Hexagonal ZnS Research Articles

Energy-saving synthesis of wurtzite ZnS nanoparticles using Yttrium as a defect regulator by hydrothermal method

In this work, Y-doped ZnS nanoparticles were synthesised using the hydrothermal method with doping percentages of 0.5%, 1%, 2.5%, and 5%. XRD study revealed that doping caused a phase transition from cubic to hexagonal, further confirmed by Raman analysis and TEM images. Morphological studies conducted by SEM and TEM provided insights into the structural changes. Diffused reflectance studies were used to evaluate the band gap, with values obtained as 3.33eV, 3.45 eV, 3.45 eV, 3.44 eV, and 3.37 eV for pure, 0.5%, 1%, 2.5%, and 5% Y-doped ZnS, respectively. Photoluminescence analysis revealed the presence of defect states in ZnS nanoparticles, indicated by peaks at 362 nm, 383 nm, and 390 nm in both pure and doped samples. The intensity of these peaks increased with Y doping, attaining its highest at 1% Y doping, while concentration quenching was observed at higher doping percentages. The EDAX analysis confirmed the successful integration of Y as a dopant in the ZnS lattice. These findings highlight the importance of optimizing the doping concentration to achieve the desired luminous features and provide valuable insights into the doping-dependent luminescence behaviour of Y-doped ZnS nanoparticles. The visible light photocatalytic activity of the nanoparticles was investigated, and it was revealed that the photocatalytic efficiency increased initially and then declined with the doping concentration increased. It was found that the ideal doping concentration for 93% degradation efficiency was 1%. The novelty of this work lies in developing a simple and energy-saving method for synthesizing hexagonal ZnS at low temperatures, which avoids the need for high temperatures and advanced anti-oxidation apparatus.

Blue-green emitting ZnS0.75O0.25:Ce3+,x%Tb3+ phosphor with tunable fluorescence lifetime

A series of ZnS0.75O0.25:0.1%Ce3+,x%Tb3+ phosphors were prepared by high temperature solid state reaction method. These phosphors exhibited two mixed phases consisting of hexagonal phase ZnS and hexagonal phase ZnO with the average particle size of 13.83 μm and emitted blue-green light. The luminescence mechanism consisted of Zn vacancy defects, the 5d1 → 2F5/2 radiative transitions of Ce3+, the 5D4 → 7F5 and 5D4 → 7F6 radiative transition of Tb3+ induced by the energy transfer of Ce3+ → Tb3+. An equation for the variation of the fluorescence lifetime of ZnS0.75O0.25:0.1%Ce3+,x%Tb3+ phosphors with concentration of Tb3+ fraction was obtained by exponential fitting. The short fluorescence lifetime could be tuned within the range of 113 μs to 550 μs with the increase of Tb3+ concentration, and the color was tunable from blue to blue-green, which is of important application in the field of high-energy particle detection.

Zinc and cadmium thioamidate complexes: rational design of single-source precursors for the AACVD of ZnS.

A series of zinc(II) thioamidate complexes [Zn{SC(iPr)NR}2]n for R = iPr (n = 2) (2), tBu (3) (n = 1), Ph (4) (n = 2) and Cy (5) (n = 2) and one cadmium(II) thioamidate complex [Cd{SC(iPr)NtBu}2]3, (6), were designed and synthesised as single-source precursors for AACVD ZnS and CdS. Solid-state structures of all four zinc(II) compounds revealed distorted tetrahedral or trigonal bipyramidal geometries, with varying tendencies for dimeric association, mediated by {Zn-S} bridging bonds. The thermogravimetric analysis identified the {tBu} derivertive, 3, as the most promising precursor based on its low decomposition onset (118 °C) and clean conversion to ZnS. This was attributed to the greater availability of β-hydrogen atoms promoting the pyrolysis mechanism. The corresponding cadmium thioamide 6 was found to crystallise as a trimetallic molecule which lacked the thermal stability to be considered viable for AACVD. Hence, 3 was used to deposit ZnS thin films by AACVD at 200-300 °C. Powder X-ray diffraction confirmed phase-pure growth of hexagonal wurtzite ZnS, with approximate crystallite sizes of 15-20 nm. Scanning electron microscopy revealed densely packed spherical nanoclusters. The morphology and crystallinity were most consistent for depositions between 250-300 °C. Energy dispersive X-ray spectroscopy indicated slightly sulfur-deficient stoichiometries.

