Studies on the electrical and optical conductivity of Barium-Nickel ferrite nanoparticles doped with Zn

doi:10.21203/rs.3.rs-4889133/v1

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Studies on the electrical and optical conductivity of Barium-Nickel ferrite nanoparticles doped with Zn

https://doi.org/10.21203/rs.3.rs-4889133/v1

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The ceramic process was used for making the Barium w-type ferrite powder, which has the composition formula BaNi2-xZnxFe16O27, where x=0.0, 0.4, 0.8, 1.2, 1.6, and 2. In essence, the single-phase w-type hexagonal structure development is confirmed by the X-ray investigation. The concentration of zinc increases along with a modest increase in the lattice constant. An analysis of the sample using UV-VIS was done. Zinc may be obtained at varying concentrations, and it is discovered that band gaps exist in the semiconducting zone. There was a consistent variation in the optical constants of absorption coefficient, extinction coefficient, refractive index, and reflection with Zn content. It can be seen that the optical and electrical conductivity rise with photoenergy, and that the samples' conductivity peak grows as the Zn content decreases. As the electric susceptibility rises, it falls . When the concentration of zinc increases, the electric susceptibility falls.

band gaps

optical conductivity

ceramic technique

nano barium ferrite

Ferrite nanoparticle research has attracted a lot of attention lately because of improvements to its electrical and magnetic characteristics, in addition to their superior physical qualities. The w-type hexa-ferrites have been used in a wide range of scientific, industrial, and technological applications, such as magnetic resonance imaging, humidity sensors, ceramic coatings for solar cells, optoelectronic devices, recording disks, microwave devices, catalysts, information storage, and electronics. [1–2]. When compared to other material categories, the optical properties of dielectric materials generally became interesting due to their sensible transmission within the optical part of the spectrum. Thus, the optical constants such as the absorption coefficient, transmission, reflection, and index of refraction are essential characteristics to describe in order to analyze the optical properties of the ferrite materials When compared to other material fields the optical properties of dielectric substances generally became interesting due to their sensible transmission within the optical part of the spectrum. Therefore, optical constants such as the absorption coefficient, transmission, reflection, and index of refraction are essential characteristics to understand the optical properties of the ferrite materials in order to investigate their optical properties. [3, 4]. The Ba-W ferrites synthesed via ceramic method confirmed a differed in that the divalent ions of metal either took up octahedral positions or inhibited grain formation in place of the tetrahedral Zn²⁺ ions as well, and the magnetic characteristics were carefully added, were replaced with divalent metal ions that either accept octahedral positions or impede grain growth. In general, nickel ferrites preferred to occupy octahedral sites, whereas zinc ferrites prefer to occupy tetrahedral sites. [5]. Within the zinc-substituted Ba (Ni2-xZnx)2Fe16O27, khoreems et al. observed that the BaNi-W was as having extremely low permeability, with an increase in permeability and a fall in FMR frequency [6, 7]. Infrared spectra across the 400–4000 cm − 1 range of frequencies were used to investigate the optical properties of BaNi2 − xZnxFe16O27 ferrite. A pair distinct bands were found in the spectra during the analysis. The refraction index, absorbing coefficients, and reflectance spectrum of the doped ferrites were calculated for different amounts of Zn doping. The results showed that the addition of zinc ions changed the material's optical characteristics, such as an increase in its absorption capacity, a decline in its refraction, and changes in its refractive index. [8]. Ferrites' electric and magnetic characteristics will change as a result of interactions between tetrahedral ions and octahedral sites. Ni2 + and Fe3 + occupy the octahedral sites, while Zn2 + and Fe3 + occupy the tetrahedral sites.Also, As Zn ion substitution rises, composition-dependent values of the dielectric constant, dielectric loss, and tanσ decrease. In addition, the synthesis process, sintering temperature, chemical composition, etc., all have a significant impact on the ferrite's characteristics [9, 10]. Understanding the different forms of band gap energy structures—direct or indirect—is crucial for selecting the right materials for devices that need to produce light. For this reason, we synthesize the BaNi2–xZnxFe16O27 (x = 0, 0.4, 0.8, 1.2, 1.6, and 2) composition ferrite using a ceramic method in this work. We also investigate the impact of Zn addition on the formation of the ferrite's structure, optical performance, and gap in band energy

