Home Physical Sciences One-pot synthesis of a network of Mn2O3–MnO2–poly(m-methylaniline) composite nanorods on a polypyrrole film presents a promising and efficient optoelectronic and solar cell device
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One-pot synthesis of a network of Mn2O3–MnO2–poly(m-methylaniline) composite nanorods on a polypyrrole film presents a promising and efficient optoelectronic and solar cell device

  • Eman Aldosari , Mohamed Rabia EMAIL logo , Hassan A. Ewais and Kenan Song
Published/Copyright: May 30, 2024
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Open Chemistry
From the journal Open Chemistry Volume 22 Issue 1

Abstract

A one-pot synthesis approach was employed to create a composite nanorod structure (Mn2O3–MnO2–poly(m-methylaniline) or Mn2O3–MnO2–PmMA) on a polypyrrole (Ppy) film. Optoelectronic and solar cell thin film devices were constructed using n- and p-type layers of Mn2O3–MnO2–PmMA and Ppy, respectively. The optical characteristics of the n-layer, coupled with the morphological behavior of its nanorods, enhance optical absorbance efficiency, reducing the bandgap value to 2.48 eV. The behavior of the optoelectronic device is chiefly determined by the significantly higher current density (J ph) value of 0.017 mA/cm2 compared to the dark current density (J o) value of 0.002 mA/cm2. Additionally, the linear dynamic range is 85 dB, and the noise ratio is 12%. The optimized values for the photosensitivity (R) and detectivity (D) at 340 nm are 0.22 mA W−1 and 0.47 × 10⁸ Jones, respectively. Even at 540 nm, these values decrease to 0.08 and 0.2 × 10⁸ Jones, respectively. For solar cell behavior, the short-circuit current (J SC) and open-circuit voltage (V OC) at 540 nm are determined, yielding values of 0.001 mA/cm2 and 0.98 V, respectively. The outstanding performance of this optoelectronic device, coupled with its solar cell behavior, positions the thin film material for a dual role in various industrial applications.

Keywords: Mn2O3–MnO2 ; poly(m-methylaniline); polypyrrole; optoelectronic; solar cell; nanocomposite

1 Introduction

Presently, fossil fuels play a vital role in meeting the global demand for electrical energy. However, it is becoming increasingly evident that the world’s growing need for electricity is on the verge of surpassing the current output capacity of fossil fuels [1,2]. This impending shortfall raises concerns about the sustainability and adequacy of relying solely on fossil fuels to meet the growing energy requirements. However, the produced gases have far-reaching consequences, affecting both the climate and human health. The implications of these pollutants include adverse impacts on air quality, the exacerbation of climate change, and potential health hazards for human populations [3,4].

The development of new and sustainable energy sources stands out as a pivotal solution to address the pressing issues associated with fossil fuel dependence. This pursuit is driven not only by the need to meet the escalating demand for electricity but also by a broader commitment to mitigate the adverse environmental and health effects associated with conventional energy production. Investing in innovative and eco-friendly energy alternatives provides an opportunity to transition toward a more sustainable and resilient energy landscape called renewable energy.

Conversely, solar cells have gained increasing attention as a prominent form of renewable energy due to their environmentally friendly nature, cost-effectiveness, potent energy conversion capabilities, and notable performance. In recent times, semiconducting polymeric nanostructures have emerged as a focal point in photocatalytic processes, primarily due to their adjustable bandgap and distinctive optical characteristics. This has led to a surge in interest in studying the potential applications of these nanostructures. Among conducting polymers, polyaniline and its derivatives stand out as exceptional because both oxidation and protonation exert reversible control over its electronic structure and electrical characteristics [5,6]. This unique feature positions polyaniline as a material of considerable interest for potential applications, leveraging a wide spectrum of associated electrical and optical properties. Moreover, the material’s outstanding environmental and thermal stability has contributed to its growing prominence. The ease of synthesis and remarkable mechanical strength further enhance its appeal, making polyaniline a versatile candidate for various applications.

