Comparison of average crystallite size by X-ray peak broadening and Williamson–Hall and size–strain plots for VO2+ doped ZnS/CdS composite nanopowder
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The paper deals with the exhaustive study and analysis of VO2+ ions doped ZnS/CdS composite nanopowder with the help of X-ray peak profile analysis (XPPA). The investigation has been carried out by applying a distinct pattern of Williamson–Hall (W–H) approach viz., uniform deformation model, the uniform stress deformation model and uniform deformation energy density model, and size strain plot (SSP). Fourier transforms infrared spectroscopy (FT-IR), scanning electron microscope and energy dispersive spectra (EDS) and transmission electron microscope (TEM) techniques. The XRD study is high manipulated order and fundamental focus is on phase identification, with some analysis on advanced concepts such as crystallite size and lattice strain have been estimated using the modified form of the W–H methods. XRD pattern confirmed that the structure of the sample belongs to the cubic system. The variation of lattice constant (a) with dopant is assigned to Vegard’s law. The root means square strain was identified from the interionic separation and lattice strain assumed on W–H models. FT-IR spectrum exhibited characteristic vibrational modes of Zn and Cd ions along with other bands. EDS analysis gives information about the elemental composition in the present sample. The shape of VO2+ ions doped ZnS/CdS composite nanopowder was spherical in TEM images. The result showed that there was a good agreement in the particle size obtained from the W–H method and the SSP method with TEM images.
KeywordsX-ray diffraction FT-IR Co-precipitation method W–H plots
The mechanical behavior of micro/nanoscale substance differs for their properties in terms of bulk nature, and it is familiar that “Small or nano range particles are stronger when compare to bulk materials in the present research”. Until now, electron microscopy is being used to analyze the small-scale techniques of objects placed on in situ and ex situ classification. The limitation of electron microscopy technique is a two-dimensional design of top surface from thin-sheet like foil of matter. Over the past twenty years, a large advancement is attained at third group synchrotrons that hard X-ray beam can target lowering down to the 100-nm size . A synchrotron is a certain class of regular particle accelerator, which can transfer the energy of the high-speed electrons into a strong-energy poly-chromatic X-ray beam . The strength of this mechanism as internal stress, research investigation for micro- and the nanoscale instrument is the estimation of stresses along with submicron clarity, the assessment of the unequal principal-stresses, and the evaluation of hydrostatic elements of the stress tensors . Synchrotron diffraction contained three types of techniques namely X-ray scattering, pair distribution function (PDF), X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS)  which can substantially provide structural characteristics of materials with a greater conclusion and completely 3D . During current research dimensions of physics, chemistry, and fabric science, transition metal oxides with nanostructure had mesmerized considerable absorption for the last couple of years concentrate of they are modern electrical and optical address with semiconductor crystals with massive binding energy (60 meV) . Currently, emergent attention has been given to composite nanoparticles taking into consideration that the association of two semiconductor nanocrystals will foremost to a sequence of novel optical and digital residences [6, 7]. Nanostructured semiconductors of type II-VI which are observed to be the leading substance because they are an advantage in a lot of fields like fuel, sensors , photoconductors, imaging, solar cells, biological detection, UV sensors, quick wavelength laser diodes, and different luminescence instruments [9, 10]. Amongst II-VI compound semiconductors nanosize particles, Zinc, and cadmium sulfide are mostly useful for the majority part of the promising materials for greater results . Zinc sulfide is a well-ordered nanoscale semiconductor compound for detecting UV , visible light considering that of its foremost energy gap of 3.68 eV (345 nm) and