IHJPAS. 36 (3) 2023 158 This work is licensed under a Creative Commons Attribution 4.0 International License 2SnO Strain of -Study the Effect of Manganese Ions Doping on the Size nanoparticles Using X-Ray Diffraction Data *Corresponding Author: taghreed.m.m@ihcoedu.uobaghdad.edu.iq Abstract In this study, SnO2 nanoparticles were prepared from cost-low tin chloride (SnCl2.2H2O) and ethanol by adding ammonia solution by the sol-gel method, which is one of the lowest-cost and simplest techniques. The SnO2 nanoparticles were dried in a drying oven at a temperature of 70°C for 7 hours. After that, it burned in an oven at a temperature of 200°C for 24 hours. The structure, material, morphological, and optical properties of the synthesized SnO2 in nanoparticle sizes are studied utilizing X-ray diffraction. The Scherrer expression was used to compute nanoparticle sizes according to X-ray diffraction, and the results needed to be scrutinized more closely. The micro- strain indicates the broadening of diffraction peaks for nanoparticles that are not ideal crystals. The extra broadening of the diffraction peak may lead to a miscalculation of the nanoparticle size. We use the Williamson-Hall method to directly compute and discuss the particle size and micro-strain of SnO2 nanoparticles and compare them with results obtained using the Scherrer method. In conclusion, the straight line has been derived due to Williamson–Hall methods demonstrating the nanoparticles' uniformity. Keywords: SnO2, Williamson-Hall, X-ray diffraction, Nanoparticles, Structural Properties 1. Introduction Many studies have been carried out intensively on wide band gap semiconductor materials over the last few years according to their potential use in various optical devices and physics applications [1]. Tin oxide SnO2 is one of the most important IV–VI semiconductors; it is n-type, has a wide band gap material around 3.6–4.0 eV [2], and has a large exciton binding energy of 130 meV [3]. The metal oxide semiconductor SnO2 has high chemical stability, low cost, high electron mobility, a long life, and a simple manufacturing technique [4]. Moreover, these characteristics make it a promising semiconductor material for different intriguing applications in technology [5]. The SnO2 nanomaterial has gotten great interest in different fields lately because of its prospective doi.org/10.30526/36.3.3052 Article history: Received 1 October 2022, Accepted 17 January 2023, Published in July 2023. Zahraa A. Kamil Department of Physics, College of Education for Pure Science Ibn-AL-Haitham, University of Baghdad, Baghdad, Iraq. zahraa.Ahmed1204a@ihcoedu.uobaghdad.edu.iq Ibn Al-Haitham Journal for Pure and Applied Sciences Journal homepage: jih.uobaghdad.edu.iq Tagreed M. Al-Saadi* Department of Physics, College of Education for Pure Science Ibn-AL-Haitham, University of Baghdad, Baghdad, Iraq. taghreed.m.m@ihcoedu.uobaghdad.edu.iq https://creativecommons.org/licenses/by/4.0/ mailto:taghreed.m.m@ihcoedu.uobaghdad.edu.iq mailto:zahraa.Ahmed1204a@ihcoedu.uobaghdad.edu.iq mailto:zahraa.Ahmed1204a@ihcoedu.uobaghdad.edu.iq mailto:taghreed.m.m@ihcoedu.uobaghdad.edu.iq mailto:taghreed.m.m@ihcoedu.uobaghdad.edu.iq IHJPAS. 