Diverse materials have been meticulously developed and applied in solar energy applications, showcasing a broad range of alternatives for improving the efficiency and performance of solar cells. Among these materials, manganese-based oxides, vanadium-based materials, cobalt-based materials, molybdenum-based materials, and polymers and organic compounds are particularly important in the advancement of solar energy technology [7,8]. Previous research has investigated a variety of materials for optoelectronic applications, including metal oxides, nitrides, and carbon-based materials such as CuO nanowires [9], graphene/GaN [10], TiN/TiO2 [11], PbI2-5%Ag [12], and Ti3C2 MXenes [13], or organic materials such as graphene/P3HT [14], PBBTPD:Tri-PC61BM [15], and ZnO/P3HT/PEDOT:PSS [16]. In these previous studies, the reported photosensitivity (R) values were generally 0.1 mA W−1 or even smaller, reaching as low as 10⁻⁴ mA W−1. Despite utilizing complex techniques and high-cost materials, the achieved sensitivity remained limited.

The synthesis of pristine polyaniline is not only straightforward but also lends itself to the production of materials with good electrical and optical properties. These properties, together with the material’s robust mechanical strength, make it a compelling choice for a variety of applications [17,18]. The material’s remarkable stability in different environmental conditions adds to its attractiveness, further fueling the interest in exploring its potential applications in various fields. Researchers have been investigating the incorporation of polyaniline composites into light sensors, like the polyaniline/cellulose acetate composite with a bandgap of 4.02 eV, and the polyvinyl alcohol/polyaniline composite with a bandgap of 2.71 eV. Despite these efforts, the light-sensing capacities of these materials remain relatively weak, indicating the need for further improvements to enhance their performance in detecting visible light [19,20]. The use of polyaniline composites in light sensors offers promising prospects due to their unique characteristics, including adjustable bandgaps and conductivity, making them suitable for optoelectronic applications. However, the main challenges involve optimizing these materials to effectively sense visible light. One method to improve the light-sensing capacities of polyaniline composites involves refining their structure to better capture and respond to visible light wavelengths. This might involve adjusting the composition ratios of polyaniline and its substrate materials, as well as exploring new composite combinations to achieve better optical properties. Moreover, enhancing the composite matrix by incorporating additional light-absorbing or sensitizing agents could boost its light-sensing capacities. These additives, such as organic dyes or plasmonic nanoparticles, can extend the composite’s absorption range into the visible spectrum and improve its photoconductivity. Another strategy for improvement is optimizing the fabrication process to ensure the uniform dispersion and alignment of composite components, thereby reducing charge carrier recombination and improving overall light sensitivity.

Herein, our current research focuses on the development of a highly sensitive and optically efficient Mn2O3–MnO2–PmMA/polypyrrole (Ppy) optoelectronic device that includes a solar cell component capable of detecting light in both the ultraviolet (UV) and visible (Vis) regions. This novel device undergoes testing under diverse light conditions, with calculated values for linear dynamic range (LDR), D, R, J SC, V OC, and noise ratio. These parameters serve as indicators of the sensitivity and efficiency of our promising thin film device.

The notable advantages of our device include its excellent sensitivity, easy preparation, and cost-effectiveness, making it well-suited for mass production and economic applications in the industrial sector. This breakthrough paves the way for the integration of our optoelectronic device into various industrial applications, offering a viable and practical solution with considerable economic benefits.

2 Experimental section

2.1 Materials

Merck in Germany supplied m-methylaniline and hydrochloric acid (HCl), while PioChem in Egypt provided KMnO4 and K2S2O8. Sodium hydroxide was obtained from El Naser Chemical Company in Egypt. Additionally, Sigma Aldrich in the USA supplied dimethylformamide and pyrrole.

X-ray powder diffraction (XRD) analysis was conducted using the Bruker D8 XRD instrument, while Fourier-transform infrared spectroscopy (FTIR) analysis utilized the Jasco 340 instrument. Additionally, transmission electron microscopy (TEM) and scanning electron microscopy (SEM) analyses were carried out utilizing the Joel and Hitachi models. Furthermore, optical UV analysis was performed using the PerkinElmer instrument. These distinct instruments were employed for their specialized capabilities in their respective analytical techniques, ensuring comprehensive and precise characterization of the materials under investigation.

2.2 Fabrication of Mn2O3–MnO2–PmMA/Ppy thin film optoelectronic and solar cell device

The synthesis of the Ppy polymer (p-layer) closely follows the methodology established in our previous studies. This involves dissolving the pyrrole monomer (0.06 M) in an acidic medium (0.5 M HCl) and introducing the oxidant (0.15 M K2S2O8) to initiate Ppy formation, resulting in a dark green precipitate [21,22]. Subsequently, the polymer undergoes purification for subsequent analysis.