Luminescence properties of ZnSxO1-x:Ce3+ phosphors with tunable short fluorescence lifetime

Fluorescence lifetime of phosphors is a critical index in the field of high energy physics and astrophysical detection. A series of ZnSxO1-x:0.05Ce3+ phosphors with tunable short fluorescence lifetime were prepared by performing high temperature solid state reaction method. The phosphors exhibited two mixed phases consisting of the hexagonal phase ZnO and the hexagonal phase ZnS. They are spherical and the average particle size is 2.24 μm. As the component content of the ZnS in ZnSxO1-x:0.05Ce3+ phosphors varies, the emission wavelength can be tuned from 448 nm to 495 nm, the short fluorescence lifetime can be tuned within the range of 6 μs–200 μs. By performing exponential fitting, we obtained the equation for the variation of fluorescence lifetime of ZnSxO1-x:0.05Ce3+ phosphors with ZnS fraction.

A DFT insight into magnetic, optoelectronic and thermoelectric properties of h-Zn1-xCuxS monolayer

In this study, we used the density functional theory (DFT) method to analyze the effect of Cu insertion on the structural stability, electronic, magnetic, optical and thermoelectric properties of the hexagonal ZnS monolayer (h-ZnS-2D). Our findings show that Cu replaces zinc sites by giving a stable planar structure in Ferromagnetic (FM) phase with slight decrease in the lattice parameter. A p-type semiconductor with a direct band gap that decreases with increasing Cu concentration was obtained. The half-metallic character found for low Cu concentrations let consider the h-Zn1-xCuxS-2D for potential applications in spintronic devices. The optical properties show that the h-Zn1-xCuxS-2D monolayers have high absorption and low transmittance in the UV range. The improved figure of merit of h-Zn1-xCuxS-2D due to increased electrical conductivity and decreased thermal conductivity with Cu content, makes these nanostructures a promising absorber for thin-film solar cells and suitable for solar thermal energy conversion technologies.

Synthesis of a Hexagonal Phase ZnS Photocatalyst for High CO Selectivity in CO2 Reduction Reactions.

ZnS materials exhibit very negative potential of the conduction band, which is promising in photocatalytic reduction reactions. Unfortunately, previously reported ZnS materials for photocatalysis are mainly in the cubic phase, which produce high activity for H2 evolutions and low activity toward CO2 reductions. Herein, a hexagonal phase ZnS photocatalyst is fabricated for highly efficient CO2 reduction reactions. The hexagonal ZnS nanoplates with the pure phase and well crystallization are synthesized via three-step solvothermal methods. In photocatalytic CO2 reduction reactions under an aqueous solution environment, the hexagonal ZnS produces a CO selectivity of 21%, which is distinctly higher than that of 0.2% for commonly used cubic ZnS. The energy band study suggests that hexagonal ZnS possesses a slightly more negative conduction band and wider bandgap than cubic ZnS. Theoretical calculations reveal that the hexagonal ZnS possesses increased electron density around Zn atoms as that of cubic ZnS. Furthermore, hexagonal ZnS exhibits relatively reduced absorption energy of CO2 reduction intermediates and increased absorption energy of H* as cubic ZnS, which result in better selectivity toward CO2 reduction reactions. This study offers deep insights into the synthesis and electronic structure of hexagonal ZnS for CO2 reduction reactions, which inspire the design of highly active photocatalysts for artificial photosynthesis.

Determination of zinc speciation in soil using synchrotron radiation and its effects on cellular organelles of Phragmites australis

It is necessary to apply modern approaches to prevent the spread/toxic effects of pollution caused by a changing climate; especially metal pollutants to the soil. Thus, the present investigation was aimed to examine chemical speciation of soil samples collected from the River floodplain and its effects on native plant species; Phragmites australis. Synchrotron radiation (SR) tools for Zn speciation in soil and scanning electron microscopy for anatomical changes in plants were applied. Speciation of Zn was a dominant pollutant in Technosols. Two local surroundings were observed for Zn corresponding to its coordination by O and by S, close to ZnS. Whereas, the mixed local surrounding was noted with Zn–S and Zn–O bonds. The analysis of X-ray absorption fine structure results revealed that Technosols contained 70 and 30% of Zn–S and Zn–O bonds, respectively. SR results could be summarized that the main contribution in Technosols was from the authigenic minerals of metals with S: würtzite (hexagonal ZnS), sphalerite (cubic ZnS), bornite (Cu5FeS4), and covellite (CuS). The investigation on growth and modifications in the ultrastructure of P. australis roots and stems showed changes in cellular tissues such as in epidermis and mesoderm, and in subcellular organelles: mitochondria, chloroplast, cell membrane, etc. It is established that the soil contamination with exceeded limits slows down the ontogenetic developments of P. australis. Our findings could provide insight into the physiochemical characteristics of polluted soil as well as information on the toxic effects of pollutants on plants based on non-destructive approaches.