Utilizing the Ceramic method in accordance with their chemical formula, the Zinc substituted Barium-Nickle ferrite (BaNi2 xZnxFe16O27 with x = 0.0, 0.4, 0.8, 1.2, 1.6, and 2) was synthesized. BaCO3, NiO, ZnO, and Fe2O3 have been mixed in accordance with their individual stoichiometric ratios to create the composition samples. Additional information, as previously indicated [10, 11, 12]. Using an agate mortar, the first ingredients—BaCo, ZnO, NiO, and Fe2O3—were weighed, combined in the proper stoichiometric ratio, and ground for six hours. After ten hours in the air at 1270K, the mixture was air dried and presintered. Within the furnace, a sensor thermocouple regulates the temperature. After three hours, the ferrites were grounded once more. A hydraulic press was then used to press the powdered grain into pellet shape. After five hours of sintered pellets at 1250K, the pellets were gradually cooled to ambient temperature. The samples were then pulverized into fin powder. Following that, several analytical techniques were used to characterize the samples. Using an X-ray crystallographic (XRD) apparatus model Shimadzu EDX-720, the samples' XRD (X-ray diffraction) patterns were obtained using Cu Kα (λ = 1.54Ả) in a 2θ range of 5° to 75° at a step size of 0.02◦/s. Spectro fluorophotometer (Shimadzu RF 5301 model) fluorescent spectra and a UV-visible absorption spectrophotometer (Shimadzu PC 1650 model) were used to examine the optical characteristics associated with this sample.

3.1. XRD analysis

The XRD spectrum of BaNi2-xZnxFe16O27 hexaferrite is displayed in Fig. 1. The investigated particles' phase compositions show that all of the impurities phases were W-type hexaferrites; no other phases were found. Put differently, this picture solely depicts a single phase of hexagonal ferrite of the w type. Additionally, it was discovered that the samples and the BaNi2 W-type hexaferrites structure of p63/mmc agreed well. With Zn doped BaNi2-xZnxFe16O27, the typical powder reflection information from JCPDS,54–0097 is equivalent. The relation (1) is used to calculate the lattice values for hexagonal constructions [13].

$$\:\frac{1}{{\varvec{d}}_{\varvec{h}\varvec{k}\varvec{l}}^{2}}=\frac{4}{3}\frac{{\varvec{h}}^{2}+{\varvec{h}\varvec{k}}^{\:}+{\varvec{k}}^{2}}{{\varvec{a}}^{2}}+\frac{{\varvec{L}}^{2}}{{\varvec{C}}^{2}}$$

where relation (1) is used to determine $\:{\mathbf{d}}_{\mathbf{h}\mathbf{k}\mathbf{l}}^{\:}$ .

The variation of the lattice factors, an as well as c, and the ratio of c/a, with respect to the amount of zinc is depicted in Fig. 2. Because Zn2 + has a greater radius of ions (0.074 nm) than Ni2+ (0.069 nm), each lattice constants grow as one increases the Zinc content. Consequently, the ion's radius of replacement Zn2 + is higher than (0.074 nm) once it is more than (0.068 nm) of Ni2 + ion.

Figure_2.The relation between lattice parameters (a, c) and Zn²⁺ concentration for BaNiZnFe₁₆O₂₇

Figure_1. X-ray diffraction patterns for BaNiZnFe₁₆O₂₇

Optical measurements

In the ambient temperature, optical measurements were performed on all of the samples. UV-visible wavelengths of absorption were used to measure the spectrum optically transmitted of BaNi2-xZnxFe16O27 (x = 0.0, 0.4, 0.8, 1.2, 1.6, and 2), as indicated in Fig_3,a. As illustrated in Fig. 3.a, Every single sample were transparent at wider wavelengths (400 nm), and no light was absorbed or dispersed in the non-absorbing region (R + T = 1). The absorption region, or wavelength that is short (𝜆=400nm), is where absorption produces the disparity (R + T = 1). The samples' transmitted light border also slightly moves to the shorter wavelength length, suggesting that this energy gap will gradually widen as Zn concentration rises. It's also important to remember that transmittance increases with wavelength in all situations between 200 and 400 nm, with a notable exception of about 350 nm.