The Mn2O3–MnO2–PmMA (n-layer) is produced in a similar procedure, albeit with some variations. Here, a stronger oxidizing agent, 0.12 M KMnO4, is used to initiate the oxidation of m-methylaniline. This leads to the generation of free radicals that combine to form PmMA. Notably, KMnO4 serves as an additional source of Mn2O3–MnO2, which becomes integrated into the polymer network. This reaction takes place in a 0.6 M HCl environment, resulting in the creation of a dark green Mn2O3–MnO2–PmMA nanocomposite thin film. Subsequent to the fabrication of these layers, these layers are treated with distilled water and dried at 60°C. Following this process, they are prepared for further characterization procedures.

2.3 Optoelectronic electrical testing

Following the construction of the Mn2O3–MnO2–PmMA/Ppy optoelectronic device, the solar cell behavior is investigated. Both sides of the device undergo coating with Ag-Paste. Electrical testing is then conducted using the CHI608E (USA) with a scanning rate of 100 mV/s, involving the examination of the current–potential relationship under various light conditions, including monochromatic wavelength light. Electrical measurements are conducted under standard room temperature conditions within a voltage range spanning from −2.0 to +2.0 V. During testing, we record both the photogenerated current (J ph) and dark current (J o) values. These measurements serve as the foundation for deriving further sensitivity and efficiency parameters. Using a metal halide lamp, specifically the vacuum lamp with a power rating of 400 W, in conjunction with optical filters, allows precise control over the energy of light transmitted through the system.

The LDR, D, R, J SC, V OC, and noise ratio are among the key parameters determined from the obtained data. These metrics collectively offer a comprehensive understanding of the solar cell’s performance and sensitivity under different illumination conditions.

So, this thorough evaluation provides insights into the device’s responsiveness to light, its ability to generate and sustain current under illuminated conditions, and its overall efficiency as a solar cell. The inclusion of monochromatic wavelength light in the testing process ensures a detailed analysis of the device’s behavior across specific wavelengths, contributing to a comprehensive understanding of its optoelectronic capabilities.

Efficiency estimation hinges on the utilization of noise ratio parameters, which are contingent upon both the dark current (J o) and photogenerated current (J ph) factors (referenced as equation (1)). Subsequently, the LDR characterizes the range of input irradiance levels, depicted in decibels (dB), within which the responsivity remains consistent (as illustrated in equation (2)). Similarly, the R values are derived estimates, factoring in the intensity of light (P) (as per equation (3)). Furthermore, the estimation of D incorporates considerations of electron charge (e) and the area of the photodetector, which is standardized at 1.0 cm2 (delineated in equation (4)). These equations and their accompanying explanations illuminate the intricate interplay between various parameters, facilitating a deeper understanding of the efficiency estimation process.

(1) Noise ratio = J o J ph × 100 ,

(2) LDR = 20 log J ph J o ,

(3) R = J ph − J o P ,

(4) D = R S / 2 e J o .

3 Results and discussion

3.1 Analyses

The chemical structure of PmMA is confirmed through the analysis of the FT-IR spectrum, as illustrated in Figure 1. The spectrum exhibits characteristic bands indicative of various functional groups within the polymer. Specifically, the N–H and C–N positions are discerned at 3,410 and 1,370 cm⁻¹, respectively. The presence of the substituent CH3-group is highlighted by the band at 2,928 cm⁻¹, whereas the C═C vibrations of the benzenoid rings appear as bands at 1,498 and 1,529 cm⁻¹. Furthermore, the vibration associated with the quinoid ring is observed at 1,640 cm⁻¹. The C–H in/out-plane vibrations contribute bands at 1,104 and 586 cm⁻¹, respectively.

Figure 1 Construction of Mn2O3–MnO2–PmMA nanocomposite by (a) FTIR and (b) XRD.
Figure 1

Construction of Mn2O3–MnO2–PmMA nanocomposite by (a) FTIR and (b) XRD.

The functional groups in PmMA and Mn2O3–MnO2–PmMA exhibit similarities, indicating the retention of key molecular components during the nanocomposite formation. However, the shifts in band positions suggest that the incorporation of Mn2O3–MnO2 introduces alterations in the electronic structure of the nanocomposite. The heightened intensity of the N–H peak, distinctive to the nanocomposite, signifies an augmentation in particle mass throughout its volume. This increase suggests a corresponding enhancement in the crystallinity behavior of the composite when compared to the pure polymer.