extreme reactivity. It has a wide range of possible applications in optoelectronics, optics, and solar energy devices [13, 14]. Cadmium sulfide with a direct bandgap of 2.42 eV (515 nm)  has a purpose in window layer materials,  LEDs  and photodetectors . Its purposes in photodetectors and solar cells when used at the part of in conjunction with narrow energy gap components like CdTe CdSe, CdO etc., in a similar way the nanocomposite matching of band gaps between any two add-ones of II-VI Semiconductor NCs, for illustration of CdSe/ZnS  CdS/ZnS , CdSe/CdS  and ZnO/ZnS  has been drastically concerned for the development of the charge transfer efficiency. The doping with transition metal ion VO2+ ions brought a tremendous alteration in structural properties. Additionally, to the easier properties, VO2+ ions doped ZnS/CdS composite nanopowder illustrates reveals further promising functions in the subject of sensors, optoelectronics , and ferroelectric memory devices. Doped ZnS/CdS composite nanopowder particles were incorporate with the assistant of remarkable physical and chemical procedure such as spray pyrolysis, RF sputtering, electrochemical deposition, chemical vapor deposition, chemical precipitation and, sol–gel methods [24, 25, 26, 27, 28, 29, 30, 31]. Among all these methods, chemical precipitation was more appropriate and suitable procedure due to simplicity, energy-efficient and eco-friendly route to produce VO2+ ions doped ZnS/CdS composite nanopowder . Secondly, comparative reviews of the suggest particle dimension from the powdered XRD, W–H models, FT-IR, SEM, EDS and TEM measurements. As the study of analytical quantity of dislocation densities are an extremely great deal with TEM investigation. The study of dislocation bend in irradiated substances is also constrained using TEM analysis . The concept of Diffraction peak profile investigation is a highly useful technique to explore the dislocation density, dislocation structure, and population distribution in the technically deformed objects due to such a reason which is a foundation to be a complementary procedure to TEM analysis [34, 35].
At present, XRD was employed in three types of diffraction techniques containing, powder diffraction, single-crystal XRD, and grazing incidence angle diffraction. A black and white X-ray beam of light is used in these experiments . XRD pattern is an acceptable approach to estimate the structural and phase characteristics of single crystals and/or polycrystalline components. Investigation of the mechanical action of micro-/nano size, structures of the electronic device highly essential. Crystallite size has an excellent coherent diffraction domain in XRD. Moreover, the average crystallite size of the particles varied as to the particle size as a result of the existence of grain boundaries and/or polycrystalline aggregates . The formation of strain in the crystalline lattices may be created by various reasons for example lattice dislocations, crystal imperfections, triple junctions, grain boundary, sinter or contract stresses, Coherency stresses stacking faults, etc., . Based on the present XRD pattern, several approaches have been employed to determine the lattice strain and crystallite dimension of elements. Under such a research scenario, we implement three models including Scherrer’s, W–H models and size–strain plot (SSP) methods. In Scherrer’s method, the crystallite size was measured using the maximum intensity of the diffraction peak in the present X-ray diffraction pattern. The Bragg width involvement produced based on crystallite size is in inverse relation to the crystallite size. Although, it should be noted that, the influence of non-uniform strain and instrumental results on the peak broadening has not been mentioned in Scherrer’s method. Thus, Scherrer’s method suggested only a lesser limitation on the average crystallite size . Along with several ways to study and/or evaluate the mean crystallite size and lattice strain attention to the peak profile analysis [Warren–Averbach (W–A) method, Fourier technique, W–H models, and Rietveld refinement technique], W–H analysis is a convenient procedure to estimate the average crystallite size and lattice strain-induced peak broadening taken account into consideration the shift in peak broadening against with an deflection angle of position 2Theta.
