materials structure. Levalois and Marie [6]studied the electrical behavior
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REVISED
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ACCEPTED FOR PUBLICATION
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PUBLISHED
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of germanium irradiated with an 880 MeV Pb beam at different uences. They showed that resistivity increased
at low uences, reached a maximum value and decreased when uence is increased. They also reported that the
energy gap of silicon carbide decreased with uence when the material was irradiated with 5.5 GeV Xe ions. On
the other hand, Andrey Kamarou [7]reported that the irradiation of gallium arsenide with 390 MeV Xe ions
reduced the number of structural defects and recrystallized the previously damaged material with 600 keV
Se ions.
ZnO is obtained in a wide variety of forms from bulk to nanoparticles samples, and it is well known that the
quality of the material is strongly affected by the growth conditions. ZnO lms have been deposited by diverse
techniques, such as sputtering evaporation, pulsed laser deposition, chemical vapor deposition, sol/gel,
electrodeposition and spray pyrolysis. In this work, the spray pyrolysis technique was used to deposit ZnO thin
lms because it is a better option than similar techniques. The main advantages can be summarized as follows
[812]. Spray pyrolysis is a simple and low-cost technique that can produce reproducible and high-quality lms
with uniform thickness. Almost any substrate material with complex geometry can be coated. No high
temperatures are required during the synthesis of the samples. It has a straightforward way to dope lms with
almost any element in any proportion by only adding it to the spray solution. Unlike vapor deposition methods,
spray pyrolysis does not require high-quality targets or a vacuum system. The lms deposition rate and
thickness can be controlled by changing the spray parameters. Layered lms can be produced by changing the
composition of the spray solution during the spray process.
In order to achieve the goal of modifying the physical properties of ZnO, in this work, we have irradiated
ZnO thin lms using a 2.5 MeV
4
He
2+
beam, with an average uence of 3.1 ×10
10
He cm
2
, and the results have
been compared with other studies that use different ions and energies as a tool to produce physical changes in
ZnO lms. In this sense, Shasha et al [13]studied the enhancement of ZnOs photocatalytic properties after N
implantation. Iqbal et al [14], Kondkar et al [3]and Vijayakumar et al [15]improved ZnO lm resistivity by
irradiating the material with C, Au and O ions, respectively. On the other hand, the studies made by
Chattopadhyay et al [16], Khawal et al [17]and Abdel-Galil et al [18]showed changes in the band gap and the
resistivity of ZnO when it was irradiated with Ar, Li and O ions, respectively. These works show that even light
ions can produce essential changes in the optical and electrical properties of the semiconductor; however,
limited reports have been found regarding the irradiation of He
2+
ions in ZnO.
The main reason for studying the He
2+
irradiation of ZnO thin lms is that very little research has been done
on the effects of chemically inert He ions on ZnO thin lms; besides, the use of He ions as projectiles avoids any
chemical interaction that other active elements could produce in the material. The use of He ions as projectiles is
benecial for controlling the number of defects without inducing amorphization because the energy deposition
process is dominated by inelastic interactions (electronic stopping)between He and target electrons, which
produces a hot electron gas that surrounds the ion trajectory (thermal spikes), decreasing the number of defects
due to a similar process that is produced during a thermal process.
2. Methods
ZnO thin lms were prepared on a substrate of soda lime glass using the spray pyrolysis technique [19,20]at 400,
450 and 500 °C. In the following, the samples will be labeled as T-400, T-450 and T-500, indicating the substrate
deposition temperature. In order to prepare the spraying solution, 10.97 g of zinc acetate 2-hydrated was
dissolved in 250 ml of deionized water. Afterward, 50 ml of acetic acid was added under agitation, ending with
the incorporation of 700 ml of ethanol. To avoid substrate cooling, the spraying process was carried out in cycles
of 3 s followed by short periods of 5 s without spraying. During ZnO lm preparation, the nozzle-to-substrate
distance was kept at 30 cm.