The shifts, whether toward the blue or red end of the spectrum, offer insights into the interactions between the inorganic and polymeric components. These shifts are indicative of changes in the electron distribution within the polymer matrix, influenced by the presence of Mn2O3–MnO2. A comprehensive summary of these functional groups for both PmMA and Mn2O3–MnO2–PmMA is presented in Table 1.

Table 1

Positions of the detected functional groups for both PmMA and Mn2O3–MnO2–PmMA

Band (cm−1) Group
Mn2O3–MnO2–PmMA PmMA
3,392 3,410 N–H [23,24]
1,616 1,640 C═C quinone form
1,498 1,529 C═C normal benzene form [25,26,27]
1,404 1,370 C–N [28]
1,107 1,104 C–H [29]
677 586 Para disubstituted ring [30]

In Figure 1(b), the XRD of the Mn2O3–MnO2–PmMA nanocomposite is juxtaposed with that of pure PmMA. The pure PmMA reveals a non-crystalline nature, evident from the absence of distinct peaks that typify crystalline substances.

Conversely, the XRD pattern of the Mn2O3–MnO2–PmMA nanocomposite demonstrates increased crystallinity, revealed by the presence of multiple sharp peaks. These peaks correspond to the existence of βMnO2, an inorganic component, or residual Mn2O3 within the polymer matrix. Specifically, the XRD peaks associated with βMnO2 are positioned at distinct angles, such as 18.1°, 28.2°, 37.2°, 43.1°, 46.9°, 62.7°, and 68.3°, representing various growth orientations. These angles are consistent with the JCPDS 24-0735 reference database [31]. Faint indications XRD peaks of Mn2O3 are identifiable at 33.6° and 55.5°. Predominantly, the nanocomposite harbors βMnO2 as the principal inorganic constituent, interweaving within the polymer matrix and augmenting the composite’s structural composition.

By employing equation (5) [32,33], it is possible to approximate the dimensions of the crystalline domains. For the Mn2O3–MnO2–PmMA nanocomposite, this calculation yields a crystalline size of 45 nm, offering valuable information about the scale of the crystals within the composite substance.

(5) D = 0.9 λ / W cos θ .

XPS is used to verify the elemental composition and oxidation states intrinsic to the synthesized Mn2O3–MnO2–PmMA nanocomposite. This analytical tool serves to investigate the inorganic architecture of Mn compounds and their interactions within the polymer framework, PmMA. Figure 2(a) depicts the elemental makeup by showing the binding energy for each component. In Figure 2(d)–(f), the pristine polymer, PmMA, along with constituent elements C, N, and intercalated Cl ions are identified at 285.3, 400.4, and 199.2 eV, respectively. The spectra for Mn, namely 2p3/2 and 2p1/2, occupy positions at (641.3 and 645.4 eV) and (653 and 654.4 eV), delineating Mn3+ and Mn4+ oxidation states [34]. This unequivocally validates the coexistence of Mn2O3 and MnO2 configurations. Furthermore, the O 1s spectrum registers at 533 eV (Figure 2(c)), serving as an additional testament to the compositional intricacies and structural attributes of the nanocomposite.

Figure 2 XPS analyses of (a) Mn2O3–MnO2–PmMA, (b) Mn, (c) O, (d) C, (e) N, and (f) Cl.
Figure 2

XPS analyses of (a) Mn2O3–MnO2–PmMA, (b) Mn, (c) O, (d) C, (e) N, and (f) Cl.

The Mn2O3–MnO2–PmMA nanocomposite exhibits distinct and notable morphological features, prominently showcasing a remarkable nanorod structure that correlates with its precisely defined crystalline properties. This specific structural attribute arises from the incorporation of Mn2O3–MnO2 into the polymer matrix, resulting in a nanocomposite that stands out for its well-defined crystalline nature, as depicted in Figure 3(b).

Figure 3 (a) Pure PmMA SEM. The Mn2O3–MnO2–PmMA nanocomposite topography and geometric behavior were estimated through the (b) SEM, (c) TEM, and (d) cross-sectional modeling.
Figure 3

(a) Pure PmMA SEM. The Mn2O3–MnO2–PmMA nanocomposite topography and geometric behavior were estimated through the (b) SEM, (c) TEM, and (d) cross-sectional modeling.