Every sample's transmission rises with wavelength around the 300–400 nm region before reaching the point of saturation at longer wavelengths. This substance can be used in reagents or solar energy cells due to its strong absorbance at wavelengths of 350 nm. Transmission is highest in the visible and infrared regions of the spectra and lowest in the ultraviolet spectrum. Figure 3.b illustrates how absorbance always decreases with wavelength; as a result, the absorbance was highest in the visible range at 334 nm and in the ultra violet zone at 234 nm. Moreover, the optical density falls with increasing Zn content. The absorption edge moves to the shorter-wavelength side as the concentration of zinc rises. Additionally, as the wavelength lengthens, it gets smaller. This implies that an electron's charge cannot be moved from the band of valence to the band of conduction by an incoming photon because its energy is not high enough to cross the energy gap. Transmission usually highest in both the visible as well as infrared regions of the spectrum and lowest in the ultraviolet. However, it is clear from Fig. 3's depiction of the spectrum's reflectance as an indicator of wavelengths that the spectrum of absorption behaves differently from the transmission spectra. Fig_3,a displays the refraction coefficient of the composite against wavelengths within the 200 nm–800 nm region. It is evident that the reflectance drops with increasing Zn concentration in the composite, whereas the reflection vs. wavelength profile stays constant. This suggests that there is minimal absorption within the near infrared and visible wavelength regions.

Absorption Coefficient(α)

The coefficient of absorbent (α) was determined calculated [14], for instance using the flowing formula, which is,

α = 2.303A/t (2)

where (t) is the specimen's thickness and A is the absorbance of the sample.

In Fig. 1,d, the greatest absorption coefficient appears twice. The first time it does so in the violet spectrum at (334nm), where the absorption ratio is 30%. At those wavelengths, direct electronic transitions are anticipated (high photon energy). The ultra violet range, with a 70% absorption ratio at (λ = 270 nm), is where the scones were formed. The figure shows that for all ferrite samples, the absorbance coefficient value declines with increasing incoming wavelength up to a specific wavelength (320–300 nm) that varies depending on the ferrite sample; at this wavelength, in the visible region, the absorbance coefficient nearly becomes invariant. When a wavelength (λ < 220nm) drops, absorption coefficient levels in the UV area also decrease. This is because of the absorption characteristics of the Zn element.

Extinction Coefficient (K)

One important characteristic of a substance's makeup that shows its ability to absorb it absorbed light at a particular wavelength is its wavelength extinction coefficient. It is computed as the proportion of light lost by absorption and scattering per unit average distance. Additionally, the fraction of light lost by absorption and scattering per unit distance is measured by the coefficient of extinction (k), which may be computed using Eq. (3) [15].

. K = αλ⁄4π (3)

In figure_3,c. It has been shown that the behavior of the sample's extinction value as a function of wavelength is comparable to that of the absorption coefficient. As the wavelength lengthens, it grows smaller. As zinc levels grow, the extinction coefficient value decreases.

The amount of light that is dissipated at this place as a result of scattering and absorption is indicated by its extension coefficient. Furthermore, it was demonstrated that the curved coefficient of absorption and curve (k) had the same character.

Optical Band Gap

Another crucial characteristic needed for optoelectronic device development is the optical gap of the band. Using the formula [16]:

α = $\:\frac{{A\left(hEg\right)}^{n}}{h}$ (4)

allowed for the calculation of the optical band gap from the coefficient of absorption optical α. Here, A is the constant that depends on the likelihood of the transition. The optical band gap is represented by the symbol Eg, the photon energy is represented by hv, and the constant n is equal to 1/2 or 2 for permitted direct or indirect transitions and 3 or 3/2 for prohibited direct or indirect transition probabilities. The Tauc plots (αhυ)2 vs(hυ) graph was used to compute the optical energy band gaps (Eg). Figure 4 plots the (αhν)^1/2 against (hυ) curves to assess the indirect band gap value of the obtained samples.