Lattice Orientation Heredity in the Transformation of 2D Epitaxial Films.

The ability to control lattice orientation is often an essential requirement in the growth of both 2D van der Waals (vdW) layered and nonlayered thin films. Here, a unique and universal phenomenon termed "lattice orientation heredity" (LOH) is reported. LOH enables product films (including 2D-layered materials) to inherit the lattice orientation from reactant films in a chemical conversion process, excluding the requirement on the substrate lattice order. The process universality is demonstrated by investigating the lattice transformations in the carbonization, nitridation, and sulfurization of epitaxial MoO2 , ZnO, and In2 O3 thin films. Their resultant compounds all inherit the mono-oriented crystal feature from their precursor oxides, including 2D vdW-layered semiconductors (e.g., MoS2 ), metallic films (e.g., MXene-like Mo2 C and MoN), wide-bandgap semiconductors (e.g., hexagonal ZnS), and ferroelectric semiconductors (e.g., In2 S3 ). Using LOH-grown MoN as a seeding layer, mono-oriented GaN is achieved on an amorphous quartz substrate. The LOH process presents a universal strategy capable of growing epitaxial thin films (including 2D vdW-layered materials) not only on single-crystalline but also on noncrystalline substrates.

Study of the Structure and Properties of ZnS Utilized in a Fluorescence Biosensor.

ZnS materials have been widely used in fluorescence biosensors to characterize different types of stem cells due to their excellent fluorescence effect. In this study, ZnS was prepared by vulcanizing nano-Zn particles synthesized using a DC arc plasma. The composition and structure of the ZnS materials were studied by X-ray diffraction (XRD), and their functional group information and optical properties were investigated by using IR spectrophotometry and UV-vis spectrophotometry. It has been found that the synthesized materials consist of Zn, cubic ZnS, and hexagonal ZnS according to the vulcanization parameters. Crystalline ZnS was gradually transformed from a cubic to a hexagonal structure, and the cycling properties first increase, then decrease with increasing sulfurization temperature. There is an optimal curing temperature giving the best cycling performance and specific capacity: the material sulfurized thereat mainly consists of cubic β-ZnS phase with a small quantity of Zn and hexagonal α-ZnS. The cubic phase ZnS has better conductivity than hexagonal ZnS, as evinced by electrochemical impedance spectroscopy (EIS). The ZnS (as prepared) shows board absorption, which can be used in fluorescence biosensors in cell imaging systems.

Front Cover: In Situ Synchrotron X‐ray Diffraction Studies of the Mechanochemical Synthesis of ZnS from its Elements (Chem. Eur. J. 49/2021)

The mechanism of the mechanochemical synthesis of cubic ZnS from its elements via ball milling was studied by in situ synchrotron diffraction experiments coupled with gas pressure measurements inside the milling vessel. The combination of both techniques reveals a heterogeneous reaction mechanism including gaseous sulfur and solid zinc. Moreover, the reaction kinetics of the phase transition from cubic to hexagonal ZnS was determined from the in situ synchrotron diffraction experiments. More information can be found in the Full Paper by C. Weidenthaler et al. (DOI: 10.1002/chem.202101260).

In Situ Synchrotron X-ray Diffraction Studies of the Mechanochemical Synthesis of ZnS from its Elements.

Mechanochemistry, as a synthesis tool for inorganic materials, became an ever‐growing field in material chemistry. The direct energy transfer by collision of the educts with the milling media gives the possibility to design environmental‐friendly reactions. Nevertheless, the underlying process of energy transfer and hence the kinetics of mechanosynthesis remain unclear. Herein, we present in situ synchrotron X‐ray diffraction studies coupled with pressure measurements performed during the formation of ZnS and the subsequent phase transition (PT) from the hexagonal to the cubic modification. Milling Zn and S8 results in the sublimation of S8, observed by a sudden pressure increase. Simultaneously, the hexagonal metastable ZnS‐modification (wurtzite) forms. Via detection of the pressure maximum, the exact start of the wurtzite formation can be determined. Immediately after the formation of wurtzite, the structural PT to the thermodynamic stable cubic modification sphalerite takes place. This PT can be described by the Prout‐Tompkins equation for autocatalytic reactions, similar to thermally induced PT in sulfur vapor at high temperatures (T>1133 K). The increase in the reactivity of the wurtzite formation is explained by the reaction in sulfur vapor and the induction of defect structures by the collisions with the milling media.

