Synthesis,effect of capping agents and optical properties of manganese‐doped zinc sulphide nanoparticles

Mn²⁺‐doped ZnS nanoparticles have been successfully synthesized by a chemical precipitation method, using non‐ionic surfactants such as PMMA and PEG. The particles were prepared in an air atmosphere at 80°C. X‐ray diffraction (XRD), transmission electron microscopy (TEM), UV‐visible and photoluminescence (PL) studies were used to investigate the effect of the capping agent on the size, morphology and optical properties of the ZnS–Mn²⁺ nanoparticles. Enhanced PL was observed from the surfactant‐capped ZnS–Mn²⁺ nanoparticles. The PL spectra showed a broad blue emission band in the range 460–445 nm and a Mn²⁺‐related yellow‐orange emission band in the range 581–583 nm. Copyright © 2012 John Wiley & Sons, Ltd.     

Optical and structural characterization of CdS/ZnS and CdS:Cu2+/ZnS core–shell nanoparticles

Core‐shell CdS/ZnS (Zn 0.025?0.125 M) and CdS:Cu²⁺(1%)/ZnS nanoparticles were successfully synthesized using a chemical method. X‐ray diffraction (XRD), high‐resolution transmission electron microscopy (HR TEM), photoluminescence (PL) and UV/Visible (UV/Vis) techniques were used to characterize the novel CdS/ZnS and CdS:Cu²⁺/ZnS core–shell nanoparticles. All absorption peaks of the synthesized samples were highly blue‐shifted from the bulk CdS and ZnS. Very narrow and symmetric PL emission was observed in the yellow region for core–shell CdS/ZnS. Furthermore, the PL emission of CdS/ZnS was tuned into orange region by incorporate the Cu ion into the core CdS lattice. Copyright © 2013 John Wiley & Sons, Ltd.     

Influence of thiol capping on the photoluminescence properties of L‐cysteine‐, mercaptoethanol‐ and mercaptopropionic acid‐capped ZnS nanoparticles

Mercaptoethanol (ME), mercaptopropionic acid (MPA) and L‐cysteine (L‐Cys) having ‐SH functional groups were used as surface passivating agents for the wet chemical synthesis of ZnS nanoparticles. The effect of the thiol group on the optical and photoluminescence (PL) properties of ZnS nanoparticles was studied. L‐Cysteine‐capped ZnS nanoparticles showed the highest PL intensity among the studied capping agents, with a PL emission peak at 455 nm. The PL intensity was found to be dependent on the concentration of Zn²⁺ and S^2– precursors. The effect of buffer on the PL intensity of L‐Cys‐capped ZnS nanoparticles was also studied. UV/Vis spectra showed blue shifting of the absorption edge. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis,characterization and optical properties of polymer‐based ZnS nanocomposites

Nanostructured polymer–semiconductor hybrid materials such as ZnS–poly(vinyl alcohol) (ZnS–PVA), ZnS–starch and ZnS–hydroxypropylmethyl cellulose (Zns–HPMC) are synthesized by a facile aqueous route. The obtained nanocomposites are characterized using various techniques such as X‐ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), UV/vis spectroscopy and photoluminescence (PL). XRD studies confirm the zinc blende phase of the nanocomposites and indicate the high purity of the samples. SEM studies indicate small nanoparticles clinging to the surface of a bigger particle. The Energy Dispersive Analysis by X‐rays (EDAX) spectrum reveals that the elemental composition of the nanocomposites consists primarily of Zn:S. FTIR studies indicate that the polymer matrix is closely associated with ZnS nanoparticles. The large number of hydroxyl groups in the polymer matrix facilitates the complexation of metal ions. The absorption spectra of the specimens show a blue shift in the absorption edge. The spectrum reveals an absorption edge at 320, 310 and 325 nm, respectively. PL of nanocomposites shows broad peaks in the violet–blue region (420–450 nm). The emission intensity changes with the nature of capping agent. The PL intensity of ZnS–HPMC nanocomposites is found to be highest among the studied nanocomposites. The results clearly indicate that hydroxyl‐functionalized HPMC is much more effective at nucleating and stabilizing colloidal ZnS nanoparticles in aqueous suspensions compared with PVA and starch. Copyright © 2015 John Wiley & Sons, Ltd.     