During the current research analysis on VO2+ ions doped ZnS/CdS composite nanopowder was synthesized through co-precipitation method. It has been found that this procedure is a simple method and rapid, gentle, energy-efficient and eco-friendly route to develop VO2+ ions doped ZnS/CdS composite nanopowder. Secondly, comparable evaluations of the essential element dimension, precise information about a small volume of sample can discern crystallite shape, as well as size and weight and atomic weight percentage in the prepared sample, can be found from TEM and SEM–EDS analysis. Subsequently, the effect of single concentration (0.01 mol%) of vanadium dopant was investigated on the morphological study of ZnS/CdS composite nanopowder. Transition metal (TM) at a small concentration does not seem to produce noticeable distortions in the structure . The unit cell parameters slightly change with dopant content which shows effectively built into the host lattice due to this there is no secondary diffraction peaks from other crystalline forms are noticed . In the present study, the crystallite size of VO2+ ions doped ZnS/CdS composite nanopowder gives the structural parameters such as average particle size (D), microstrain (ε) and dislocation density (δ) values are evaluated from Scherrer’s method and W–H Analysis. The average crystallite size from XRD is highly correlated with TEM analysis. In extension, the lattice strain was approximated with three W–H models, specifically, (UDM), (USDM), (UDEDM), and (SSP). This analysis outperforms the study which has been made so far.
All chemical reagents which are of the analytical grade, and have been purchased from pure Merck chemical supplies, India. The new synthesized route of a VO2+ ion-doped ZnS/CdS composite nanopowder were used in particular Zinc acetate Zn(CH3COO)2, Cadmium acetate Cd(CH3COO)2, Sodium sulfide (Na2S), Vanadium pentoxide (V2O5) and Ethanol were used as sources. Deionized water was used for all dilution and sample preparation. All the chemicals are above are 99% purity. All the glass wear used in this experimental was acid washed.
2.2 Preparation of VO2+ ions doped ZnS/CdS composite nanopowder
VO2+ ions doped ZnS/CdS composite nanopowder was successfully synthesized by co-precipitation method at room temperature. The powder form of a zinc acetate 0.2 mol% was dissolved in 50 mL same amount of water–ethanol matrix to an equal molar amount of Na2S aqueous solution were mixed drop by drop. The collection of sample mixture was stirred magnetically at 80 °C until a homogeneous milky white precipitate formed. This is the indication of the formation of ZnS nanoparticles. For the next step, 0.09 mol% of cadmium acetate powder was dissolved in a 50 mL equal volume of the water–ethanol matrix which is added to the above colloidal solution then stirred steadily. After 10 min, 0.1 mol% of Na2S 50 mL (prepared in a deionized water–ethanol matrix) solution was mixed dropwise in the above solution, subsequently, after 4 h of continuous stirring, the milky white solution turned to pale yellow colored voluminous precipitate appeared which indicates the composition of ZnS/CdS nanoparticles. Lastly, 0.01 mol% of V2O5 dissolved in 50 mL identical volumes of water–ethanol matrix added to the above composite solution and stirred constantly for 3 h. The obtained solution was washed several times with deionized water to remove undesirable impurities. Then the solution was kept in an ultracentrifuged at 10,000 rpm for about 30 min. The fine powder was collected and dried in a hot air oven at 120 °C for 2 h and grind with agate motor by hand milling. Finally synthesized VO2+ ions doped ZnS/CdS composite nanopowder was obtained and characterized by different techniques.
Powder X-ray diffraction pattern (XRD) of the prepared sample is recorded on Shimadzu XRD 6100 diffractometer. Fourier Transformed Infrared (FT-IR) spectrum was recorded by using KBr pellet on Shimadzu IR Affinity-Is in the range 4000–400 cm−1. Scanning Electron Microscope (SEM) and Energy Dispersive X-ray Spectroscopy (EDS) images were taken from ZEISS EVO 18. Transmission electron microscope (TEM) images are recorded on HITACHI H-7600 and CCD CAMERA system AMTV600 by dispersing the samples in ethanol.
