A facile and green synthesis of superparamagnetic Fe3O4@PANI nanocomposite with a core–shell structure to increase of triplet state population and efficiency of the solar cells

doi:10.1016/j.jece.2020.104942

Journal of Environmental Chemical Engineering

Volume 9, Issue 1, February 2021, 104942

https://doi.org/10.1016/j.jece.2020.104942 Get rights and content

Highlights

•
A new synthesis of novel nanocomposite of superparamagnetic Fe3O4@PANI.
•
Fabrication of novel solar cell by Fe3O4@PANI as an active layer for first time.
•
Preparation of nanocomposite and cell is facile, green and efficient and low-cost.
•
Presentation of various mechanisms for Fe3O4 effect to increase triplet state.

Abstract

The superparamagnetic nanocomposite of Fe₃O₄@PANI by using solid-state (solvent-free) in-situ polymerization method is synthesized, characterized, and designed for application in polymer solar cells (PSCs). The structural, optical, electrochemical, morphological, and photovoltaic properties of Fe₃O₄@PANI are investigated. The results indicate that the Fe₃O₄ @PANI with a core-shell structure is synthesized successfully. The magnetic properties of Fe₃O₄@PANI exhibit superparamagnetic property with a saturation magnetization of 44.09 emu/g. Cyclic voltammetry measurements are conducted to ascertain the position of both the HOMO (−5.26 eV) and LUMO (−3.65 eV) levels, and the chemical band gap is found in the range 1.61 eV. The maximum power conversion efficiency (PCE) of the PSCs based on FTO_│TiO_2│PANI@Fe₃O_4│Al system reaches 1.53% with an open circuit voltage (V_oc) of 0.46 V, a short circuit current density (J_sc) of 4.24 mA/cm², and a fill factor (FF) of 0.47 under AM 1.5 G (60 mW/cm²) illumination. In the following, the role of superparamagnetic nanoparticles of Fe₃O₄ in increasing solar cell efficiency is studied. In this structure, the magnetic field of Fe₃O₄ increases the population of triplet state in PANI and subsequently cell efficiency. Both active layer synthesis and cell construction are green, simple, cheap, stable, and have relatively high yields. It is concluded that such cells offer a promising new approach to commerce the new solid-state polymer solar cells.

Graphical Abstract

Introduction

One of the most interesting research topics is intrinsically conductive polymers (ICPs), due to special characteristic and countless application [1], [2]. These groups of polymers are intrinsically conductive due to a conjugated system electron system in their structures [3]. Polyethyne was the first discovered ICP by Shirakawa, et al. [4], [5]. Following studies on ICPs, other polymers such as polyaniline (PANI) and their derivatives, polythiophene (PT), polypyrrole (PPY) have been synthesized and introduced a new group of conducting polymers [6], [7], [8], [9]. PANI is a very popular conducting polymer because of its easy synthesis, low-cost monomer, high stability, its adjustable characteristics comparing other conducting polymers and its countless usage in different industries is interesting [10], [11], [12], [13]. The electronic industry is one of the industries in which PANI has many applications in making solar cells. [14], [15], [16], [17]. One type of solar cell is polymeric solar cell (PCE) which according to the photovoltaic process in its active layer the absorbed sunlight was converted into electric energy [18], [19], [20]. The output of electric energy in these materials is very important [21]. Recently, reported molecular design schemes have shown to the generation of two triplets from alone singlet state (singlet fission) as a promising trend for the generation of multi-excitons in organic systems [22]. In other words, it seems that characteristics of electric conduction which is suitable for PANI can have a very important role in the output of the producing electric energy in these system [23], [24]. Although PCEs have low output rather than other silicon solar cells, scientists believe that making these solar cells in a bigger dimension and low expense can be a reason that we ignore their low efficiency [25], [26], [27]. The basis of the work of solar cells; the light exposure to a P-N junction in the particular case and the production of electron-hole pairs which are separated by the potential barrier, creating a voltage that drives a current through an external circuit [28], [29], [30]. Excitons (bound electron-hole pairs) are photo-excited states in organic semiconductors and they have two spin states: a singlet state and a triplet state [31], [32], [33]. Spins play an important role in solar cells, increasing the efficiency of solar cells requires increased excitons lifetime (Fig. 1) [34], [35].

The magnetic field and/or mixing magnetic nanoparticles can be used in the anodic side of the solar cell structure for increasing the lifetime of the exciton [36], [37], [38], [39]. Application of nanomagnets in the solar cell have been reported by researchers [17], [40], [41], [42]. They showed that the using magnetic materials in the active layer of the solar cell is an effective factor for increasing the efficiency of solar cells [17], [43], [44], [45] by producing local magnetic fields in creating the spin-orbit coupling which can increase the triplet state relative to the singlet state [17], [46], [47]. Indeed, the triplet state has a much longer exciton diffusion lifetime which can promote solar cell yield. As a result, the likelihood of the exciton reaching an electron-acceptor/electron-donor interface is much higher. In our previous work [17], a novel superparamagnetic core-shell nanocomposite of poly(m-aminobenzenesulfonic acid) and Fe₃O₄ nanoparticles was synthesized by in-situ in the presence of FeCl₃⋅6H₂O as oxidant under solid-state condition. Based on our results, the polymer-hybrid solar cell which was fabricated using FTO/TiO₂/NCPABS-Fe₃O₄/Al, demonstrated a high conversion efficiency (PCE, η) by 4.43%. One of the factors influencing the source of this great success is presence of covalently grafted -SO₃H groups in PABS on the surface of TiO₂ [17]. The results were shown that in-situ preparation of superparamagnetic nanoparticles of Fe₃O₄ during polymerization of aniline derivatives increased the efficiency of solar cells.