Structural and optical properties of Cu‐doped ZnS nanoparticles formed in chitosan/sodium alginate multilayer films

Chitosan/alginate multilayers were fabricated using a spin‐coating method, and ZnS:Cu nanoparticles were generated within the network of two natural polysaccharides, chitosan and sodium alginate. The synthesized nanoparticles were characterized using an X‐ray diffractometer (XRD), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS) and atomic force microscopy (AFM). The results showed that cubic zinc blende‐structured ZnS:Cu nanoparticles with an average crystal size of ~ 3 nm were uniformly distributed. UV–vis spectra indicate a large quantum size effect and the absorption edge for the ZnS:Cu nanoparticles slightly shifted to longer wavelengths with increasing Cu ion concentrations. The photoluminescence of the Cu‐doped ZnS nanoparticles reached a maximum at a 1% doping level. The ZnS:Cu nanoparticles form and are distributed uniformly in the composite multilayer films with a surface average height of 25 nm. Copyright © 2013 John Wiley & Sons, Ltd.     

Luminescence study of monodispersed ZnS nanoparticles

Monodispersed ZnS nanoparticles have been successfully synthesized by a chemical precipitation method in an air atmosphere using polyvinylpyrrolidone (PVP) and sodium hexametaphosphate (SHMP) as surfactants. The synthesized nanoparticles were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectrometer (FT‐IR), UV–Vis optical absorption and photoluminescence (PL) spectra. Prepared surfactants capped ZnS nanoparticles are highly homogeneous and well dispersed. Optical absorption spectra showed a strong blue shift from the uncapped particles due to the quantum confinement effect. The capped ZnS emission intensity is enhanced than more the uncapped particles. The size of the synthesized particles is around 4–6.5 nm range. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis of ZnSe and ZnSe:Cu quantum dots by a room temperature photochemical (UV‐assisted) approach using Na2SeO3 as Se source and investigating optical properties

In this study, ZnSe and ZnSe:Cu quantum dots (QDs) were synthesized using Na₂SeO₃ as the Se source by a rapid and room temperature photochemical (UV‐assisted) approach. Thioglycolic acid (TGA) was employed as the capping agent and UV illumination activated the chemical reactions. Synthesized QDs were successfully characterized using X‐ray diffraction (XRD), transmission electron microscopy (TEM), photoluminescence (PL) and UV–visible (UV–vis) spectroscopy, Fourier transform‐infrared (FT‐IR), and energy dispersive X‐ray spectroscopy (EDX). XRD analysis demonstrated the cubic zinc blend phase QDs. TEM images indicated that round‐shaped particles were formed, most of which had a diameter of about 4 nm. The band gap of the ZnSe QDs was higher than that for ZnSe in bulk. PL spectra indicated an emission with three peaks related to the excitonic, surface trap states and deep level (DL) states. The band gap and QD emission were tunable only by UV illumination time during synthesis. ZnSe:Cu showed green emission due to transition of electrons from the Conduction band (CB) or surface trap states to the ²T₂ acceptor levels of Cu²⁺. The emission was increased by increasing the Cu²⁺ ion concentration, such that the optimal value of PL intensity was obtained for the nominal mole ratio of Cu:Zn 1.5%.     

Effect of particle size on activation energy and peak temperature of the thermoluminescence glow curve of undoped ZnS nanoparticles

This paper reports the effect of particle size on the thermoluminescence (TL) of undoped ZnS nanoparticles. ZnS nanoparticles were prepared using a chemical precipitation method in which mercaptoethanol was used as the capping agent. The nanoparticles were characterized by X‐ray diffraction, field emission gun‐scanning electron microscopy and high‐resolution transmission electron microscopy. When the concentrations of mercaptoethanol used are 0, 0.005, 0.01, 0.015, 0.025, 0.040 and 0.060 M, the sizes of the nanoparticles are 2.86, 2.81, 2.69, 2.40, 2.10, 1.90 and 1.80 nm, respectively. Initially, the TL intensity of UV‐irradiated ZnS nanoparticles increases with temperature, attains a peak value I_m for a particular temperature T_m, and then decreases with further increases in temperature. The values of both I_m and T_m increase with decreasing nanoparticle size. Whereas the activation energy decreases slightly with decreasing nanoparticle size, the frequency factor decreases significantly as the nanoparticle size is reduced. The order of kinetics for the TL glow curve of ZnS nanoparticles is 2. Expressions are derived for the dependence of activation energy (E_a) and T_m on nanoparticle size, and good agreement is found between the experimental and theoretical results. Copyright © 2015 John Wiley & Sons, Ltd.     