Optical manipulation of nebulizer spray pyrolysed ZnS thin films for photodetector applications: Effect of Al, Sn and Sb doping

Abstract In this work, we report the structural, morphological, optical and photo-sensing properties of pure as well as Al, Sn and Sb-doped ZnS thin films, with the prospect of photo-sensing and photo-detection applications. ZnS, ZnS:Al(1%), ZnS:Sn(1%) and ZnS:Sb(1%) thin films are fabricated by the spray pyrolysis method. These thin films exhibit polycrystalline nature and crystallize in hexagonal wurtzite ZnS structure. Optical properties reveal the semiconductor behavior of all the films. The optical bandgap (Eg) values, which are around 3.67 eV, 3.43 eV, 3.32 eV and 3.56 eV for ZnS, ZnS:Al(1%), ZnS:Sn(1%) and ZnS:Sb(1%) thin films, respectively, decrease with Al, Sn and Sb-doping. On the other hand, doping of Al, Sn and Sb into the ZnS lattice enhances the photo-sensing parameters such as responsivity (R) and external quantum efficiency (EQE). Al-doping into the ZnS does not affect detectivity (D*) but Sb-doping results in a decrement of D*-value. ZnS:Sn(1%) photo-detector exhibits the highest R, EQE and D*-values of 1.05 × 10−1 AW−1, 33.9% and 4.29 × 1010 Jones, respectively, among all the fabricated photo-devices. Thus doping of post-transition (Al, Sn) and metalloid (Sb) elements into the ZnS host lattice significantly alter the optical and photo-sensing properties of the present thin films.

An insight into the structure, luminescent characteristics and Judd-Ofelt analysis of (1-x) ZnS-(x) Dy2O3 phosphors

We report a white light emitting of (1- x) ZnS - (x) Dy2O3 with x = 0, 0.1, 0.2 and 0.3 phosphor synthesized via conventional solid state reaction method. The crystal structure, modes of vibrations, morphology, NIR-UV absorption and luminescence characteristics were discussed. The X-ray diffraction study confirmed the single phase of hexagonal ZnS and cubic Dy2O3 structure. The intensity parameters Ω2, Ω4 and Ω6 were estimated for x = 0.1, from the optical absorption spectra using Judd-Ofelt theory, since the optimal doping concentration is about 10mol%. The optical band gap energy of the samples varied from 3.41 to 3.49 eV. The photoluminescence spectra has an intense strong emission at 582 nm corresponding to 4F9/2 → 6H13/2 transition due to a forced electric dipole (ED) allowed transition with selection rule ΔL = 2 and ΔJ = 2. The transition radiative parameter (AR) and the stimulated emission cross section, σe values suggested that (1- x) ZnS - (x) Dy2O3 with x = 0.1 phosphor material is suitable for white LED applications. The nephelauxetic ratio and the bonding parameter of concentration x = 0.1 were calculated. The negative value of bonding parameter indicated that Dy3+ ion and ZnS material is bonded ionically. The CIE chromaticity coordinates, Yellow to Blue intensity ratio, Color Purity and Correlated Color Temperature were also estimated. The CIE coordinates of the samples lie in the white light region and this type of white light luminescence phosphors could be promising phosphors for w-LEDs and optoelectronic devices applications.