In order to study the effect of the irradiation of He
2+
ions on the optical, electrical, morphological and
structural properties of ZnO thin lms, the samples were irradiated using a 2.5 MeV
4
He
2+
beam, with an
average uence of 3.1 ×10
10
He cm
2
.
Before (as-grown samples)and after He
2+
irradiations (irradiated samples), ZnO samples were studied by
the following techniques to measure the changes in their physical properties. The elemental analysis and the
thickness of the lms were carried out at the 3 MV Pelletron accelerator with Rutherford Backscattering
Spectrometry (RBS). The RBS analysis was performed with a 2.5 MeV alpha beam of 1 mm in diameter. The
incident and the scattering angles were 0°and 167°, respectively. The scattered ions coming from the elastic
reaction between the alpha particles and the elements that form the sample were acquired by a silicon surface
barrier detector. RBS spectrum is obtained by the analog signals that leave the detector and is processed by a
multichannel analyzer. The SIMNRA code [21]was used to t the RBS spectra. Transmittance studies were
performed at room temperature, in the 3001000 nm range, with an Agilent HP 8453 UVvis
spectrophotometer. The microstructure of the ZnO thin lms was conducted by x-ray Diffraction Analysis
2
Mater. Res. Express 9(2022)116403 A López-Suárez et al
(XRD)analysis, using a Bruker D8 Advanced Diffractometer, with Cu k
α
radiation. The morphology of the
samples, as well as their particle size, were analyzed with the Scanning Electron Microscope (SEM)FEG JEOL
JSM-7800. Resistivity measurements were carried out with a Jandel Multi Height Micro position probe
equipment, using the four-point probe method.
3. Results and discussion
3.1. RBS analysis
The SRIM 2013 simulation code [22]was used to calculate the ion beam energy loss and the projected range
when the projectiles collide with the target atoms. According to this code, the projected range of the He
2+
ions in
the sample (ZnO +soda lime)is 8.67 μm. This distance is greater than the ZnO lmsthickness (100 nm on
average), which ensures that the He ions cross the lm and stop in the substrate; inducing ionization and
excitation effects when the projectiles interact with the electrons of the target and defects in the material when
they collide with their nucleus.
During an RBS experiment, the projectile loses energy as it impinges on the nucleus of an element that
composes the material. This lost energy is directly related to the stopping power of the projectile. If the stopping
power data of the He
2+
ions is known [22]and the energy loss of the projectiles is directly measured from the
RBS spectrum, then the thickness of the lms (X) can be calculated from the following equation [23]:
[] ()
e
=D
XE1
where ΔEand [ε]are the energy loss and the stopping power of the He ions, respectively, as they interact with
each element that composes the sample.
The thickness of the samples was calculated with equation (1)and the results are summarized in table 1.
The results in table 1show a small increment in lm thickness as deposition temperature is increased, and it
is the result of the improvement in lm adhesion as substrate temperature rises, as a consequence of the
enhancement of the nucleation centers, which can enlarge lm thickness.
Zn traces in the substrate were found during the SIMNRA analysis, indicating the lm element diffusion
through the substrate. The depth where Zn traces were detected increases slightly (817, 838, and 842 nm)as the
deposition temperature rises from 400 to 500 °C. The diffusion is due to the energy transfer from the deposition
plate to the substrate produced during the synthesis of the lms.
The quantitative elemental composition of the samples was obtained through the RBS analysis using a 2.5
MeV alpha particles beam. Zn and O signals from the lm, and Si and O, as a part of the substrate, were identied
by the SIMNRA code [21], which allows for obtaining the elemental composition of the materials. Figure 1
shows the elemental percentage concentration of Zn and O in the ZnO thin lms for each deposition
temperature. Inset, the atomic ratio of Zn/O in the lm is displayed.