Tuneable luminescence properties of EDTA‐assisted ZnS:Mn nanocrystals from a yellow‐orange to a red emission band

Luminescence technology has been improved with the help of semiconductor nanoparticles that possess novel optical and electrical properties compared with their bulk counterpart. The aim of this study was to design semiconductor nanocrystals in their pure (ZnS) or doped form (ZnS:Mn) with different concentrations of Mn²⁺ ions by a wet chemical route stabilized by ethylenediamine tetra‐acetic acid (EDTA) and to evaluate their luminescence properties. The nanocrystals were characterized by physicochemical techniques such as X‐ray diffraction (XRD), High‐resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SEAD), EDS, and ultraviolet (UV)–visible light and photoluminescence (PL) studies. These results showed the presence of cubic phase and spherically shaped nanocrystals. A blue shift with respect to their bulk counterpart was observed. PL emission spectra were observed with a fixed blue peak and the yellow‐orange bands were red shifted towards the red region under the same excitation wavelength. The orange‐red bands were attributed to the radiation transition of electrons in 3d5 unfilled shells of Mn²⁺ ions [⁴T₁(⁴G)‐⁶A₁(⁶S)]; the ZnS matrix varied with Mn²⁺ concentration. Shift and increase in the intensity of the PL and absorption bands were observed with increase in Mn content. The study showed that Mn²⁺‐doped ZnS nanocrystal emission bands can be tuned from the yellow‐orange to the red regions under a controlled synthesis process and could be used as promising luminescent emitters in the biology field upon functionalization with suitable materials. Further studies on construction with various other materials will be useful for practical applications.     

Thermoluminescence of mercaptoethanol‐capped ZnS:Mn nanoparticles

The thermoluminescence (TL) of nanoparticles has become a matter of keen interest in recent times but is rarely reported. This article reports the synthesis of ZnS:Mn nanocrystals using a chemical route, with mercaptoethanol (ME) as the capping agent. The particle sizes for the nanocrystals were measured by X‐ray diffraction (XRD) and also by studying transmission electron microscopy (TEM) patterns. The particle sizes of the synthesized samples were found to be between 1 and 3 nm. For samples with different concentrations of the capping agent, it was found that the TL intensity of the ZnS:Mn nanoparticles increased as the particle size decreased. A shift in the peak position of the TL glow curve was also seen with decreasing particle size. The TL intensity was found to be maximal for samples with 1.2% of Mn. A change in the peak position was not found for samples with different concentrations of Mn. The half‐width glow peak curve method was used to determine the trap‐depth. The frequency factor of the synthesized samples was also calculated. The stability of the charge carriers in the traps increases with decreasing nanoparticle size. The higher stability may be attributed to the higher surface/volume ratio and also to the increase in the trap‐depth with decreasing particle size. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis,characterization and thermoluminescence studies of Mn‐doped ZnS nanoparticles

ZnS:Mn nanoparticles were prepared by a chemical precipitation method and characterized by X‐ray diffraction (XRD), field emission gun scanning electron microscope (FEGSEM), and high resolution transmission electron microscopy (HRTEM). Capping agent (mercaptoethanol) concentrations used were 0 M, 0.005 M, 0.01 M, 0.015 M, 0.025 M, 0.040 M, and 0.060 M, and resulted in nanoparticles sizes of 2.98 nm, 2.9 nm, 2.8 nm, 2.7 nm, 2.61 nm, 2.2 nm and 2.1 nm, respectively. The thermoluminescence (TL) glow curve was recorded by heating the sample exposed to UV‐radiation, at a fixed heating rate 1°C sec^–1. The TL intensity initially increased with temperature, attained a peak value I_m for a particular temperature, and then decreased with further increase in temperature. The peak TL intensity increased with decreasing nanoparticle size, whereas the temperature corresponding to the peak TL intensity decreased slightly with reducing nanocrystal size. As a consequence of increase in surface‐to‐volume ratio and increased carrier recombination rates, the TL intensity increased with decreasing nanoparticle size. It was found that, whereas activation energy slightly decreased with decreasing nanoparticle size, the frequency factor decreased significantly with reduction in nanoparticle size. Copyright © 2015 John Wiley & Sons, Ltd.     