Solid state low temperature synthesis approach for ZnO-ZnS nanoheterostructure with functionality as a photocatalyst for H2 production and for DSSC

Herein, we demonstrate a facile, template free, scalable, solid-solid, single step synthesis approach to produce ZnO/ZnS nanoheterostructure. Commercially available ZnO and thiourea have been used as precursors. Interestingly, it is observed that ZnO particle is covered with ZnS and the ZnS shell thickness can be varied depending on the sulfidation time. The crystal structures, morphology of samples are verified by XRD, FETEM and EDX. The XRD results show the mixed phases of hexagonal ZnO and ZnS. The broad peak of ZnS clearly reveals the nanocrystalline nature and also increase in intensity of peak with respect to sulfidation time. The optical spectra of the samples exhibits two band absorption edges and blue shift in the absorption edge depending on the ZnS thickness deposited. Particle size of the ZnS (5–3 nm) coated on the ZnO by varying the sulfidation time influences the performance of the DSSC and photocatalytic H2 evolution from water has been investigated, systematically. The DSSC performance of ZnO/ZnS nanoheterostructure shows maximum efficiency of 3.30% with increment in Jsc (9.04 mA/cm2). The performance is much better than pristine ZnO and earlier report of ZnO-ZnS nanostructure. This good performance is due to excellent light absorbing capability of the ZnO/ZnS nano heterostructure by providing ZnO core by providing easy electron transfer at the interface and the ZnS shell facilitate to reduce the recombination of diffuse electrons with either the dye or the electrolyte. The H2 evolution rate reported herewith is 3209 and 1685 μmol h−1g−1 under UV and Natural sunlight, respectively which is significantly higher than pristine ZnS and ZnO. The H2 evolution rate increases with decrease in particle size of ZnS which is quite ovibius because lowering particle size exhibits increase in surface area. The fabrication of ZnO/ZnS nanoheterostructure is the simple and cost effective, which can open new avenues strategy for large scale applications of the novel materials in the energy storage and photovoltaic devices.

Enhanced antibacterial activity of Ag-doped ZnS nanoparticles synthesised by a microwave-assisted polyol method

ABSTRACT Silver doped zinc sulphide nanoparticles were synthesised by a microwave-assisted polyol method. Characterisation of nanoparticles was performed using XRD, FESEM-EDXand UV-visible spectroscopy to investigate chemical structure, crystalline phase, particle size and surface morphology. Antibacterial properties of synthesised nanoparticles were investigated by determining their MIC and MBC values and kinetic of bactericidal activity against Staphylococcus aureus(ATCC 6538) and Escherichia coli(ATCC 25922). Characterisation of the synthesised nanoparticles showed formation of single phase of hexagonal wurtzite ZnS structure with Ag+ substitution at 1.6% Zn/Ag molar ratio. MIC values were determined as 250 and 500 µg/ml against Staphylococcus aureus and Escherichia coli, respectively and time kill profiles showed efficient and rapid bactericidal activity of the synthesised Ag-doped ZnS nanoparticles. Results of this study suggest a synthesis strategy for Ag-doped ZnS nanoparticles with potent and broad spectrum antibacterial properties that can widen the range of applications of these nanoparticles.

Speciation of Zn and Cu in Technosol and evaluation of a sequential extraction procedure using XAS, XRD and SEM-EDX analyses.

Metal speciation, linked directly to bioaccessibility and lability, is a key to be considered when assessing associated human and environmental health risks originated from anthropogenic activities. To identify the Zn and Cu speciation in the highly contaminated, technogenically transformed soils (Technosol) from the impact zone near the industrial sludge reservoirs of chemical plant (Siverskyi Donets River floodplain, southern Russia), the validity of the BCR sequential extraction procedure using the X-ray absorption fine-structure and X-ray powder diffraction (XRD) analyses was examined after each of the three stages. After the removal of exchange and carbonate-bonded Zn and Cu compounds from Technosol (first stage of extraction), the resulting residual soil showed enrichment in a great diversity of metal compounds, primarily with Me-S and Me-O bonds. The number of compounds with a higher solubility decreased at the subsequent stages of extraction. In the residual soil left over after extracting the first and second fractions, the dominant Zn-S bond appeared as würtzite (hexagonal ZnS) that made up more than 50%, while the Cu-S bond was almost completely represented only by chalcocite (Cu2S). The XRD analysis revealed the authigenic minerals of metals with S: sphalerite (cubic ZnS), würtzite (hexagonal ZnS), covellite (CuS) and bornite (Cu5FeS4). The scanning electron microscopy data confirmed that würtzite was the dominant form of Me with sulfur-containing and carbonate-containing minerals. The Zn-S bond was the main component (57%), whereas the Cu-O bond was dominant in the residual fraction (the fraction after the third-stage extraction). The results revealed that the composition of the residual fractions might include some of the most stable and hard-to-recover metal compounds of technogenic origin. Thus, the application of the novel instrumental methods, coupled with the chemical fractionation, revealed the incomplete selectivity of the extractants in the extraction of Zn and Cu in long-term highly contaminated soils.