These nanorods, which constitute the nanocomposite’s structure, exhibit varying lengths, spanning from 150 to 1.1 µm, and widths that range between 80 and 300 nm. What distinguishes these nanorods even further is their distinct geometric arrangement, with shapes ranging from hexagonal to pentagonal. This geometric configuration serves as a fundamental factor contributing to the nanocomposite’s exceptional optical performance. In sharp contrast, the pure PmMA material lacks any discernible geometric arrangement. Instead, it appears as a collection of irregular granules characterized by porous structures that aggregate together, as evident in Figure 3(a).

Further insights into the Mn2O3–MnO2–PmMA nanocomposite’s structure are provided by the TEM analysis in Figure 3(c), which effectively captures the rod-like geometric nature of the material. A specific rod with dimensions approximately 200 nm in length and 80 nm in width is depicted in this microscopic evaluation. To enhance the verification of this geometric behavior, Figure 3(d) offers a glimpse into the cross-sectional attributes and surface roughness of the fabricated Mn2O3–MnO2–PmMA nanorod. This figure notably reinforces the confirmation of the hexagonal shape, aided by the presence of minute particles enveloping the rod’s surface. This phenomenon is a consequence of the polymer deposition process. The composition of this potentially effective Mn2O3–MnO2–PmMA nanocomposite includes percentages of manganese, oxygen, nitrogen, carbon, and chlorine, estimated at 1.66, 14.02, 8.64, 68.19, and 7.49%, respectively.

So, the morphological analysis of the Mn2O3–MnO2–PmMA nanocomposite unveils a striking nanorod structure with distinct geometric shapes, ranging from hexagonal to pentagonal. This arrangement is in stark contrast to the irregular granular structure observed in pure PmMA. The TEM analysis further substantiates the rod-like nature of the nanocomposite, while the cross-sectional view reinforces the hexagonal shape and the surface features resulting from the polymer deposition process.

The optical characteristics of the Mn2O3–MnO2–PmMA composite nanorods and pure PmMA are assessed through absorbance measurements, as depicted in Figure 4(a). A discernible contrast in optical behavior is evident between these two materials, with the incorporation of Mn2O3–MnO2 inorganic constituents within the polymer filler notably enhancing the optical response. This enhancement is particularly pronounced, extending the absorbance spectrum to around 600 nm, which falls within the middle of the Vis range. In contrast, the pure PmMA exhibits an absorbance spectrum limited to 400 nm, confined to the UV range, with a minor band appearing in the Vis range. The significant integration of Mn2O3–MnO2 with the pure PmMA polymer facilitates pronounced electron transitions between these inorganic materials and the polymer. This integration results in the formation of a singular material exhibiting increased photon absorbance, consequently inducing electron transitions under these photon absorbance conditions. The synergistic effect arising from the combination of these inorganic materials with the pure polymer fosters compatibility in the electron transition process, enhancing overall material performance.

Figure 4 (a) Optical absorbance and (b) the Tauc equation relation for bandgap evaluation for PmMA and Mn2O3–MnO2–PmMA composite nanorods.
Figure 4

(a) Optical absorbance and (b) the Tauc equation relation for bandgap evaluation for PmMA and Mn2O3–MnO2–PmMA composite nanorods.

In both the pristine polymer and the nanocomposite, this behavior is attributed to the pi–pi* transition of electrons upon exposure to UV or Vis light. Accumulation of these excited electrons occurs at the polymer surface. However, in the nanocomposite, these electrons extend their reach to interact with the incorporated inorganic Mn2O3–MnO2 filler. The influence of these inorganic constituents becomes evident in the assessment of the material’s bandgap through the Tauc equation (equation (6)) [35,36]. This evaluation reveals a reduction in the bandgap from 2.94 to 2.48 eV, underscoring the impact of the inorganic material integration into the polymer matrix

(6) α h ν = A ( h ν − E g ) 1 / 2 .

3.2 Electrical study

The investigation of the electrical characteristics of Mn2O3–MnO2–PmMA/Ppy optoelectronic and solar cell devices is undertaken. In this assessment, the Mn2O3–MnO2–PmMA component serves as the n-type material, while Ppy functions as the p-type material. The workstation CHI608E is employed to conduct the evaluation by analyzing the current density and potential relationship at −2.0 to +2.0 V.

