To determine the thickness of the ZnO films, a Veeco Dektak 150 profilometer was used. The equipment performs a 3 mm scan over the surface using a microtip. The scan begins 1 mm before the step incorporated in the film and ends 2 mm on the film. The measurements were taken on substrates with ZnO multilayer films, obtaining an average thickness of 1 μm.
3.2. Scanning electron microscopy
The morphological characterization of the piezoelectric film was using a JEOL JSM-7600F scanning electron microscope with a magnification of 10,000x, 20,000x and 30,000x respectively. Upon analysis of the film and its composition, a rough surface was observed, indicating strong adhesion of the piezoelectric material to the substrate. Furthermore, the uniformly rough surface observed suggests a homogeneous and consistent piezoelectric behavior throughout the device.
Nanostructured flakes have been observed in micrographs of ZnO, which not only facilitate the piezoelectric phenomenon, but also provide bulk material with a high level of mechanical strength [
41]. This mechanical strength prevents the material from fracturing or cracking when used in vibrational devices, as illustrated in
Figure 11. Moreover, an analysis of scanning electron microscope (SEM) images confirmed the presence of 250-nanometer diameter nanospheres, thereby confirming the successful production of nanostructured films.
The production of a ZnO nanostructured film represents a significant advantage in energy harvester manufacturing. The unique physical and chemical properties of ZnO nanostructures are capable of significantly enhancing energy collection efficiency [
42]. Particularly noteworthy is the discovery of 250-nanometer ZnO nanospheres in this study, which highlights the successful production of nanostructures using cost-effective synthesis and deposition techniques. This finding represents an important contribution, demonstrating the potential of practical and economical equipment in achieving the ideal form of nanostructures.
These ZnO nanospheres exhibit a high degree of porosity, resulting in a large surface area and excellent electrical conductivity, thereby increasing their energy capture capability [
43]. Moreover, their uniform size and shape allow them to effectively bind together in a nanostructured film, further enhancing their efficiency in energy collection [
44]. It was also possible to observe the high quality of the ZnO film, exhibiting homogeneity and being free of visible defects on the surface.
Furthermore, the thickness of the substrate was measured, resulting in 52.1 mm, as shown in
Figure 12. This measurement corresponds to the model used for the simulations of the energy harvesting device, providing important validation of the simulation results. These significant findings provide valuable insights for the development of future piezoelectric devices for harvesting energy.
3.3. X-ray Diffraction (XRD)
In order to confirm the presence of zinc oxide and its growth phase in the nanostructured ZnO films, X-ray diffraction was performed to obtain the materials' crystal structure. The diffraction pattern of the ZnO samples revealed the presence of wurtzite phase ZnO with preferential growth on the (101) plane, as
Figure 13 shows). Additionally, well-defined peaks at 35°, which are characteristic of ZnO in the wurtzite crystal structure [
45], were observed.
The absence of other materials in the diffraction pattern suggests that the synthesis and deposition processes of the piezoelectric films were successful and free of impurities. These findings provide valuable insights into the crystal structure and growth phase of ZnO nanostructured films, thus confirming their potential suitability for use in piezoelectric energy harvesting applications.
Furthermore, all samples demonstrated high crystallinity, indicating the quality of the crystal structure and the uniformity of crystal orientation [
45]. The annealing process applied to the films was found to be within the temperature range that promotes grain growth, which is closely related to the piezoelectric response of the material [
46]. Additionally, the grain size of the films plays a crucial role in light transmission, which is essential for the efficiency of the piezoelectric energy harvester.
However, it was observed that films subjected to a thermal treatment at 550°C over time showed detachment from the substrate, which is likely due to the mechanical stress and deformation induced by the high temperature [
47]. Therefore, it is recommended that a lower annealing temperature be used to produce suitable films for the process.
The crystal size of ZnO was theoretically calculated using equation (1) based on the (002) peak.
The method employed for calculating the size of nano crystallites (L) using XRD radiation involves the measurement of the full width at half maximum (β) of the peaks located at any 2θ angle in the pattern, given a wavelength of λ (in nm), expressed in radians. The results show a correlation between the annealing temperature and the crystallite size in ZnO samples. It was found that as the annealing temperature increases, the crystallite size in the samples also increases. Specifically, sample Z450 exhibited a crystallite size of 18.22 nm, while sample Z500 and Z550 displayed sizes of 29.10 nm and 29.36 nm, respectively. This increase in crystallite size can be attributed to the higher thermal energy present at higher annealing temperatures, which allows atoms to move more freely and promotes crystal growth [
48].
