ZnS, as one of the first semiconductors discovered and a rising material star, has embraced exciting breakthroughs in the past few years. To shed light on the design principles and engineering techniques of ZnS for improved/novel optoelectronic properties, the fundamental mechanisms and commonly employed strategies are proposed in this review. Recent progress on modifications of ZnS allows it to be extensively and effectively used in versatile applications, including transparent conductors, UV photodetectors, luminescent devices, and catalysis, which are clearly and comprehensively summarized in this work. Novel functional devices springing up from the newly developed ZnS-based materials are highlighted as well. This review not only provides a scientific insight into the advances of ZnS-based materials, but also touches on the future opportunities in this inspiring field.

Design Principles and Material Engineering of ZnS for Optoelectronic Devices and Catalysis

We find two different surface structures, (1×2) and (1×1), for H2S‐treated InP(001). They depend upon exposure of H2S at about 350 °C. The coverage of sulfur is estimated to be about a half monolayer and one full monolayer for the (1×2) and (1×1) structures, respectively. The (1×1) structure is reconstructed to the (1×2) structure upon annealing at about 550 °C. It is suggested that sulfur is bonded to only In atoms and substitutes some of the phosphorus atoms below the first layer. Inverse photoemission spectra show strong reduction in intensity of 1.2 eV peak above the Fermi level for a clean InP(001)‐(4×2) surface upon adsorption of H2S. This reduction implies a decrease in unoccupied surface states due to dangling bonds of indium dimers on the clean surface. The result of adsorption of oxygen on the (1×2) and (1×1) surfaces indicates significant passivation to oxidation of the surfaces.

Surface Structures and Electronic States of H2S-treated InP(001) Studied by LEED,STM,XPS,and IPES (Proceedings of International Symposium on Surfaces and Thin Films of Electronic Materials--October 3-4,1995,Sanaru Hall,Hamamatsu Campus,Shizuoka University)

The principles of the present invention are used to reduce the conduction band offset between chalcogenide emitter and pnictide absorber films. Alternatively stated, the present invention provides strategies to more closely match the electron affinity characteristics between the absorber and emitter components. The resultant photovoltaic devices have the potential to have higher efficiency and higher open circuit voltage. The resistance of the resultant junctions would be lower with reduced current leakage. In illustrative modes of practice, the present invention incorporates one or more tuning agents into the emitter layer in order to adjust the electron affinity characteristics, thereby reducing the conduction band offset between the emitter and the absorber. In the case of an n-type emitter such as ZnS or a tertiary compound such as zinc sulfide selenide (optionally doped with Al) or the like, an exemplary tuning agent is Mg when the absorber is a p-type pnictide material such as zinc phosphide or an alloy of zinc phosphide incorporating at least one additional metal in addition to Zn and optionally at least one non-metal in addition to phosphorus. Consequently, photovolotaic devices incorporating such films would demonstrate improved electronic performance.

Method of making photovoltaic devices with reduced conduction band offset between pnictide absorber films and emitter films

The present invention provides strategies for improving the quality of the insulating layer in MIS and SIS devices in which the insulator layer interfaces with at least one pnictide-containing film. The principles of the present invention are based at least in part on the discovery that very thin (20 nm or less) insulating films comprising a chalcogenide such as i-ZnS are surprisingly superior tunnel barriers in MIS and SIS devices incorporating pnictide semiconductors. In one aspect, the present invention relates to a photovoltaic device, comprising: a semiconductor region comprising at least one pnictide semiconductor; an insulating region electrically coupled to the semiconductor region, wherein the insulating region comprises at least one chalcogenide and has a thickness in the range from 0.5 nm to 20 nm; and a rectifying region electrically coupled to the semiconductor region in a manner such that the insulating region is electrically interposed between the collector region and the semiconductor region.

Photovoltaic devices incorporating thin chalcogenide film electrically interposed between pnictide-containing absorber layer and emitter layer

Using first-principles total energy method, we have studied the structural and electronic properties of Ga- and P-terminated GaP(001)(1×2) surfaces adsorbed with one monolayer of sulfur. It was found that the sulfur atoms prefer to occupy bridge sites and the periodicity becomes (1×1) on both Ga- and P-terminated surfaces. The S-Ga bond was confirmed to be stronger than the S-P bond. The electronic analysis showed that the surface state within the energy gap on the Ga-terminated GaP surface was noticeably reduced by the sulfur adsorption, while such reduction does not occur on the P-terminated surface due to the S-P antibonding state. The nearly filled S dangling bonds on the Ga-terminated surface make this surface resistant to contamination.

First-principles study of sulfur passivation of GaP(001) surface at one-monolayer coverage

Based on first-principles calculations, we explored a good candidate for achieving low-resistance and high carrier concentration of n-type ZnS by a dual-donor codoping method, where the ionization energy was effectively reduced. We found that the SnZn-FS pair has a shallow donor level of 17.2 meV, a small formation energy of 1.27 eV and a high binding energy of 1.28 eV. The density of states analysis showed that the SnZn-FS pair induces the downward shift of the conduction band minimum by about 0.15 eV, while the basis electronic structure does not change. Thus, the SnZn-FS pair is likely to be a best n-type dopant for ZnS.

Dual-donor codoping approach to realize low-resistance n-type ZnS semiconductor

Using density functional theory, we have studied surface structural and electronic properties of sulfur adsorption on As-terminated and In-terminated InAs(001) surfaces with the coverage (Θ) of 0.5ML and 1ML. Based on adsorption energy calculations, we found that at Θ=0.5ML, S adatoms preferred to replace the As atoms at As-terminated InAs(001)(2×1) surface. For 1ML S adsorption on InAs(001)(2×1) surface, the most stable adsorption geometry is S-S dimers covered on the In-terminated surface. This result is different from that for 1ML S adsorption on GaP(001) and InP(001) surfaces, and it is consistent with the experimental results. The electronic band structure analysis showed that the surface state density around the Fermi level was considerably diminished for 0.5ML S adsorption on As-terminated InAs(001)(2×1) surface at substitution site. The surface state density of S-S dimer adsorption on In-terminated (2×1) surface was strengthened due to one excess valence electron on the surface.

Surface structure and electronic property of sulfur passivation of InAs(001) surface: A first-principles study

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Dual-donor codoping approach to realize low-resistance n-type ZnS semiconductor

Surface structure and electronic property of sulfur passivation of InAs(001) surface: A first-principles study