The testing protocol involves the use of a metal halide (light source), generating white light for illumination. The light emitted can be finely controlled across various wavelengths using optical filters, enabling the provision of monochromatic lights with distinct energies. During this assessment, the resulting current densities are meticulously examined to derive important parameters such as R (responsivity), LDR and D (detectivity).

In particular, the produced current densities have a great role in the determination of R, LDR, and D, providing insights into the performance of the Mn2O3–MnO2–PmMA/Ppy thin film devices under different conditions. R is a reflection of the device’s behavior to convert incident light into an electrical signal and is crucial in understanding its efficiency. LDR reveals the sensitivity of the device to light variations. D quantifies the ability of the device to detect low optical signals and is an essential parameter for assessing its practical utility.

Additionally, key metrics such as J SC and V OC are integral to understanding the overall behavior of the Mn2O3–MnO2–PmMA/Ppy thin film devices. J SC denotes the maximum current generated under short-circuit conditions, representing the device’s ability to collect charge carriers efficiently. V OC, the voltage across the device terminals in the absence of current flow, provides insights into the device’s photogenerated potential.

This comprehensive evaluation aims to unravel the intricate electrical behavior of the Mn2O3–MnO2–PmMA/Ppy thin film devices under various illuminations, facilitating the way for a deeper illustration of their optoelectronic and solar cell functionalities. The systematic analysis of these parameters contributes to the elucidation of the device’s performance characteristics, facilitating advancements in the development of efficient and responsive optoelectronic technologies.

The electrical characteristics of Mn2O3–MnO2–PmMA/Ppy optoelectronic and solar cell devices are thoroughly explored under both dark and illuminated conditions, with the evaluation focused on the generated J o (dark current) and J ph (photocurrent) values (Figure 5(a)). The substantial increase in the J ph value compared to J o confirms the remarkable responsivity of this material to light, attributed to the efficient generation of hot electrons during electron–hole pair formation within the n-layer, Mn2O3–MnO2–PmMA. Meanwhile, the holes readily transfer to the Ppy layer (p-type), resulting in the production of J ph values (0.017 mA cm⁻²), significantly higher than the J o value of 0.002 mA cm⁻². This substantial improvement underscores the material’s enhanced responsiveness to light. Figure 5(b) depicts the electrical characteristics of the fabricated PmMA polymer. The constrained J ph and J o values, measured at −0.003 and −0.001 mA/cm2, respectively, highlight the restricted electrical performance of this pristine polymer compared to the promising composite comprising Mn2O3–MnO2–PmMA.

Figure 5 Electrical characteristics of (a) Mn2O3–MnO2–PmMA/Ppy optoelectronic and solar cell device under dark and light and (b) of the pristine PmMA polymer.
Figure 5

Electrical characteristics of (a) Mn2O3–MnO2–PmMA/Ppy optoelectronic and solar cell device under dark and light and (b) of the pristine PmMA polymer.

The LDR is then calculated as 85D, a promising value indicating the high sensitivity of the device to changes in light conditions. Additionally, the noise ratio (J o/J ph) is found to be a minimal 12%, suggesting negligible interference and a high signal-to-noise ratio, further enhancing the device’s reliability.

Furthermore, the key parameters J SC and V OC are determined, yielding values of 0.001 mA cm⁻² and 0.98 V, respectively. While the J SC value is considered satisfactory, the V OC value is particularly promising. The substantial open-circuit voltage indicates the device’s capability to maintain a high voltage across its terminals even when no current is flowing, which is crucial for efficient power conversion in solar cells. This promising V OC value suggests the potential of the Mn2O3–MnO2–PmMA/Ppy thin film device for effective solar energy conversion.

So, the comprehensive evaluation of the electrical behavior of these optoelectronic and solar cell devices reveals their exceptional performance under both dark and illuminated conditions. The increased photocurrent, coupled with favorable LDR and noise ratio values, signifies the material’s great potential for light-sensing applications. The calculated J SC and V OC values further underscore the promising attributes of the device, positioning it as a viable candidate for efficient solar energy harvesting.