The results in gure 1reveal that as temperature increases, the Zn/O ratio approaches one; until at 500 °C,
the desirable stoichiometric lm is nally obtained. The excess of O at lower temperatures could be explained as
follows. As the lm is being deposited, oxygen atoms move into the ZnO structure as interstitial atoms, but as
temperature rises, interstitial oxygen atoms bond with hydrogen atoms and form an H
2
O molecule, which can
evaporate and leave the material.
3.2. Optical results
The optical properties of the ZnO thin lms were studied by employing the optical transmittance curves in the
range of 3001000 nm. From these data, the value of the band gap of the semiconductor was calculated.
The results of the transmittance spectra are presented in gure 2, which shows curves with a at appearance.
The transmittance spectra of the as-grown samples indicate the presence of very transparent lms, revealing
values over 80% transmittance in the visible region of the spectrum. The curves show low transmittance values
in the region below 400 nm; which are associated with the ZnO nanoparticlesfundamental absorption bands. In
Table 1. Thickness values of
ZnO thin lms obtained by
RBS analysis.
Sample Thickness (nm)
T-400 93 ±4
T-450 105 ±5
T-500 109 ±5
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Mater. Res. Express 9(2022)116403 A López-Suárez et al
the case of the as-grown lm T-400, an increment in the transmittance value around 360 nm was detected. This
enhancement can be related to the reduction of the density of the lm grain boundaries. Above this point,
transmittance values tend to increase in all cases, indicating a low amount of impurities in the lms [24].
Optical transmittance spectra of the irradiated ZnO lms show similar curves to the as-grown lms for
T-450 and T-500; meanwhile, the irradiated sample T-400 shows a signicant enhancement in the transmittance
value around 360 nm, which doubles the value of the as-grown lm T-400 in this region. This fact assumes the
reduction of defects in the lattice material. It is supported by gure 6(b), where the nucleation and crystal growth
of the ZnO nanometric particles are favored by He
2+
irradiation. This behavior is also observed in materials
subjected to thermal treatments, and it is due to a rapid and local temperature increase which improves lm
crystallinity.
In material science, the removal of lattice defects from crystals is usually done by thermal annealing. The
electronic stopping generated during ion irradiation when the projectile interacts with the electrons target and
loses part of its energy produces a hot electron gas that surrounds the ion trajectory, known as a thermal spike.
Thermal spikes increase temperature throughout the path of the projectile in a very short time, causing
passivation of defects, particle nucleation and improving the crystallinity, as is supported by gures 6(a)and (b).
In this sense, thermal spikes could be similar to annealing.
The thermal spike model [25]describes the damage induced by swift heavy ions and applies to any metal,
semiconductor or insulator material. When a high-energy ion penetrates a material, it rst interacts with the
target electrons, causing their excitation and ionization and lowering their energy due to an electronic energy
Figure 1. Elemental percentage concentration of the elements that compose the ZnO thin lms. The Zn/O ratio of each sample is
displayed in the inset.
Figure 2. Comparative spectra of the optical transmittance curves of the (a)as-grown ZnO and (b)irradiated ZnO lms.
4
Mater. Res. Express 9(2022)116403 A López-Suárez et al
loss. When the ion has lost part of its energy interacting with the materials electrons, it collides with the target
nuclei and nuclear energy loss occurs, producing defects in the crystal lattice. The thermal spike model is based
on the electronic excitation of the material and induces a spike along the path of the ion.
The thermal spike process involved during ionic irradiation can be explained in 4 steps [26,27]. In the rst
step, the incident ions transfer their energy to the target electrons through ion-electron collisions. Secondly,
electron-electron collisions take place and share their energy with cold electrons. During the third step, energy is
transferred to the lattice via electron-phonon coupling. Finally, energy is dissipated among atoms.
The transmittance data allow us to calculate the energy band gap of the lms using the Tauc [17]relation.