3 Results and discussion
3.1 Structural properties
Interplanar spacing (dhkl) from XRD, JCPDS data card for corresponding <h k l> planes, percentage of variation of d, and FWHM for VO2+ ions doped ZnS/CdS composite nanopowder
<h k l>
% of contraction in d
<1 1 1>
<1 1 1>
<2 0 0>
<2 0 0>
<2 2 0>
<2 2 2>
<3 1 1>
<2 2 2>
3.2 Debye–Scherer’s procedure
3.3 Approximation of microstrain (ε)
3.3.1 Williamson–Hall (W–H) models
3.4 Uniform deformation model (UDM)
Geometric parameters for synthesized VO2+ ions doped ZnS/CdS composite nanopowder
ε × 10−3
ε × 10−3
ε × 10−3
ued (kJ m−3)
εa × 10−3
εRMS × 10−4
3.5 Uniform stress deformation model (USDM)
3.6 Uniform deformation energy density model (UDEDM)
3.7 Size-strain plot (SSP)
The ‘Gaussian feature well-known shows strain’ and the “crystallite measurement” profile through Lorentzian function . A different class of evaluation the dimensions stress plot specifications can also be obtained through SSP plot for anisotropic line broadening
From all methods, the estimated values from the y-cut of the graphs consistent with the conventional crystallite size are found to be 11.36, 11.77, 11.12 and 8.71 nm respectively as shown in Table 2. This is almost similar and also in the order of nanoscale. From the SSP approach, the crystallite dimension value is in well-matched with Scherrer’s method and is in evaluation with W–H models. From these studies, our values are more appropriate to the literature report 
3.8 Estimation of RMS strain
The XRD peak broadening reveals crystallites size, microstrain, and instrumental broadening. In another way the cause of strain is interrelated to lattice irregularity, RMS strain gives the distortion value. The higher the value of RMS strain, the lesser is the crystallite size.
3.9 Structural parameter (texture coefficient)
If TC(hkl) (~ 1) for every <hkl> planes, then the nanoparticles are with a randomly oriented crystalline similar to the JCPDS card reference.
TC(hkl) (> 1) implies that the VO2+ ions doped ZnS/CdS nanoparticles include a larger degree of orientation alongside C-axis.
Zero < TC(hkl) < 1 point out the lack of grains aligned in that path. Finally, the average crystallite dimension and the strain values estimated from all W–H models reveals to very suitable and intimately to interrelated Fig. 2d–f.
4 FTIR study
FTIR vibrational band assignments of VO2+ ions doped ZnS/CdS composite nanopowder
Vibrational frequency (cm−1)
C–O carboxylic acid
Symmetric bending vibration of H2O
5 Morphological studies
In this paper, VO2+ ions doped ZnS/CdS composite nanopowder was successfully synthesized by co-precipitation procedure and characterized by XRD, FT-IR, SEM–EDS and TEM analysis. Generally, XRD is adapted to support the evaluation of crystallites with a broad (or) multi-modal size distribution. From the X-ray peak broadening studies, it was noticed the intensity of the X-ray diffraction line depends on the elemental composition of the sample and its preparation conditions. The set of all values of VO2+ ions doped ZnS/CdS composite nanopowder belong to the cubic structure. Observed X-ray diffraction peaks can be related to planes of atoms to assist in analyzing the atomic microstructure of a prepared sample. Both microstrain and crystallite size can be analyzed only when the broadening due to both are equivalent. The amount of microstrain is large the maximum observable crystallite size will be small. Due to vanadium ion doping causes the decrease in the crystallite size and enhanced the dislocation density, microstrain, and inter-planar spacing and also some lattice distortion will be created in the structure of the host material. Also, the estimated values of the mean particle size from the modified W–H plot and SSP methods are held a good agreement with TEM analysis.
J. Madhavi would like to thank Acharya Nagarjuna University, Guntur for providing URF. Prof. RVSSN Ravi Kumar would like to thank the UGC-DSA1 and DST-FIST, New Delhi for providing financial assistance to the Department of Physics, Acharya Nagarjuna University to carry out the present research work.
Compliance with ethical standards
Conflict of interest
The author(s) declare that they have no conflict of interests.
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