Eu2+‐induced enhancement of defect luminescence of ZnS

The Eu²⁺‐induced enhancement of defect luminescence of ZnS was studied in this work. While photoluminescence (PL) spectra exhibited 460 nm and 520 nm emissions in both ZnS and ZnS:Eu nanophosphors, different excitation characteristics were shown in their photoluminescence excitation (PLE) spectra. In ZnS nanophosphors, there was no excitation signal in the PLE spectra at the excitation wavelength λ_ex > 337 nm (the bandgap energy 3.68 eV of ZnS); while in ZnS:Eu nanophosphors, two excitation bands appeared that were centered at 365 nm and 410 nm. Compared with ZnS nanophosphors, the 520 nm emission in the PL spectra was relatively enhanced in ZnS:Eu nanophosphors and, furthermore, in ZnS:Eu nanophosphors the 460 nm and 520 nm emissions increased more than 10 times in intensity. The reasons for these differences were analyzed. It is believed that the absorption of Eu²⁺ intra‐ion transition and subsequent energy transfer to sulfur vacancy, led to the relative enhancement of the 520 nm emission in ZnS:Eu nanophosphors. In addition, more importantly, Eu²⁺ acceptor‐bound excitons are formed in ZnS:Eu nanophosphors and their excited levels serve as the intermediate state of electronic relaxation, which decreases non‐radiative electronic relaxation and thus increases the intensity of the 460 nm and 520 nm emission dramatically. In summary, the results in this work indicate a new mechanism for the enhancement of defect luminescence of ZnS in Eu²⁺‐doped ZnS nanophosphors. Copyright © 2016 John Wiley & Sons, Ltd.     

Luminescence study on Mn,Ni co‐doped zinc sulfide nanocrystals

Zinc sulfide (ZnS) doped with transition metal has been used as phosphor for various optoelectronic applications. In the present report, ZnS:Mn doped and ZnS:Mn,Ni co‐doped were prepared using chemical co‐precipitation method using polyvinyl pyrolidone as a surfactant. The structural studies were carried out using an X‐ray diffraction technique; optical studies have been performed using ultraviolet–visible light absorption and photoluminescence (PL) spectroscopy. The presences of functional groups were confirmed using Fourier transform infrared spectroscopy. The X‐ray diffraction study and Reitveld analysis confirms the formation of cubic phase with crystalline size 2–3 nm for undoped and doped ZnS nanoparticles. A novel and enhanced luminescence characteristic have been observed in PL spectra. The luminescence intensity of Mn,Ni co‐doped ZnS in the blue region is much higher of that of ZnS. The PL results indicate that the doping of Ni creates shallow trap states or luminescence centres in the forbidden energy gap, which quenches the Mn states emission. Concentration quenching has been observed in Mn‐doped ZnS nanoparticles. From CIE coordinates, it is seen that the yellow and blue light emission of ZnS:Mn,Ni co‐doped nanophosphor may be a promising candidate for display devices and phosphor converted light‐emitting diode applications.     

Synthesis of cubic ZnS microspheres exhibiting broad visible emission for bioimaging applications

Biocompatible ZnS microspheres with an average diameter of 3.85 µm were grown by solvo‐hydrothermal (S‐H) method using water–acetonitrile–ethylenediamine (EDA) solution combination. ZnS microspheres were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), high‐resolution transmission electron microscopy (HRTEM), Fourier transform (FT)‐Raman spectroscopy and Fourier transform infrared spectroscopy (FTIR) techniques. The broad photoluminescence (PL) emissions from 380–580 nm that were seen from the ZnS microspheres attributed to the increase in carrier concentration, as understood from the observed intense Raman band at 257 cm^–1. Cytotoxicity and haemocompatibility investigations of these ZnS microspheres revealed its biocompatibility. ZnS microspheres, along with biological cell lines, were giving visible light emission and could be used for bioimaging applications. Copyright © 2015 John Wiley & Sons, Ltd.     