36 (3) 2023 159 uses in gas sensors, catalytic, electrochemical, anodes in lithium batteries, optoelectronic devices, and biomedical applications due to its suitability, cost, high photosensitivity, and stability [6]. There are different techniques employed to synthesize and obtain the SnO2 nanoparticles, such as thermal oxidation, the sol-gel procedure, chemical vapor deposition, and spray pyrolysis [7]. Novel physical features arising from size uniformity reduction and dispersion of SnO2 are very important challenges for the present and future strategies of nanodevice applications in sensor, optical, and electronic fields [8]. Of the various methods mentioned that have the ability to produce large volumes of nanomaterial, the sol-gel method is the most simple, popular, inexpensive, and industrially applicable compared with other existing methods [9]. Nanometer-sized materials and semiconductor particles have unique features with a large potential for applications. Metal oxide semiconductors have been intensively used because of their low cost. Among the different metal oxide semiconductors, SnO2 is attracting more attention since it has higher conduction and is transparent [10]. Since nanoscale tin oxide SnO2 piqued curiosity, many researchers have devoted considerable efforts to synthesizing SnO2 nanostructures with varied morphologies, such as nanoparticles, nanowires, nanorods, nanotubes, nanosheets, and 3D nanospheres [11]. To achieve defect-free nanoparticles, we must make efforts during the synthesis of nanoparticles since a crystal flaw will influence the attributes of the resultant nanostructure materials. The crystal materials become perfect when they have extended, indefinitely uniform configurations in directions. In fact, crystals aren't flawless because, as size expands, there is an eternal variation. The effect of divergence from crystalline perfectly can be shown from the altered diffraction peak's widening [12]. According to broadening, we can calculate the fundamental crystallite size and lattice strain. However, the size of the coherent diffraction domain has been measured by crystalline size. The contact or sinter stress, grain boundary stress, and nonlinear stress cause lattice strain and stacking faults, which measure the distribution of lattice constants for crystal imperfection. Bragg peaks were influenced by lattice strain and crystallite size, which increased peak width intensity with shifting peak locations. Crystal structure, mechanical characteristics (strain and stress), and lattice parameters are influenced by pre- and post-heating treatment in the Sol-gel method [13]. In the present work, the SnO2 nanoparticle was prepared via a simple aqueous solution growth technique. The crystallite sizes for SnO2, which are derived via X-ray diffraction, are is using the W-H plotting approach while accounting for microstrain and compared with the mean particle sizes computed due to Scherrer’s equation. Scherrer’s equation has been used to compute crystallite size according to the adjusted line width. 2. Experimental Details Tin dioxide nanoparticles were prepared using the sol-gel method as follows: 5.259 g of tin chloride (SnCl4.5H2O) was dissolved in 150 ml of deionized water while stirring continuously for 40 minutes. Then, 6 ml of ammonia (NH3) was added to adjust the pH function while continuing to stir until it turned into a white gelatinous liquid. Using filter paper, the solution was filtered by continuous washing with distilled water. The sample was dried in a drying oven at 70°C for 7 hours. The sample was incinerated in an oven at 200°C for 24 hours. Finally, the material was ground with a ceramic mortar and converted into fine (nano) particles of SnO2. The other sample doped with manganese ions was prepared by adding manganese nitrate in the same way at a molar ratio of 5%. IHJPAS. 