() ( ) ()a=-hv A hv E 2
12
In equation (2),αis the absorption coefcient of the material, hv is the photon energy, Ais a constant related
to the refractive index of the semiconductor and Eis the band gap. The absorption coefcient is dened as:
()=
a-
I
I
e3
x
2
1
where I
1
is the intensity of light as it reaches the materials surface, I
2
is the intensity of light penetrating the
material and xis the thickness of the lm. The ratio I
2
/I
1
in equation (3)is dened as the transmittance T,so
getting the absorption coefcient from the transmittance values is natural.
Once the absorption coefcient is calculated, the value (αhv)
2
is plotted as a function of the photon energy,
as is depicted in gure 3. The band gap of the material is achieved from the extrapolated linear part of the curve
when it intercepts the photon energy axis, as can be noticed in gure 3.
The band gap values of the as-grown and irradiated ZnO lms are depicted in gure 4. Firstly, the results
reveal a decrease in the optical band gap with temperature. This behavior has been observed by several groups
and depends on different factors, such as crystallite dimension, quantum size effects, changes in the density of
impurities, variations in crystallinity, defects, lm thickness, residual stresses and strains. In particular, the band
gap decrement is related to an improvement in crystallinity [28], a reduction in the lattice strain [29,30],an
increase in crystallite size [31]and an increase in lm thickness [32]. In our work, these variables are related to
substrate temperature, so the reduction in band gap with substrate temperature is related to lm thickness, as is
shown in table 1; to the increase in crystallite size and to the reduction in the microstrain of the lm, as is
observed in table 2, and to the improvement in crystallinity as is veried in the SEM micrographs.
Figure 4also revealed a decrement in the energy band gap of the samples after irradiation. The optical band
gap of the as-grown lms varied from 3.11 to 3.21 eV; meanwhile, this value changed from 3.09 to 3.18 eV in the
case of the irradiated samples. The reduction in the optical band gap with He
2+
irradiation has been observed by
Shasha et al [13], Khawal et al [17]and Abdel-Galil et al [18]and is related to oxygen vacancies and zinc
interstitials that produce changes in the crystalline matrix, which narrow the optical band gap.
3.3. Structural results
In order to study the crystalline structure of the ZnO thin lms, XRD analysis was acquired. The main diffraction
peaks (100),(002),(101),(102),(110)and (103)of a wurtzite-type hexagonal structure were identied in the
diffractograms of gure 5[33]. The spectra show that the lms are polycrystalline and have a preferred growth
orientation along the c-axis.
Figure 3. Energy band gap variations in (a)as-grown ZnO and (b)irradiated ZnO lms.
5
Mater. Res. Express 9(2022)116403 A López-Suárez et al
The wide of the strongest peak in an XRD diffractogram and Scherrers formula [34]are used to calculate the
average crystallite size (D).
()
l
bq
=Dk
cos
4
where kis the shape factor (0.9),λis the wavelength of the Cu K
α
,θis the Bragg angle, and βis the FWHM of the
strongest peak of the XRD spectrum.
Some lattice strains could be developed during lm formation and are related to crystal imperfections. The
microstrains (ε)were calculated with equation (5)[35]:
Figure 4. Comparative optical band gap values of the as-grown and the irradiated ZnO thin lms.
Figure 5. Diffraction pattern of ZnO (a)as-grown ZnO and (b)irradiated ZnO lms.
Table 2. The average crystallite size and micro strain values before and after irradiation.
As-grown Irradiated As-grown Irradiated
Sample Average crystallite size (nm)Average crystallite size (nm)Microstrain ×10
3
Microstrain ×10
3
T-400 21.43 41.67 2.85 1.47
T-450 33.25 43.34 1.84 1.41
T-500 35.74 47.10 1.71 1.30
6
Mater. Res. Express 9(2022)116403 A López-Suárez et al
()ebq
=cot
4
5
Table 2displays the average crystallite size and the microstrain for the as-grown and irradiated ZnO thin
lms. The results show that the average crystallite size increases with temperature. This fact is due to the rate of
the deposition reaction that increases with temperature and consequently the crystallites grow faster, resulting in
a larger size [36].