Luminescence investigation of a cerium‐doped yttrium vanadate phosphor

Cerium (Ce³⁺)‐doped (1, 3, and 7 mol%) yttrium vanadate phosphors were prepared using a co‐precipitation technique. The structural and optical properties of the synthesized samples were studied using X‐ray diffraction (XRD), Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), high‐resolution transmission electron microscopy (HR‐TEM), optical absorption, and photoluminescence (PL) spectroscopy techniques. The tetragonal structure and the formation of the nanosized crystallites in the YVO₄:Ce phosphor were confirmed using XRD analysis. HR‐TEM morphology showed rod‐like nanoparticles of different sizes. Optical absorption spectra demonstrated strong absorption bands at 268 and 276 nm. PL spectra showed strong peaks at 546, 574, and 691 nm following excitation at 300 nm. The calculated CIE chromaticity coordinates demonstrated that YVO₄:Ce could be used as a novel phosphor for the development of light‐emitting diode lamps.     

Characterization and luminescence properties of CaMgSi2O6:Eu2+ blue phosphor

A blue CaMgSi₂O₆:Eu²⁺ phosphor was prepared by the solid‐state reaction method and the phosphor characterized in terms of crystal structure, particle size, photoluminescence (PL), thermoluminescence (TL) and mechanoluminescence (ML) properties using X‐ray diffraction (XRD), transmission electron microscopy (TEM), PL spectroscopy, TLD reader and ML impact technique. The XRD result shows that phosphor is formed in a single phase and has a monoclinic structure with the space group C2/c. Furthermore, the PL excitation spectra of Eu²⁺‐doped CaMgSi₂O₆ phosphor showed a strong band peak at 356 nm and the PL emission spectrum has a peak at 450 nm. The depths and frequency factors of trap centers were calculated using the TL glow curve by deconvolution method in which the trap depths were found to be 0.48 and 0.61 eV. The formation of CaMgSi₂O₆:Eu²⁺ phosphor was confirmed by Fourier transform infrared spectroscopy. The ML intensity increased linearly with the impact velocity of the piston used to deform the phosphor. It was shown that the local piezoelectricity‐induced electron bombardment model is responsible for the ML emission. Finally, the optical properties of CaMgSi₂O₆:Eu²⁺ phosphors are discussed. Copyright © 2015 John Wiley & Sons, Ltd.     

Blue emitting ZnO nanostructures grown through cellulose bio‐templates

This paper presents a green and cost‐effective recipe for the synthesis of blue‐emitting ZnO nanoparticles (NPs) using cellulose bio‐templates. Azadirachta indica (neem) leaf extract prepared in different solvents were used as biological templates to produce nanostructures of wurtzite ZnO with a particle size ~12–36 nm. A cellulose‐driven capping mechanism is used to describe the morphology of ZnO NPs. The scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD), Fourier transform infra‐red (FTIR) and photoluminescence (PL) studies showed that solvents affect the growth process and the capping mechanism of bio‐template severely. Structural changes in ZnO NPs were evident with variation in pH, dielectric constants (DC) and boiling points (BP) of solvents. Furthermore, an energy band model is proposed to explain the origin of the blue emission in the as‐obtained ZnO NPs. PL excitation studies and the theoretical enthalpy values of individual defects were used to establish the association between the interstitial‐zinc‐related defect levels and the blue emission. Copyright © 2015 John Wiley & Sons, Ltd.     