36 (3) 2023 160 3. Results and Discussion The crystallographic characterization of the synthesized structure material and phase purity of pure SnO2 doped with Mn ions is done by using the XRD pattern technique. It reveals the rutile tetragonal structure of SnO2 nanocrystals. The XRD diffraction of the sample showed that the top peaks were due to the complex of pure SnO2 nanoparticles. It can be listed as a tetragonal structure. We can show and record five distinct tin oxide peaks and detect them due to the patterns in the range (10°–80°) assigned to the planes (110), (101), (111), (211), and (301). The diffraction peaks were assigned to the tetragonal structure of tin dioxide. The crystallographic structure suggests that it is unaffected by the doping sample. In Table 2, it can be noted that the lattice parameters and unit cell size increase after adding the Mn3+ ions to the samples of SnO2 nanoparticles. The increase in the lattice parameters may be due to the smaller ionic radius of Mn3 + (0.65 Å) which was substituted in place of the Sn4 + (0.69 Å) site. The tin oxide phase didn’t change. Lattice constants are computes according to Match!3 software. Results are shown in Table 2. However, the density of tin oxide is calculated for the samples using X-ray data with an expression [14, 15]: 𝜌 = 𝑁 𝑀𝑤 𝑁𝐴𝑉 (1) Where, N, 𝑀𝑤 , 𝑁𝐴and 𝑉 are the number of atoms in the unit cell, molecule weight, Avogadro’s number, and lattice volume. The results of the density calculation from the X-ray are noted in the table: the density decreases with impurity according to equation (1), it is inversely proportional to the size of the unit cell. The data in Table 1 show agreement with the standard results. Figure 1. X- Ray diffraction of two samples of pure SnO2 nanoparticles and doped with Mn. 20 30 40 50 60 70 80 In te n si ty ( a .u .) 2 Theta (degree) 1 20 30 40 50 60 70 80 in te n si ty (a .u ) 2 Theta (degree) 2 (110) (110) (110) (101) (110) (110) (200) (110) (110) (211) (110) (110) (200) (110) (110) (110) (110) (110) (211) (110) (110) (101) (110) (110) (220) (110) (110) (220) (110) (110) (301) (110) (110) (301) (110) (110) IHJPAS. 36 (3) 2023 161 Table 1. Lattice constant and density of SnO2 nanoparticles. 𝜌 (g/cm3) Unit cell Volume (Å3) lattice constant (Å) Sample c a=b 7.0028 71.438 3.185 4.738 1 6.9648 71.850 3.202 4.737 2 Crystallite Size and Strain Scherer Method X-ray data were used for correlation peaks with crystallite size and lattice strain due to the dislocations [16] and vacancies [17]. The crystallite size of SnO2 nanoparticles can be determined using the Scherer equation with the extension method of the X-ray line that is given by [18, 19]. FWHM = K.λ D.cosθ (2) Where FWHM is the full width of the diffraction peak at half-maximum, K denotes the shape factor ≅ 0.89, λ= 0.15406 nm ,D is the crystallite size and θ denotes the x-ray incident angle.. Crystal defects are caused by peak broadening that’s caused by lattice strain and crystallite size. Peak broadening is related to the size of crystallites inversely; it is the result of a mix of instrumental effects and sample dependent. Using the connection, the FWHM corresponding to the tin oxide diffraction peak is calculated using the following equation [20]. FWHM = 𝛽𝑚𝑒𝑎𝑠𝑢𝑟𝑒𝑑 2 + 𝛽𝑖𝑛𝑠𝑡𝑟𝑢𝑚𝑒𝑛𝑡𝑎𝑙 2 (3) Williamson Hall Uniform Deformation Model (UDM) However, it can get a good rough estimation of crystallite size according to the Scherrer equation. Moreover, the precision of this method is well known, but it overlooks the microstrain and its effect on the diffraction pattern. It can benefit from the analysis of Williamson-Hall [21]. The Willamson-Hall plot method is used to evaluate the change in crystallite size and strain as a function of angle [20]. According to the Williamson-Hall procedures, the contribution of Bragg's individual to line enlargement is given as [22–24]: βcosθ = kλ D + 4 ε sinθ (4) Where (D) is the crystallite size of an X-ray diffraction peak, (βD) and (βε) are the contributions of crystallite size and the strain to the expansion of the peak. In Eq. 2, on the inside, the strain was assumed to be uniform in all crystal directions, implying a model of uniform deformation. The crystallite size is determined to indicate the strain depending on the slope of the fitting line [25]. Figure (2) shows sin θ plots with β cosθ to find the results of uniform deformation Where K is 0.94 and λ the wavelength at the target = 1.5406 Å. IHJPAS. 