It is worth noting that the size of the crystallite can significantly affect the piezoelectric and optical properties of the material, thus having a significant impact on the efficiency of piezoelectric energy harvesters [
43]. As shown in
Figure 14, the diffractogram of the ZnO films in the (002) crystal plane exhibited a minor shift towards compression with increasing temperature. This shift was analyzed using the Stoney equation [
49], revealing a tensile shift for the Z450, Z500, and Z550 films at 2θ of 34.46, 34.54, and 34.59, respectively. These findings highlight the importance of carefully controlling annealing temperature to optimize the crystallite size and ensure efficient performance of ZnO-based piezoelectric energy harvesters.
Figure 14 shows the X-ray diffraction patterns of ZnO films on the (002) crystal plane. As the temperature increases, a small compression shift is observed, which was analyzed using the Stoney equation.
The compressive stress of the ZnO films was calculated and found to be -2.81 GPa for Z450, -2.07 GPa for Z500, and -1.85 GPa for Z550. Based on its higher intensity in the (002) crystallographic plane, the Z450 film was selected for electrical characterization to determine the power output of the piezoelectric generator.
3.4. Electrical characterization
A custom vibration system was designed and constructed to control a vibration source for research on vibration energy harvesting devices. The system employs a modified subwoofer from a commercial DVD home theater audio system as the vibration source to meet research requirements.
Figure 15a illustrates the schematic for the custom vibration system, which incorporates a commercial audio loudspeaker with a designated area for test samples mounted on the loudspeaker cone. A laboratory function generator produces the excitation signal, and a unity gain power amplifier supplies the current necessary to drive the subwoofer's low impedance.
A broadband vibrometer serves as the reference accelerometer, while an oscilloscope measures and displays the energy harvesting output signal. The selection of an 8-inch subwoofer was based on its size, robust construction, and compatibility with the intended modifications. A 3D-printed plastic plate was designed and affixed to the speaker cone using adhesive glue, creating a flat surface at the cone's center. Additionally, a unique part was printed for the energy harvester device pickup, elevating the test surface above the embedded cone area and mitigating the strong magnetic influence from the loudspeaker. The subwoofer is housed in a custom acrylic enclosure.
Figure 15b presents a photograph of the complete vibration system featuring the micromachined substrate without deposited films and offers a close-up view of the fabricated device area with piezoelectric film and seismic masses, displaying intricate construction details. The vibration amplitude of the exciter is assessed using a calibrated reference vibrometer, while the size and frequency of oscillations are regulated by a function generator configured to produce a zero-offset sine wave output. Overall, the custom vibration system delivers a controllable vibration source that is ideally suited for research on vibration energy harvesting devices.
To provide the necessary current gain for the low impedance of the subwoofer, a power amplifier was required. Specifically, the audio mono TPA3118 60w Arduino voltage amplifier model was used. This amplifier was selected due to its ability to provide the required gain and its compatibility with the experimental setup. The amplifier was mounted within the setup, as shown in
Figure 15, and was used to amplify the voltage signal in order to drive the subwoofer. The use of this amplifier allowed for precise control over the output signal and ensured that the subwoofer received the necessary amount of power to produce the desired sound.
The experiment was conducted with a total of 10 repetitions, which were deemed sufficient to obtain reliable and meaningful results [
50]. The collectors were placed within a 3D printed mold to maintain stability during the agitation process. The excitation frequency was varied from 0 to 60 Hz to identify the resonance frequency of both sets of beams experimentally, as shown in
Figure 16. The experiment revealed the existence of a piezoelectric effect, as the vibrations were observed to influence the generator.
Data collected from the experiment were processed, and a standard deviation of 0.084 was observed in the external beams, while the central beam had a standard deviation of 0.097. These values indicate that the data are relatively close to the mean and that there is little variation in the dataset [
51]. Overall, the experimental setup and results demonstrate the effectiveness of the electromagnetic shaker and provide important insights into the behavior of the fabricated collectors. During the measurement, the average maximum voltage observed for the external beams was 1.08 V, while for the central beam it was 180 mV. As depicted in
Figure 16, an increase in voltage occurred as the resonance frequency was approached, which was experimentally evaluated to be 35 Hz and 58.5 Hz for each set of beams, respectively.
