Tailoring the photoluminescent and electrical properties of tin-doped ZnS@PVP polymeric composite films for LEDs applications

doi:10.1016/j.spmi.2021.106838

Superlattices and Microstructures

Volume 151, March 2021, 106838

https://doi.org/10.1016/j.spmi.2021.106838 Get rights and content

Highlights

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Tailoring the photoluminescent properties of Zn_1-xSn_xS@PVP have been investigated for LEDs applications.
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XRD measurements reveal the amorphous nature of the prepared polymeric composite films.
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Three emission peaks for ZnS@PVP polymeric film are noticed.
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An extra emission peak located at 480–502 nm is observed for Zn_1-xSn_xS@PVP films.
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The dc-electrical conductivity of Zn_1-xSn_xS@PVP polymeric composite films is enhanced.

Abstract

In the present work, tailoring the photoluminescent and electrical properties of Zn_1-xSn_xS@PVP polymeric composite films has been achieved for LEDs applications. Un-doped and 1.0 wt % of Sn-doped ZnS in polyvinyl pyrrolidine (Zn_1-xSn_xS@PVP) polymeric composite films were prepared using solution casting technique. The effect of Sn molar ratio x (x: 0 to 0.3) on the morphological, structural, photoluminescent and electrical properties is explored using a scanning electron microscope, X-ray diffraction (XRD), photoluminescence (PL) and DC electrical conductivity studies. XRD measurements reveal the amorphous nature of both bare PVP and Zn_1-xSn_xS@PVP polymeric composite films. The PL spectra measurements of the prepared films exhibit broad emission peaks with maxima intensities ranged from 400 to 417 nm. The Gaussian fitting method is used to de-convolute the PL emission bands of bare PVP and Zn_1-xSn_xS@PVP polymeric composite films. Three emission peaks for ZnS@PVP polymeric film are noticed at 392, 430 and 476 nm. An extra emission peak located at the green light region (480–502 nm) is observed for Zn_1-xSn_xS@PVP composite films. The electrical conductivity of the prepared Zn_1-xSn_xS@PVP polymeric composite films is enhanced thirty times more than that of bare PVP one. The prepared Zn_1-xSn_xS@PVP polymeric composite films could play an important role in LEDs applications.

Graphical abstract

Introduction

In the last two decades, polymers have played a significant role in various aspects of life. Polymers have occupied this high level because of their unique characteristics over other materials. The uniqueness includes the optical, electrical, mechanical and structural properties. Additionally, the ability of producing polymers in different shapes, volumes and amounts make them favorable in various applications. Also, polymers are preferable over other materials as semiconductors to play the role of host matrices due to their flexibility, abundance, stability and low-cost [[1], [2], [3]]. Recently, a pronounced trend is remarked toward polymers composites and blends for many applications issues. Engineering the polymers' properties could be achieved using different techniques under limited conditions [4,5]. To accomplish this goal, blending polymers or filling them with specific materials is the well-known procedures that have been utilized. Chitin, nylon, polyvinyl alcohol (PVA) and polyvinyl pyrrolidine (PVP) polymers are the most ones that are used in different applications due to their availability, inexpensively and human-friendly. For example, chitin is the most available bio-polymers in nature that qualifies it for medical applications [[6], [7], [8]]. Nylon with its abundance and cheapness plays a great role in our daily life. PVA possesses a semi-crystallinity character that makes it an active participant in industrial issues as photovoltaics as an example [[9], [10], [11], [12]]. PVP with it's amorphous nature, stability, water-solubility and bio-compatibility could effectively participate in environmental-friendly applications [10,13]. As a result, the previous polymers could greatly be utilized either individually or as hosts' matrices to produce polymeric composites blends.