Due to the existence of two distinct slopes, the (αhv)^1/2 against (hυ) curves have an S-shape, which suggests that phonons are involved in the absorption process [17–18]. Figure 4 displays the plots from the synthesized samples. The energy of the indirect band gap (Eg). obtained for each of the synthesized samples by extrapolating the straight line at (αhυ)^1/2=0. The plots of the sample preparations are shown in Fig. 4. The energy value of the indirect band gap (Eg). For every variable sample that was synthesized, the anticipated indirect band values of energy for BaNi2-xZnxFe16O27 (x = 0.0, 0.4, 0.8, 1.2, 1.6, and 2) are shown in the table based on the assumption of a straight line at (αhν)^1/2=0. 1. The results obtained show that a band gap expands (Fig. 4) with increasing Zn2 + level, which may be an indication of confined quantum processes [19_20]. It has been found that Eg can be influenced by crystallite size, with smaller crystallites producing more discrete levels of energy and, thus, higher Eg [21]. The blue shift observed in all Zn-doped specimens (x = 0.0, 0.4, 0.8, 1.2, 1.6, 2) suggests the possibility of visible-light photoactivity. The optical energy that exists in the band gap increases with particle size, in contrast to the characteristics of light in general. The blue shift observed in all Zn-doped specimens (x = 0.0, 0.4, 0.8, 1.2, 1.6, 2) suggests the possibility of visible-light photoactivity. Unlike the typical characteristics of quantum bonding, the band the gap's optical energy increases as particle size decreases. Paul ONOCHIE, et al. [22]. shown that when Zn concentration is raised, doping Zn2 + results in a band gap rise.

Table 1

shows the BaNi2-xZnxFe16O27 ferrites composites' optical band gap Values..
Sample	Zn Concentration	Band gap (ev)
BaNi₂ Fe₁₆O₂₇	0	2.78 ev
BaNi_1.6Zn_0.4Fe₁₆O₂₇	0.4	2.89 ev
BaNi_1.2Zn_0.8Fe₁₆O₂₇	0.8	2.79 ev
BaNi_0.8Zn_1.2Fe₁₆O₂₇	1.2	2.91 ev
BaNi_0.4Zn_1.6Fe₁₆O₂₇	1.6	2.93 ev
BaZn₂Fe₁₆O₂₇	2	2.94 ev

Refractive Index(n)

When evaluating materials with optical properties for use in integrating optical devices, it is important to consider their refraction index, which acts as an important design factor for the device. Nonetheless, the index of refraction (n) is regarded as being one of the most important properties of optical substances because of its connection to the local field within the material and the electronic polarisation of ions. The formula (5) [23] is used to compute the index of refraction.

n = [(1 + R)/(1-R)] +[(4×R)/(1-R)²-k²]^1/2 (5)

the value of R stands for refraction, and k for the coefficient of extinction.

the coefficients of extinction for specimens in which Zn changes see Fig. 5. It's important to keep in mind that the refractive index is a measurement that rises with wavelength but starts to decrease in the visible spectrum. It can be shown that the refractive index generally drops with an increase in the quantity of Zn nanoparticles. For a more detailed description, the refractive index increases with increasing wavelength up to 334 nm and then drops with increasing wavelength. As the amount of Zn in the solution grows, the curve's form remains constant. With the increase in photonic energy and the increase in Zn content for the sample, the extinction coefficient values and refractive index generally show an increasing trend. the use of photonic energy This spectrum and dopant dependence of optical constants (n, k) will be important in establishing the materials' suitability for usage in optical data storage devices.

Optical Conductivity

A good method for examining the atomic structure of matter is optical conductivity. depends heavily on the material's refractive index and absorption coefficient and links the present density to a material's sensitivity to various light wavelengths in the electric field. The optical conductivity of BaNi_2 − xZn_xFe₁₆O₂₇ (x = 0.0, 0.4, 0.8, 1.2, 1.6, and 2) ferrite at different light photon energies with different Zn concentrations is investigated using Eq. (6) [24].

$$\:{\sigma\:}_{opt}=\frac{\:nc}{4}$$

α: is the absorbing coefficient, n is the refraction index, and c is the light velocity. BaNi_2 − xZn_xFe₁₆O₂₇ (x = 0.0, 0.4, 0.8, 1.2, 1.6, and 2) ferrite's optical conductivity is shown in Fig. 6 as a function of input photon energy.

. Observations reveal that the optical conductivity rises with the energy of light irradiation and that it starts to expand quickly at 5 eV and reaches a maximum value of approximately 5.5 eV. Its value is over 20 times higher than the preceding value.