This represents a 0.78% difference from the FEM simulation results for the external beams. In the case of the central beam, there was a 2.7% difference when comparing the experimental displacement with the ANSYS simulation. These results are within the 5% difference range that is commonly accepted in the literature when comparing simulated and experimental data.
Furthermore, to observe the piezoelectric response, the shaker's excitation was randomly stopped, and the beams' response was measured, obtaining the results shown in
Figure 17 for the outer beams and
Figure 18 for the central beam. The results showed that the external beams had a significant piezoelectric response, reaching an average voltage of 1.08 volts during excitation.
When the mechanical vibrations provided by the shaker were inhibited, the voltage values approached zero. Both
Figure 17 and
Figure 18 display the voltage values obtained, and it is evident that a significant voltage drop occurs when the excitation is interrupted.
The results suggest that the external beams have a higher piezoelectric response than the internal beam, indicating that they may be suitable for certain applications that require a strong piezoelectric response.
As stated above, the results demonstrated that the piezoelectric film operated correctly, as there was no energy collection when the device was left without movement. The central beam generated between 155 and 180 mV when oscillating at a frequency of 58.5 Hz, as illustrated in
Figure 18. The measurements taken suggest that the piezoelectric film on the central beam is effective at generating energy when the beam vibrates at its resonance frequency. The results are promising and indicate that the device may have practical applications in generating energy from mechanical vibrations.
On the other hand, to demonstrate the measurements taken to calculate the power generated by an energy harvesting device, the experiment involved the use of resistors of varying values ranging from 49.5 kΩ to 464 kΩ, while the devices were kept at their resonance frequency at different times. The resulting data obtained from these measurements have been presented in
Table 1.
It is worth noting that the devices were maintained at their resonance frequency throughout the mentioned experiment. This was likely done to ensure that the device was operating at its maximum efficiency, which would provide more accurate results. The central beam generated a voltage of 80 mV and recorded an average maximum power output of 16.2 nW when a resistance of 100 kΩ was used. In contrast, the outer beams produced a maximum voltage of 860 mV and a maximum average power output of 1.84 µW when a resistance of 200 kΩ was used. The behavior of power output for the central beam is shown in
Figure 17a, while the same behavior for the outer beams is presented in
Figure 17b.
The voltage measurements obtained from the central and outer beams suggest that the outer beams are more effective at generating voltage than the central beam. However, the central beam recorded a higher power output at the given resistance level. It is important to highlight that the maximum power output was achieved when the beams were vibrating at their resonance frequency.
This suggests that the device operates most efficiently at its resonant frequency and could be optimized for performance by tuning it to this frequency. Additionally, the graphs provided in
Figure 19a,b show how power output varies with changing resistance values, providing a visual representation of the experiment's findings.
In light of the gathered results from various research studies on energy harvesting by piezoelectric systems and in comparison, with the findings of this research, which employed piezoelectric materials such as Polyvinylidene Fluoride (PVDF) or Lead Zirconate Titanate (PZT),
Table 2 warrants significant attention.
One notable aspect of this energy collector's production is the omission of PZT, which eliminates the release of lead into the environment during the deposition process of the piezoelectric film. This significant change significantly diminishes the environmental impact that typically arises from the production of such devices.
Moreover, this study employs piezoelectric film thicknesses that are 50% lower than those used by other authors who achieve greater power outputs, such as those reported in references [
53] and [
52]. It is also noteworthy that up to 200% less piezoelectric material was used during the design and fabrication of the energy harvester in this study, leading to considerable savings in chemical use and creating a more environmentally conscious process in line with the objectives of the 2030 Agenda.
In addition, the set of external beams has been found to generate a higher amount of electrical power than other recent works in the field of energy harvesting, including those carried out by the University of Applied Sciences Zittau Görlitz in Germany [
59] and the Department of Electrical and Electronic Engineering at Imperial College London in England [
56].
Further analysis reveals that the central beam generates 50% more power than reported in 2022 [
58] and is capable of producing up to three times more voltage when subjected to vibrations at its resonance frequency. These findings have significant implications for manufacturing costs and potential consumer base and provide an opportunity for greater energy harvesting in the coming decade.