Table 2also shows that crystallite size increases after irradiation in all the cases, especially in sample T-400,
where the increment was almost 50%. It is noticeable that He
2+
ion irradiation favors crystal growth and
improves ZnO lms crystallinity, as was veried by SEM studies. Khan et al [37]observed the increment of
crystallite size with ion irradiation when they irradiated ZnO thin lms with Ni
2+
ions. They concluded that the
increment of crystallite size is related to the reduction in strain due to an annealing effect (thermal spikes)
produced during irradiation.
The only case where irradiation is not improving crystallinity is at sample T-400, where the diffractions lines
(100)and (101)are barely visible. At 400 °C, the formation of the lm begins, and its diffraction peaks are tiny, so
any sputtering effect induced by the He
2+
projectiles during irradiation may be responsible for the loss of
crystallinity of the ZnO lm.
Figure 5also shows an increase in the intensity of the diffraction peaks as the growth temperature of the lms
increases, both in as-grown and irradiated samples. This fact can be attributed to the increase in the
concentration of Zn atoms in the ZnO lm as the temperature of the substrate increases. This is veried in
gure 1, where the elemental concentrations of the lms are displayed. This behavior has been observed by
Durgajanani et al [38], Benny et al [39], and Zaier et al [40].
The lattice parameters of the as-grown and irradiated ZnO lms were calculated using equation (6), which
relates the interplanar distance, the Miller index, and the lattice constants in a hexagonal structure. The results
are presented in table 3.
⎜⎟
()
()
=++ +
d
hhkk
a
l
c
13
4
6
hkl
2
22
2
2
2
The results indicate that irradiation shrinks the lattice parameters, which is related to compressive stresses
owing to the substitution of He
2+
ions in the lattice. This is a direct consequence of ionic irradiation since,
during this process, the He
2+
ions collide with the Zn and O atoms, losing energy due to collisions with the
nuclei that form the material. These nuclear collisions can trigger the formation of point defects, such as
vacancies, interstitials, and displacements of atoms in the lattice. In this way, He
2+
ions can substitute Zn and O
atoms in the crystal lattice. However, since He has a smaller atomic radius than Zn and O, the crystal structure
tends to shrink, and a decrement in lattice parameters is observed [14,37].
3.4. Morphological results
In order to analyze the surface morphology and to measure the grain size of the as-grown and irradiated ZnO
lms at different substrate temperatures (400, 450, and 500 °C)SEM analysis was performed. Comparative
micrographs of the lms are shown in gure 6, where a total coverage substrate with ZnO grains is observed in all
the images. They reveal that the particles that compose the lms are nanometric in size, show spherical and ake-
like structures and are modied by irradiation. Micrographs also show that their density, size, and shape are
strongly dependent on the deposition temperature.
When comparing the irradiated samples with the as-grown ones, it is observed that ionic irradiation favors
the nucleation and the formation of grains, especially at low deposition temperatures. With the naked eye, a
decrease in the size of the grains that make up the irradiated samples T-400 (gure 6(b)) and T-450 (gure 6(d))
is observed. However, it is also noticed an increase in the size of the particles that compose the irradiated lm
T-500 (gure 6(f)). Micrographs also exhibit a better lling of pores after irradiation, which is related to an
increment of local annealing effect, just as was previously explained.
Table 3. Comparison of the lattice parameters of the as-grown and
irradiated ZnO thin lms.
As-grown Irradiated As-grown Irradiated
Sample a (nm)a(nm)c(nm)c(nm)
T-400 0.3351 No detected 0.5445 0.5438
T-450 0.3378 0.3360 0.5457 0.5444
T-500 0.3382 0.3367 0.5460 0.5449
7
Mater. Res. Express 9(2022)116403 A López-Suárez et al
Micrographs related to as-grown samples T-400 (gure 6(a)) and T-450 (gure 6(c)) show diffuse particles
with irregular forms. Nevertheless, the irradiation process tends to homogenize the size and shape of the
particles. A bimodal particle size distribution is also appreciated, especially in the irradiated samples.