36 (3) 2023 162 Figure 2. UDM analysis of pure SnO2 nanoparticles and doped with Mn. Depending on Hooke's law, the stress σ is linear proportional to strain ε at elastic limit and can be calculated using [25]. 𝑌 = 𝜎 𝜀 (5) Where, Y is a Young’s modulus in the (hkl) planes. We assume the lattice deformation stress is to be uniform. As a result, in the second component of the equation, this is reduced to modify Eq. (4) to give [22]: 𝛽𝑐𝑜𝑠𝜃 = 𝑘𝜆 𝐷 + 4𝜎𝑠𝑖𝑛𝜃 𝑌 (6) The relation between 4𝑠𝑖𝑛𝜃 𝑌 and 𝛽𝑐𝑜𝑠𝜃 is linear and reduces to stress 𝜎 [26]. Elasticity modulus relates to the elastic compliances Aij at semiconductor nanoparticles according to equation [27]: 1 Y = 𝐴11 − (𝑘2𝑙2+𝑙2ℎ2+ℎ2𝑘2)(2𝐴11−2𝐴12−𝐴44) (ℎ2+𝑘2+𝑙2) (7) Where the elastic compatibilities are given by 𝐴11 = (𝑎11+𝑎12) (𝑎11−𝑎12)(𝑎11+2𝑎12) , 𝐴12 = (−𝑎12) (𝑎11−𝑎12)(𝑎11+2𝑎12) , and 𝐴44 = 1 𝑎44 The elastic compliance is estimated according to the experimental values of the elastic constants a11, a12 and a44, and equal to 316 GPa, 56 GPa and 115 GPa [28]. Figure 3. The USDM analysis of pure SnO2 nanoparticles and doped with Mn. y = -0.0017x + 0.0086 0 0.002 0.004 0.006 0.008 0.01 0.012 0 1 2 3 β co sɵ 4sinɵ 1 y = 0.0009x + 0.0031 0 0.001 0.002 0.003 0.004 0.005 0.006 0.007 0.5 1 1.5 2 2.5 3 β co sɵ 4sinɵ 2 y = 1E+08x + 0.003 0 0.001 0.002 0.003 0.004 0.005 0.006 0.007 0 1E-11 2E-11 3E-11 β co sθ 4sinθ/y 2y = -3E+06x + 0.0058 0 0.002 0.004 0.006 0.008 0.01 0.012 0.E+00 1.E-11 2.E-11 3.E-11 β co sθ 4sinθ/y 1 IHJPAS. 36 (3) 2023 163 The energy density model (EDM) However, the crystal size, stress parameters, and strain are calculated using the energy density and uniform deformation. Under this assumption, the crystals are defined in Eq.(4) and considered homogeneous and isotropic . In general, the energy density U is considered independent and can be determined from the relationship (5)[29]: 𝑈 = 1 2 𝜀2𝑌 (8) Inserting Eq.(8) in Eq.(6) to get the energy relation and strain utilizing by relation [27, 28]. 𝛽cosθ = 𝑘𝜆 𝐷 + (4𝑠𝑖𝑛𝜃( 2𝑈 Y ) 1 2) (9) Figure (4) indicate the plote between the 4sinθ (2/Y)1/2 and 𝛽cosθ . Figure 4. The UDEDM analysis of pure SnO2 nanoparticles and doped with Mn. Size-Strain Plot Model Due to the isotropic nature of the crystals, the Lorentzian and Gaussian functions are used to define crystallite size and strain [30].The linear relation between (dβcosθ)2 as a function of 𝑑 2βcosθ is given by [27] (dβcosθ)2= 𝐾 𝐷 (𝑑 2βcosθ) ( 𝜀 2 ) 2 (10) The strain and crystallite size are determined using the linear fit of the supplied results data and plotted (dβcosθ)2 as a function of 𝑑 2βcosθ and the y-intercept, as shown in Figure 5. y = 47.177x + 0.0055 0 0.002 0.004 0.006 0.008 0.01 0.012 0 0.000005 0.00001 β co sɵ 4sinɵ(2/y)^0.5 1 y = 262.25x + 0.0028 0 0.001 0.002 0.003 0.004 0.005 0.006 0.007 0 0.000005 0.00001 0.000015 β co sθ 4sinθ(2/y)^0.5 2 IHJPAS. 36 (3) 2023 164 Figure 5. The SSP analysis of pure SnO2 nanoparticles doped with Mn. Table 3.The results of D, 𝜀, and other factors calculated from different models. 4. Conclusion The structure of SnO2 nanoparticles has been synthesized by sol-gel autocombustion. 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