The Mn2O3–MnO2–PmMA/Ppy thin film optoelectronic device’s response to controlled monochromatic wavelengths, achieved through optical filters at 340, 440, 540, and 730 nm, is shown in Figure 6(a) and (b). The device has a remarkable sensitivity to UV light, evidenced by the optimal J ph value of −0.021 mA cm⁻² at −2.0 V. This exceptional behavior aligns with the optical absorbance curve depicted in Figure 4(a), confirming the device’s heightened responsiveness in the UV region. The high energy of UV light facilitates the efficiency of electron collection to the conducting band, generating free electrons capable of surface movement, ultimately resulting in the observed J ph value. The calculated energy for photons with a wavelength of 340 nm, based on the equation (E = hv), is 3.8 eV – an energy surpassing the bandgap value of 2.48 eV (Figure 4(b)).

Figure 6 Electrical characteristics of Mn2O3–MnO2–PmMA/Ppy optoelectronic and solar cell devices under various monochromatic light through (a) current density–potential relationship and (b) the J ph values at −2.0 V.
Figure 6

Electrical characteristics of Mn2O3–MnO2–PmMA/Ppy optoelectronic and solar cell devices under various monochromatic light through (a) current density–potential relationship and (b) the J ph values at −2.0 V.

Furthermore, the optoelectronic device has a response in the Vis region, yielding a J ph value of −0.009 mA cm⁻² at −2.0 V. This response is attributed to the behavior of the device in the Vis region, where the energy of photons is 2.8 eV, surpassing the bandgap value (Figure 4(b)). Notably, the response is particularly evident for photons at 540 nm (Vis region), with a generated J ph of −0.007 mA/cm² at −2.0 V.

As the energy of photons decreases to 1.8 eV at 730 nm, falling below the bandgap value of 2.48 eV, the optical region encounters limitations. In this scenario, the reduced photon energy is insufficient for facilitating the transfer of hot electrons. Consequently, the J ph value closely approximates the J o value observed in the dark, indicating that the optoelectronic device is unable to operate effectively within this specific optical region (−0.005 mA/cm2). The inadequacy of photon energy to induce the transfer of hot electrons underscores the device’s dependency on sufficient energy levels for its functionality. The optical limitations in this spectral range impede the generation of photocurrent, emphasizing the critical role of matching photon energy to the bandgap for the efficient operation of the Mn2O3–MnO2–PmMA/Ppy thin film optoelectronic device. This understanding of the device’s response across different optical regions is crucial for optimizing its performance and guiding its application in areas where specific energy levels are requisite for effective optoelectronic processes.

The assessment of the efficiency of the Mn2O3–MnO2–PmMA/Ppy optoelectronic and solar cells encompasses a comprehensive exploration under diverse monochromatic wavelengths, unveiling the distinct sensitivities of this thin film. The parameters R and D are crucial in this evaluation, determined by equations (3) and (4), respectively [37]. These equations gauge the thin film devices’ performance in converting photons into detectable hot electrons. Figure 7(a) and (b) show the variation of R and D values across different wavelengths.

Figure 7 Efficiency performance of Mn2O3–MnO2–PmMA/Ppy optoelectronic and solar cell devices under various monochromatic photons by (a) R and (b) D values.
Figure 7

Efficiency performance of Mn2O3–MnO2–PmMA/Ppy optoelectronic and solar cell devices under various monochromatic photons by (a) R and (b) D values.

The analysis reveals that the optimal R and D values at 340 nm, attaining 0.22 mA W−1 and 0.47 × 10⁸ Jones, respectively. Even at 540 nm, where these values decrease to 0.08 and 0.2 × 10⁸ Jones, they remain relatively high, indicating robust photon conversion to hot electrons. This versatility in response to various optical regions positions the thin film device as a promising candidate for optoelectrical applications in the industrial sector, particularly in light sensing.

Furthermore, this opens up possibilities for the synthesis of thin-film solar cells utilizing the thin-film technique. The utilization of two layers of polymer materials in the fabrication process enhances cost-effectiveness. The notable performance of the device in converting photons to hot electrons underscores its potential for thin-film solar cell applications, contributing to the advancement of economical and efficient photovoltaic technologies.

In comparison with previous studies, the outcomes of this investigation, detailed in Table 2, underscore the favorable behavior of the Mn2O3–MnO2–PmMA/Ppy thin film in optoelectronic applications. The robust R and D values, coupled with the device’s response across varied optical regions, reinforce its potential for industrial implementation and highlight its superiority in comparison to alternative studies.