Microwave-assisted synthesis of praseodymium (Pr)-doped ZnS QDs such as nanoparticles for optoelectronic applications

Praseodymium (Pr)-doped ZnS nanoparticles were synthesized using a low-cost microwave-assisted technique and investigations on their structure, morphology, optical properties, Raman resonance, dielectric properties, and luminescence were conducted. Broad X-ray diffraction peaks suggested the formation of low-dimensional Pr-doped ZnS nanoparticles with a cubic structure that was validated using transmission electron microscopy (TEM)/high-resolution TEM analysis. The energy gaps were identified using diffuse reflectance spectroscopy and it was found that the values varied between 3.54eV and 3.61eV for different samples. Vibrational experiments on Pr-doped ZnS nanoparticles revealed significant Raman modes at ~270 and ~350 cm⁻¹ that were associated with optical phonon modes that are shifted to lower wavenumbers, indicating phonon confinement in the synthesized products. The photoluminescence (PL) spectra of all samples demonstrated that the pure and Pr-doped ZnS nanoparticles were three-level laser active materials. Energy-dispersive X-ray spectroscopy and mapping study confirmed the homogeneous presence of Pr in ZnS. TEM studies showed that the particles were of very small size and in the cubic phase. The samples had high dielectric constant values between 13 and 24 and low loss values, according to the dielectric analysis. With an increase in frequency and a change in the Pr content of ZnS, an intense peak could be seen in the PL spectra at a wavelength of 360 nm, and some other peaks observed corresponded to the transition of Pr³⁺. The produced nanoparticles were appropriate for optoelectronic applications due to their short dimension, high energy gap, high dielectric constant, and low loss values.     

Rapid,controllable, one‐pot and room‐temperature aqueous synthesis of ZnO:Cu nanoparticles by pulsed UV laser and its application for photocatalytic degradation of methyl orange

Zinc oxide (ZnO) and ZnO:Cu nanoparticles (NPs) were synthesized using a rapid, controllable, one‐pot and room‐temperature pulsed UV‐laser assisted method. UV‐laser irradiation was used as an effective energy source in order to gain better control over the NPs size and morphology in aqueous media. Parameters effective in laser assisted synthesis of NPs such as irradiation time and laser shot repetition rate were optimized. Photoluminescence (PL) spectra of ZnO NPs showed a broad emission with two trap state peaks located at 442 and 485 nm related to electronic transition from zinc interstitial level (I_Zn) to zinc vacancy level (V_Zn) and electronic transition from conduction band to the oxygen vacancy level (V_O), respectively. For ZnO:Cu NPs, trap state emissions disappeared completely and a copper (Cu)‐related emission appeared. PL intensity of Cu‐related emission increased with the increase in concentration of Cu²⁺, so that for molar ratio of Cu:Zn 2%, optimal value of PL intensity was obtained. The photocatalytic activity of Cu‐doped ZnO revealed 50 and 100% increasement than that of undoped NPs under UV and visible irradiation, respectively. The enhanced photocatalytic activity could be attributed to smaller crystal size, as well as creation of impurity acceptor levels (T₂) inside the ZnO energy band gap.     

Thermoluminescence and photoluminescence studies on γ‐ray‐irradiated Ce3+,Tb3+‐doped potassium chloride single crystals

Single crystals of KCl doped with Ce³⁺,Tb³⁺ were grown using the Bridgeman–Stockbarger technique. Thermoluminescence (TL), optical absorption, photoluminescence (PL), photo‐stimulated luminescence (PSL), and thermal‐stimulated luminescence (TSL) properties were studied after γ‐ray irradiation at room temperature. The glow curve of the γ‐ray‐irradiated crystal exhibits three peaks at 420, 470 and 525 K. F‐Light bleaching (560 nm) leads to a drastic change in the TL glow curve. The optical absorption measurements indicate that F‐ and V‐centres are formed in the crystal during γ‐ray irradiation. It was attempted to incorporate a broad band of cerium activator into the narrow band of terbium in the KCl host without a reduction in the emission intensity. Cerium co‐doped KCl:Tb crystals showed broad band emission due to the d–f transition of cerium and a reduction in the intensity of the emission peak due to ⁵D₃–⁷F_j (j = 3, 4) transition of terbium, when excited at 330 nm. These results support that energy transfer occurs from cerium to terbium in the KCl host. Co‐doping Ce³⁺ ions greatly intensified the excitation peak at 339 nm for the emission at 400 nm of Tb³⁺. The emission due to Tb³⁺ ions was confirmed by PSL and TSL spectra. Copyright © 2015 John Wiley & Sons, Ltd.