Influence of annealing temperature of ZnS-coated TiO2 films on the performance of dye-sensitized solar cells

This work deals with ZnS-coated TiO2 films prepared via liquid phase deposition and immersion techniques and then applied as photoanode of dye-sensitized solar cells. The samples underwent annealing treatment at various annealing temperatures. The morphology of TiO2 is nanograss and covered by agglomerate and hexagonal ZnS layer. The anatase crystallite size, absorption peak wavelength and optical reflectance increase with annealing temperature. However, the energy gap decreases with the temperature. The device utilizing the sample annealed at 400 °C performed the highest η of 0.24 % due to this device owns the lowest leak current and the longest carrier lifetime.

ZnS:Cu powders with strong visible-light photocatalysis and pyro-catalysis for room-temperature dye decomposition

In this work, strong visible-light photocatalysis and pyro-catalysis for dye decomposition was observed in hexagonal wurtzite phase ZnS:Cu. As described herein, ZnS:Cu ceramic is shown to be a visible-light-responsive material with a band gap of ~2.77 eV. Under visible-light irradiation, the photocatalytic decomposition ratios of ZnS:Cu on 5 mg/L Rhodamine B, methylene blue, and acid orange 7 solutions reach 99.2%, 95.9%, and 78.8%, respectively. With respect to pyro-catalysis results, the decomposition ratio for acid orange 7 in the same concentration is 82.2%. For photo-/pyro-bi-catalysis, the decomposition ratio can reach ~95%. In summary, the ZnS:Cu ceramics exhibit strong visible-light photocatalysis and pyro-catalysis, making it a viable solution for decomposing synthetic dyes wastewater through utilizing the visible-light energy and cold-hot cycling.

Cyclic utilisation of waste tires as nanostructured anode materials for Li-ion batteries

ABSTRACT The cyclic utilization of waste tires has been a major problem that plagued the industry. In this paper, we explore a novel method of resource integration and application to solve this problem by using waste tires as the electrode materials. The waste tires were carbonized and coated with sucrose to prepare nano sulfur-carbon (NSC) and carbon-coated nano sulfur-carbon (NSC/C) materials. The results of the microstructures and morphologies showed that the NSC was composed of hexagonal ZnS nanoparticles and amorphous carbon. Electrochemical tests showed that the uncoated NSC composite had a high capacity of 426.6 mAh g-1, but it also presented a low initial efficiency with poor rate and cycling performance. After coating, the NSC/C exhibited an acceptable specific capacity of 374 mAh g-1 with lower capacity fading and superior cycling performance than NSC. Materials obtained from carbonized waste tires have great potential for use as anode materials in lithium-ion batteries.

Effects of structure on photoluminescence characteristics of Mn2+-doped ZnS quantum dots for anti-counterfeiting ink application

The zinc-blende-to-wurtzite transition of thioglycolic acid (TGA)-capped ZnS:Mn2+ QDs prepared at 80 °C in air has been observed with the increasing TGA/Zn2+ ratios. Effects of structure on the photoluminescence characteristics of ZnS:Mn2+ QDs were studied in this paper. The relative PL intensity ratio of the Mn2+ orange-red emission and the ZnS blue emission (IOE/IBE) and color purity (CP) (CP ≈ 65.6%) were maximum with the optimal molar ratio of TGA/Zn2+ = 3, which indicate the efficient transmission of excitation energy from the ZnS host to the Mn2+ impurity. Furthermore, the investigated result shows that the energy transfer in the cubic ZnS host lattice is more efficient than that of the hexagonal ZnS and the color correlated temperature (CCT) values increase with increasing the TGA/Zn2+ ratio. The crystal field strength (Dq) values of ZnS:Mn2+ QDs decrease from 603 cm−1 to 455 cm−1 with the increasing of the TGA/Zn2+ ratio from 0 to 6, respectively. The ZnS:Mn2+ QDs were applied in anti-counterfeiting ink, which was written on a glass sheet. The image was then excited by normal light and 385 nm UV light excitation, which emitted orange-red color with the UV light excitation. These investigated results can be particularly suitable for security ink applications or optoelectronic devices. Moreover, the zinc-blende-to-wurtzite phase transition in this study will be of great importance for the family of ZnS-based doped quantum dots.