In order to measure the average size of the particles before and after irradiation, the J-Image code was used.
Results displayed in gure 7support what is observed in the micrographs of gure 6regarding the two different
behaviors concerning the change in the particle size. The samples prepared at lower temperatures show a
decrease in the average size of their particles after irradiation; meanwhile, in the sample synthesized at the higher
temperature, the size of their particles increases with ionic irradiation. The explanation could be the following.
During a pyrolysis process, deposition temperature is quite essential to form the particles thatcompose the lm.
When the temperature is low, the particles are not fully formed, so when He
2+
ions collide with the material, a
sputtering effect induced by the ion irradiation produces fractures in the grains, resulting in a decrease in the
average particle size of the sample. In the case of the sample T-500, the grains are completely formed, and the
irradiation produces particle nucleation due to the heat produced by the thermal spikes. As reported by Sharma
et al [41], this coalescence effect increases the average particle size. We can also notice that the sample deposited
Figure 6. SEM micrographs of the ZnO thin lms T-400 (a)as-grown, (b)irradiated, T-450 (c)as-grown, (d)irradiated and T-500 (e)
as-grown, (f)irradiated.
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Mater. Res. Express 9(2022)116403 A López-Suárez et al
at the lower temperature shows slight changes in particle size after irradiation. This effect has been observed by
Kalita et al [42]. They explained that tiny particles are more tolerant to ionic irradiation because their large
number of grain boundaries act as sinks for the defects induced during irradiation.
3.5. Electrical results
Figure 8shows the variation of electrical resistivity of the as-grown and irradiated ZnO lms. The curves show a
decrement in resistivity at 450 °C and then an increase at 500 °C, indicating a variation related to the deposition
temperature. The evolution of electrical resistivity with temperature can be explained by the combination of two
properties of semiconductors: their behavior with temperature, which in the case of ZnO decreases with
temperature, and their stoichiometry deviations. In our case, the decrement of resistivity in the range of 400 to
450 °C is explained based on the nature of ZnO, which predicts that this variable decreases with temperature. On
the other hand, the enhancement of resistivity in the range of 450 to 500 °C is due to the atomic composition of
the semiconductor, that at 500 °Cts the perfect ZnO stoichiometry, as can be veried in gure 1. There are
several reports [4345]of temperature-dependent resistivity in ZnO thin lms following the same resistivity
evolution as ours.
Figure 7. Average particle size of the as-grown and irradiated ZnO lms.
Figure 8. Variation of resistivity of the as-grown and irradiated ZnO lms.
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Mater. Res. Express 9(2022)116403 A López-Suárez et al
The comparison of the resistivity of the as-grown and irradiated ZnO thin lms results is also exhibited in
gure 8. The results indicate that ZnO thin lms become more resistive after ion irradiation, and that resistivity
could be tailored in ZnO by changing the substrate temperature during the pyrolysis process. In the case of the
as-grown samples, the resistivity of the lms shows a value of 23.08 ×10
2
Ωcm at 400 °C, then the value drops
to 2.18 ×10
2
Ωcm at 450 °C, and nally, the resistivity is increased, getting a value of 18.25 ×10
2
Ωcm at
500 °C. The irradiated lms follow similar behavior as the pristine ones, where resistivity takes a very close value
to the as-grown sample of 29.04 ×10
2
Ωcm at 400 °C. At 450 °C, resistivity has a value of 19.51 ×10
2
Ωcm and
at 500 °C, the electrical resistivity value is 37.49 ×10
2
Ωcm.
