ZnS nanostructures: From synthesis to applications

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Abstract

Zinc sulfide (ZnS) is one of the first semiconductors discovered. It has traditionally shown remarkable versatility and promise for novel fundamental properties and diverse applications. The nanoscale morphologies of ZnS have been proven to be one of the richest among all inorganic semiconductors. In this article, we provide a comprehensive review of the state-of-the-art research activities related to ZnS nanostructures. We begin with a historical background of ZnS, description of its structure, chemical and electronic properties, and its unique advantages in specific potential applications. This is followed by in-detail discussions on the recent progress in the synthesis, analysis of novel properties and potential applications, with the focus on the critical experiments determining the electrical, chemical and physical parameters of the nanostructures, and the interplay between synthetic conditions and nanoscale morphologies. Finally, we highlight the recent achievements regarding the improvement of ZnS novel properties and finding prospective applications, such as field emitters, field effect transistors (FETs), p-type conductors, catalyzators, UV-light sensors, chemical sensors (including gas sensors), biosensors, and nanogenerators. Overall this review presents a systematic investigation of the ‘synthesis-property-application’ triangle for the diverse ZnS nanostructures.

Introduction

Nanostructured materials are not only in the forefront of the hottest fundamental materials research nowadays, but they are also gradually intruded into our daily life [1], [2], [3]. “There’s plenty of room at the bottom, the principles of physics, as far as I can see, do not speak against the possibility of maneuvering things atom by atom, put the atoms down where the chemist says, and so you make the substance…”, this famous statement of legendary Richard Feynman made in 1959 with immense foresight has been realized in less than half a century by consistent efforts and significant contributions from the scientific community across the globe [4].

Nanostructured materials are a new class of materials, having dimensions in the 1–100 nm range, which provide one of the greatest potentials for improving performance and extended capabilities of products in a number of industrial sectors [5]. Nanostructures can be divided into zero-dimensional (0D when they are uniform), one-dimensional (1D when they are elongated), and two-dimensional (2D when they are planar) based on their shapes. The recent emphasis in the nanomaterials research is put on 1D nanostructures at the expense of 0D and 2D ones, perhaps due to the intriguing possibility of using them in a majority of short-term future applications. There is a large number of new opportunities that could be realized by down-sizing currently existing structures into the nanometer scale (<100 nm), or by making new types of nanostructures. The most successful examples are seen in the microelectronics, where “smaller” has always meant a greater performance ever since the invention of transistors: e.g. higher density of integration, faster response, lower cost, and less power consumption [1].

Zinc sulfide (ZnS) is one of the first semiconductors discovered [6] and it has traditionally shown remarkable fundamental properties versatility and a promise for novel diverse applications, including light-emitting diodes (LEDs), electroluminescence, flat panel displays, infrared windows, sensors, lasers, and biodevices, etc. Its atomic structure and chemical properties are comparable to more popular and widely known ZnO. However, certain properties pertaining to ZnS are unique and advantageous compared to ZnO. To name a few, ZnS has a larger bandgap of ∼3.72 eV and ∼3.77 eV (for cubic zinc blende (ZB) and hexagonal wurtzite (WZ) ZnS, respectively) than ZnO (∼3.4 eV) and therefore it is more suitable for visible-blind ultraviolet (UV)-light based devices such as sensors/photodetectors. On the other hand, ZnS is traditionally the most suitable candidate for electroluminescence devices. However, the nanostructures of ZnS have not been investigated in much detail relative to ZnO nanostructures.

In this article, we will provide a comprehensive review of the state-of-the-art research activities related to ZnS nanostructures, including their synthesis, novel properties studies and potential applications. We begin with a historical background of ZnS, description of its structure, chemical and electronic properties, and the possible reasons for the investigation of this nanomaterial, followed by a survey of ZnS nanostructures with various morphologies and corresponding synthesis methods and experimental parameters. Using various facile techniques nanoparticles, nanorods, nanowires, nanobelts/nanoribbons, nanosheets, nanotubes, core/shell nanostructures, hierarchical nanostructures, complex nanostuctrues and heterostructures of ZnS have been synthesized under specific growth conditions so far. Subsequently, we will discuss the critical experiments determining the electrical, chemical and physical properties of the nanostructures, in regard of synthetic conditions. This will be followed by the main objective of the review which is the prospects of ZnS diverse structures in various functional devices. The recent progress on the improvement of their properties and finding novel potential applications, such as the latest achievements in using various ZnS nanostructures as field emitters, field effect transistors (FETs), p-type conductors, catalyzators, UV-light and chemical sensors (including gas sensors), biosensors, and nanogenerators will be highlighted.

Section snippets

Fundamental properties of ZnS

ZnS has two commonly available allotropes: one with a ZB structure and another one with a WZ structure. The cubic form is the stable low-temperature phase, while the latter is the high-temperature polymorph which forms at around 1296 K [7]. For the purpose of comparison, Fig. 1 shows three different views of these structures. The differences can be described either in terms of the relative handedness of the fourth interatomic bond or by their dihedral conformations. Alternatively, ZB consists of

Synthesis of ZnS nanostructures

Nanostructures have attracted steadily growing interest due to their fashinating properties, as well property–microstructure correlation [6], [20]. They can be divided into three kinds, namely 0D, 1D, and 2D nanostructures based on their shapes.

Luminescence properties of ZnS nanostructures

Luminescence is the generation of light. As pointed out in a recent review [304], light can be emitted via a number of luminescent processes, which include photoluminescence (PL), cathodoluminescence (CL), electroluminescence (EL), electrochemiluminescence (ECL), and thermoluminescence (TL). Table 15 lists typical types of luminescence and their origins. In this section, we present some typical luminescence properties of ZnS nanostructures.

Field emission phenomena

Field-emission (FE) (also known as electron field-emission) is an emission of electron induced by external electromagnetic fields. FE can take place from solid and liquid surfaces, or individual atoms into vacuum or open air, or result from promotion of electrons from the valence to conduction band in semiconductors. FE was explained by quantum tunneling of electrons in the late 1920s, in which electrons pass from an emitting material (which is negatively biased) to the anode through a barrier

Conclusions and outlooks

In this paper, we provide a comprehensive review on the synthesis of ZnS nanostructures, starting from 0D nanostructures (0D nanocrystals, 0D core/shell nanocrystals and 0D hollow nanocrystals), continuing with 1D nanostructures (nanowires, nanorods, nanotubes, nanobelts, nanoribbons, aligned nanowires and nanobelts, complicated nanostructures, longitudinal heterostructured nanostructures, coaxial (core/shell) heterostructured nanostructures, side-by-side heterostructures, doped 1D

Acknowledgements

This work was supported by National Science Foundation of China (Grant Nos. 51002032, 21001028 and 21074023), the innovative team of Ministry of Education of China (IRT0911), Grants-in-Aid for Scientific Research (B), Japan Society for the Promotion of Science (JSPS) (No. 22760517), and the World Premier International Research Center (WPI) Initiative on Materials Nanoarchitectonics (MANA), MEXT, Japan. The authors are indebted to corresponding publishers/authors for the kind permissions to

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