Table 2

Evaluated efficiency of the fabricated Mn2O3–MnO2–PmMA/Ppy thin film optoelectronic and solar cell device through the R-value calculation

Structure Wavelength (nm) Bais (V) R (mA W−1)
Ti3C2 MXenes [13] 405 5 0.07
ZnO/P3HT/PEDOT:PSS [16] 365 2 0.1
PBBTPD: Tri-PC61BM [15] 350 5 10−4
PbI2-5%Ag [12] 532 6 NA
TiN/TiO2 [11] 550 5 —
CuO nanowires [9] 390 5 —
GaN-graphene [10] 365 7 0.003
Graphene-PbI2 [38] 550 2 NA
P3HT [14] 325 1 NA
ZnO/RGO [39] 350 5 1.3 × 10−3
Se/TiO2[40] 450 1 5 × 10−3
GO/Cu2O [41] 300 2 0.5 × 10−3
ZnO-CuO [42] 405 1 3 × 10−3
ZnO/Cu2O [43] 350 2 4 × 10−3
TiO2-PANI [44] 320 0 3 × 10−3
CuO/Si [45] 405 0.2 0.003
PC71BM [46] 300 2 0.005
Mn2O3–MnO2–PmMA/Ppy optoelectronic (this work) 340 2 0.22

In conclusion, this study not only elucidates the efficient performance of the Mn2O3–MnO2–PmMA/Ppy thin film in optoelectronic and solar cell applications but also positions it as a promising and cost-effective candidate for industrial utilization. The findings have great insights into the thin film’s behavior across different wavelengths, paving the way for achieving optoelectronics and thin-film solar cell technologies.

4 Conclusions

Utilizing a one-pot synthesis method, a composite nanorod structure consisting of Mn2O3–MnO2–PmMA (n-layer) on a Ppy film (p-layer) was created and tested electrically as optoelectronic and solar cell thin film devices. The optical features of the n-layer, combined with the nanorods’ morphological behavior, enhance optical absorbance efficiency, resulting in a reduced bandgap value of 2.48 eV. The n-type Mn2O3–MnO2–PmMA composite is evaluated with a crystalline size of 45 nm. These nanorods, which constitute the nanocomposite’s structure, exhibit varying lengths, spanning from 150 to 1.1 µm, and widths that range between 80 and 300 nm. The primary determinant of the optoelectronic device’s performance is the notably higher photocurrent density (J ph) value of 0.017 mA/cm2 in comparison to the J o of 0.002 mA/cm2. Furthermore, the LDR is 85%, and the noise ratio is 12%. The optimized values for photosensitivity (R) and detectivity (D) at 340 nm are achieved at 0.22 mA W−1 and 0.47 × 108 Jones, correspondingly. Even at 540 nm, these values decrease to 0.08 and 0.2 × 108 Jones, respectively. Regarding solar cell behavior, the J SC and V OC at 540 nm are determined, yielding values of 0.001 mA/cm2 and 0.98 V, respectively. The exceptional performance of this optoelectronic device, along with its solar cell characteristics, positions the thin film material for a dual role in various industrial applications.

Acknowledgments

Researchers Supporting Program Number (RSPD2024R845), King Saud University, Riyadh, Saudi Arabia.

  1. Funding information: Researchers Supporting Program Number (RSPD2024R845), King Saud University, Riyadh, Saudi Arabia.

  2. Author contributions: Mohamed Rabia: Experimental, writing, and analysis; Eman Aldosari: Writing, analysis, and Funding; Hassan A. Ewais and Kenan Song: Supervision and revising.

  3. Conflict of interest: Authors state no conflict of interest.

  4. Ethical approval: The conducted research is not related to either human or animal use.

  5. Data availability statement: The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

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Received: 2024-03-01
Revised: 2024-04-11
Accepted: 2024-04-29
Published Online: 2024-05-30

© 2024 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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https://doi.org/10.1515/chem-2024-0039
Keywords for this article
Mn2O3–MnO2; poly(m-methylaniline); polypyrrole; optoelectronic; solar cell; nanocomposite
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  153. Integrative in silico evaluation of the antiviral potential of terpenoids and its metal complexes derived from Homalomena aromatica based on main protease of SARS-CoV-2
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  155. Simultaneous extraction and quantification of hydrophilic and lipophilic antioxidants in Solanum lycopersicum L. varieties marketed in Saudi Arabia
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