A lot of previous works has been taken place using polymers as hosts to formulate composites blends for specific desired purposes [[14], [15], [16], [17], [18], [19], [20]]. The majority of these works concerns in investigating the properties of the polymeric blends via controlling the fillers’ concentration in the polymeric host. But minor works concern in exploring the polymeric composite blends properties through adjusting the compositional ratios of the fillers, whereas its concentration remains constant. Following the former strategy, Alharthi et al. [5] filled PVA polymer with different amounts of Ag₂S semiconductor for visible light optoelectronic devices. Also, in our previous work [4], the optical PVA/PVP polymeric blend has in-situ been engineered by filling it with different ratios of SnS semiconductor. While following the second strategy, Heiba et al. [21] showed the pronounced influence of the compositional ratios of Cd_1-xMn_xFe₂O₄ on the optical and structural properties of PMMA polymeric composite blends. Moreover, the optical and photoluminescent properties of Al-doped ZnS nanoparticles were investigated by Reddy et al. They concluded that Al-doped ZnS NPs exhibited a broad emission peak ranged from 350 nm to 650 nm [22].

In this work, we prepared 1.0 wt % of tin-doped ZnS as a filler in PVP polymer (Zn_1-xSn_xS@PVP) to produce polymeric composite films for light emitting diodes (LEDs) applications. ZnS is favorable to play the role of the filler in PVP polymer because of its non-toxicity and high stability. Moreover, ZnS is considered as a wide bandgap semiconductor (3.72 eV [23,24]) that makes it easy to tune its physical properties for such an application. These applications include optoelectronics, sensors, solar cells and magnetic devices [25,26]. Tin (Sn) as a non-toxic and earth-abundant material [27,28] could be effectively used as a dopant element with molar ratios from 0 to 0.3 in ZnS semiconductor. The morphology, structural, photoluminescence and electrical properties of the prepared Zn_1-xSn_xS@PVP polymeric composite films have been investigated.

Section snippets

Methods and materials

The materials used in this study were of analytical grade. The precursors' source of Zn, Sn and S (ZnCl₂, SnCl₂:2H₂O and Na₂S:9H₂O respectively) were obtained from Sigma-Aldrich Co. Alfa Aesar Co. was the source of the PVP polymer (M.W. 40,000 g/mol). Double distilled water (DDW) was the solvent of all dilutions and precursors' preparation. The solution casting technique was used to prepare Zn_1-xSn_xS@PVP polymeric composite films as discussed in our previous works [4,5]. Briefly, for each

The surface morphology analysis

The surface morphology of the bare PVP and Zn_1-xSn_xS@PVP (x: 0, 0.1 and 0.3) polymeric composite films is examined using a scanning electron microscope (SEM) as displayed inFig. 1 (a)–(d) respectively. From Fig. 1 (a) which relates to the SEM of the bare PVP film, it is clear that the PVP surface is clear, smooth and free from any bright spots, contaminations or aggregations. While according to the SEM micrographs of Zn_1-xSn_xS@PVP polymeric composite films that illustrated in Fig. 1 (b)–(d),

Conclusions

Bare PVP, un-doped ZnS and Sn doped ZnS filled PVP with 1.0 wt% (Zn_1-xSn_xS@PVP) polymeric composite films were prepared using solution casting technique for LEDs applications. The scanning electron microscope measurements ensure the homogeneous distribution of Zn_1-xSn_xS as a filler in the host PVP matrix. The amorphous structural nature of the prepared Zn_1-xSn_xS@PVP polymeric composite films is confirmed by XRD measurements. The photoluminescence spectra of the prepared polymeric films exhibit

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.

Acknowledgment

The Authors thank Taif University Researchers Supporting Project number (TURSP-2020/12), Taif University, Taif, Saudi Arabia.

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Tailoring the photoluminescent and electrical properties of tin-doped ZnS@PVP polymeric composite films for LEDs applications

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Methods and materials

The surface morphology analysis

Conclusions

Declaration of competing interest

Acknowledgment

Journal of Materials Research and Technology

Opt. Mater.

Prog. Polym. Sci.

Phys. B Condens. Matter

Spectrochim. Acta Mol. Biomol. Spectrosc.

J. Mol. Struct.

J. Sci.: Advanced Materials and Devices

Mater. Sci. Semicond. Process.

Opt. Mater.

J. Alloys Compd.

Mater. Lett.

Phys. B Condens. Matter

Surfaces and Interfaces

Mater. Chem. Phys.

J. Alloys Compd.

J. Alloys Compd.

Solid State Ionics

Solid State Sci.

Phys. B Condens. Matter

Solid State Commun.

Opt. Mater.

Int. J. Electrochem. Sci.

Thin Solid Films

Solid State Ionics

Solid State Ionics