In the line to improve the efficiency of our previous results on the superparamagnetic core-shell nanocomposites [48], in this study the novel modified nanocomposites of polyaniline were synthesized in the presence of Fe₃O₄. Application of these nanocomposites in the structure of the solar cell improved the efficiency of the solar cell from 0.71% [48] to 1.53%.

The purpose of this research is the synthesis and study of the nanocomposite of parent polyaniline to find the effect of substituent such as -SO₃H group. We also applied Fe₃O₄ as enhancer phase and an active layer in PSCs under green and solvent-free chemical condition. The presence and increase of Fe₃O₄ magnetic nanoparticles led to an intensification of PCE. The process of the preparation and improvement the quality of this polymer-based nanocomposite is cost effective. It can be used as a light-sensitive layer in photovoltaic cells to obtain electrical energy from sunlight in addition to applications in other optoelectronic systems [49], [50].

Section snippets

Materials and equipment

All chemicals were purchased from Sigma-Aldrich and Merck companies. Fourier-transform informs infrared (FT-IR) spectra were recorded between 400 and 4000 cm⁻¹ from KBr pellets on a JASCO spectrophotometer. Ultraviolet–visible (UV–vis) spectra were recorded between 200 and 1000 nm on a PG instrument Ltd model T80⁺ UV–vis by dissolving the production N-methyl-2-pyrrolidone (NMP).

Scanning electron microscopy (SEM) was performed by MIRA3 Tescan-XMU at 10 kV equipped with energy dispersive X-ray

FT-IR spectroscopy

Fig. 2 shows the FT-IR spectra of nanocomposites A-D and their main peaks are summarized in Table 2. The assigned bands for the nanocomposite D is as follow:

The absorption peaks are found to be at 1590 cm⁻¹ is due to C˭C double bond quinoid (Q) rings, 1496 cm⁻¹ is due to vibration of C˭C double bond associated with the benzenoid (B) ring, 1293 cm⁻¹ is due to the combination of C−N in quinoid and benzenoid sequences. Peaks around 1267 and 1164 cm⁻¹ indicate the characteristics of polaron and

Conclusions

In summary, nanocomposites A-D with different ratios of oxidant FeCl₃0.6 H₂O were successfully synthesized using a simple and cost-effective technique under green chemistry condition as well as the increasing of the efficiency of the fabricated FTO_│TiO_2│Fe₃O₄@PANI_│Al device from them can be related to the magnetic field produced by the superparamagnetic Fe₃O₄ nanoparticles. It can be confirming by difference mechanisms such as a spin-orbit coupling and SF, that can increase the triplet state of

CRediT authorship contribution statement

Fatemeh Sadegh: PhD student, Investigation, Methodology, Validation, Writing - original draft. Ali Reza Modarresi-Alam: Supervisor, Conceptualization, Investigation, Methodology, Validation, Data curation, Writing original draft, Writing - review & editing. Meissam Noroozifar: Advisor, Data curation, Validation, Writing - review & editing. Kagan Kerman: Advisor, Data curation, Writing - review & editing.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

The authors acknowledge the financial support of a grant from the Graduate Council of the University of Sistan and Baluchestan and National Nanotechnology the Initiative funded by Iranian government.

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A facile and green synthesis of superparamagnetic Fe3O4@PANI nanocomposite with a core–shell structure to increase of triplet state population and efficiency of the solar cells

Highlights

Abstract

Graphical Abstract

Introduction

Section snippets

Materials and equipment

FT-IR spectroscopy

Conclusions

CRediT authorship contribution statement

Declaration of Competing Interest

Acknowledgements

J. Ind. Eng. Chem.

Acta Biomater.

Biosens. Bioelectron.

Polymer

J. Environ. Chem. Eng.

Prog. Nat. Sci.

J. Environ. Chem. Eng.

Prog. Polym. Sci.

Synth. Met.

Organic Electron.

Synth. Met.

J. Environ. Chem. Eng.

Green Energy Environ.

Optik

Int. J. Hydrog.

Coord. Chem. Rev.

J. Environ. Chem. Eng.

J. Environ. Chem. Eng.

J. Adv. Res.

Synth. Met.

Appl. Surf. Sci.

Colloids Surf. A Physicochem. Eng. Asp.

Synth. Met.

Synth. Met.

Synth. Met.

Spectrochim. Acta A Mol. Biomol. Spectrosc.

Mater. Lett.

Org. Electron.

Synth. Met.

J. Power Sources

J. Environ. Chem. Eng.

J. Mol. Struct.

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50th anniversary perspective: conducting/semiconducting conjugated polymers. a personal perspective on the past and the future

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Counter electrodes from double-layered polyaniline nanostructures for dye-sensitized solar cell applications

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High-efficiency polymer solar cells with water-soluble and self-doped conducting polyaniline graft copolymer as hole transport layer

J. Phys. Chem. C

A facile and green synthesis of superparamagnetic Fe₃O₄@PANI nanocomposite with a core–shell structure to increase of triplet state population and efficiency of the solar cells

Single-layer solar cell based on nanostructure of polyaniline on fluorine-doped tin oxide: a simple, low-cost and efficient FTO_│ n-PANI_│ Al cell