Several groups have studied the behavior of electrical resistivity as ZnO is irradiated with different types of
ions and energies. However, their results show either enhancement or decrement of this value, so no conclusions
can be drawn. In this sense, some groups have found an increase in electrical resistivity after ion irradiation. For
instance, Iqbal et al [14]worked with 800 keV C ions, concluding that the increment of resistivity with
irradiation is due to the creation of defects in ZnO induced by the ion beam. They also mention that the ZnO
structure was disordered due to the irradiation, which increases resistivity. Kondkar et al [3]used 75 MeV Au
ions in their work. They attribute the resistivity enhancement to the increase in grain boundary scattering, which
occurs as a consequence of nano-hillock formation in the irradiated lms. They also assume that the increase in
grain boundary scattering reduces the electronic mobility, increasing the materials resistivity. Vijayakumar et al
[15]argued that the rise in electrical resistivity with 100 KeV O irradiation is due to oxygen interstitials and Zn
vacancies produced during implantation that act as acceptors.
On the other hand, other reports show a decrease in electrical resistivity after ion irradiation. For instance,
MatSunami et al [46]conducted their research using 100 keV Ne ions and concluded that the decrement of
resistivity is due to an increase in carrier density. Lyadov et al [47]reported that the low resistivity found in their
implanted ZnO lms with 30 KeV Ag ions is due to a high value of free electron concentration. Zhen et al [48]
studied the resistivity of ZnO after 5 keV H ions irradiation and concluded that its decrement should be a
consequence of the hydrogen that forms a shallow donor in the ZnO.
We consider that the enhancement of electrical resistivity values after ion irradiation (See gure 8)is related
to the irradiation process. During ion irradiation, the projectiles can deect the electrons of the atoms that form
the material. Consequently, the mean free path for electron movement gets shorter and its drift velocity is
reduced. This reduction causes a decrement in charge carrier mobility, increasing resistivity. On the other hand,
He
2+
ions produced thermal spikes during irradiation, which improved the lmscrystallinity, enhancing the
electrical resistivity of ZnO thin lms.
4. Conclusions
The present work studied the effect of
4
He
2+
ion irradiation on the optical, structural, morphological and
electrical properties of ZnO thin lms. The UVvis results revealed a decrement in the energy band gap of the
lms after irradiation. This reduction is related to structural defects, especially oxygen vacancies and zinc
interstitials that produce changes in the crystalline matrix, narrowing the optical band gap. The wurtzite-type
hexagonal structure of the ZnO is maintained after irradiation. It is noticeable that He
2+
ion irradiation favors
crystal growth, improves the crystallinity of ZnO lms and increases crystallite size as a consequence of the
reduction in strain due to thermal spikes. The results indicate that irradiation shrinks the lattice parameters,
which is related to compressive stresses due to the substitution of He
2+
ions in the lattice. The SEM images reveal
that the particles that compose the lms are nanometric in size, show spherical and ake-like structures, and are
modied by irradiation. Micrographs also show that their density, size, and shape strongly depend on the
deposition temperature. The samples also follow different patterns concerning their average particle size after
irradiation. While the average particle size of the samples prepared at lower temperatures decreased after
irradiation, the opposite occurred with the sample synthesized at the higher temperature. The electrical results
indicate that ZnO thin lms become more resistive with ion irradiation and that resistivity values could be
tailored by changing the substrate temperature during the pyrolysis process.
Acknowledgments
The authors would like to thank the technical assistance of Roberto Hernández, Diego Quiterio, Karim López,
Francisco Javier Jaimes, Mauricio Escobar and Antonio Morales.
10
Mater. Res. Express 9(2022)116403 A López-Suárez et al
Data availability statement
The data that support the ndings of this study are available upon reasonable request from the authors.
Funding
This work was supported by UNAM DGAPA-PAPIIT, grant IN101122.
Conict of interest declaration
The authors declare that they have NO afliations with or involvement in any organization or entity with any
nancial interest, or non-nancial interest in the subject matter or materials discussed in this manuscript.
ORCID iDs
Alejandra López-Suárez https://orcid.org/0000-0002-2864-7573
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