The increase in the optical conductivity in the energy of photons range from 3.2 to 5.58 eV is responsible for the rise in coefficients of absorption in this region. Two optical conductivity thresholds exist because of the separate wavelengths in each of the regions. The discrete wavelengths at each of these regions have been accountable for the two photo conductivity peaks that are observed. There is a crucial wavelength in the visible and UV regions where this material appears to be more absorbent. As the Zn level of the samples decreases, so does their conductivity peak. Furthermore, it has been noted that the coefficient of absorption directly affects optical conductivity. However, these samples showed values of σopt in the ultraviolet wavelength range between 8.8 ×10⁹ to 1×10¹¹ s^− 1 and in the visible light zone between 9.1x10⁸ to 8.8x10⁹ s^− 1, indicating that the samples remain photosensitive. The samples' optical conductivity results agreed with previous research [25, 26, 27].

The relation [26] has been utilized to compute the electrical conductivity.

$$\:{\sigma\:}_{e}=\frac{2\:{\sigma\:}_{opt}}{\alpha\:}$$

Figure 7: the electrical conductivity of BaNi2-xZnxFe16O27 ferrites plotted versus length of wave

The electrical conductivity relationship with wavelength is seen in Fig. 7. The electrical conductivity dropped as the Zn content rose. But as the wavelength increased, it declined until it exceeded 400 nm, at which point it began to increase.

A dielectric material's degree of polarization as it responds to an applying electric field is indicated by its electrical susceptibility. A material's capacity to polarize in reaction to a field and, as a result, lower the overall electrical field inside the component increases with its electric susceptibility. Using the following relation, electrical susceptibility (χ) has been computed from the optical constants. [28]

$$\:{\epsilon\:}_{r}={\epsilon\:}_{^\circ\:}+4\pi\:{}_{C}={n}^{2}+{K}^{2}$$

$$\:{}_{c}=\frac{{n}^{2}-{k}^{2}-{\epsilon\:}_{0}}{4\pi\:}$$

which ε₀ represents the constant for dielectric without either free carrier contribution.

Electrical susceptibility has an average value of about 0.0961 at wavelength = 800 nm. The electric susceptibility (χ) versus wavelength is shown in Fig. 8. The electrical susceptibility value fell between 2.8 to 0.86 as the Zn content rose.

The ferrite (BaNi2-xZnxFe16O27 with x values x = 0.0, 0.4, 0.8, 1.2, 1.6, and 2) has been synthesized using a ceramic technique. a single-phase hexagonal structure's development has been verified by the XRD analysis results. The crystalline lattice structure constant's parameters rise when zinc levels rise, which is because zinc ions have higher ionic radii than nickel ions. exhibits changes in crystallite size as zinc concentration rises. Barium-based ferrites (BaNi2-xZnxFe16O27) had a crystallite size of 36.5 nm at x = 0.0 at first, but after substituting zinc (x = 0.4), the crystallite size dropped to 35.18 nm. then progressively rose to 36.7 nm as the concentration of zinc rose to x = 2. Nickel acts as a crystallite inhibitor, as seen by the rise in the size of crystals with the zinc content. The samples' gaps in band energy, which was determined using the Tauc plot, rose from 2.258 eV to 2.8306 eV as the level of zinc increased. Every sample's transmittance rises as wavelength increases in the 300–400 nm region before reaching a saturation point at longer wavelengths. This material exhibits significant absorption at 350 nm wavelengths. As the Zn content increases, the absorption edge shifts toward the short- wavelength side. For all ferrite samples, the absorption coefficient value declines with increasing wavelength up to a specific wavelength (320–300 nm) in the visible area, where α almost becomes invariant. In the ultraviolet (UV) region, the absorbance coefficients value is drop as the wavelengths (𝜆<220nm) drops. This is because zinc is an absorbing material element. The refraction index and extinction value coefficients exhibit a generally rising trend in tandem with increases in photonic energy and sample Zn content. Deciding if this system is suitable for employment in optical data storage devices will be made easier by looking at the spectrum and doping agent correlation of optical parameters (n, k) with the optoelectronic energy. As the Zn level of the samples decreases, so does their conductivity peak. Verifying the continued good photosensitivity of these specimens. The findings indicate that the band gap rose as Zn2 + content rose.

Acknowledgements

Authors are most grateful for the, Al-Razi University –Yemen, for providing their lab to carry out the present work.

Author Contributions

All authors have contributed the creation of this manuscript: Sadiq. H. Khoreem: Investigation, Formal analysis, Data Curation and Resources, Software methodology, Visualization, Writing—Review & Editing, formal analysis. A. H. AL-Hammadi: Writing first draft,Project administration, Supervision and Resources, Validation and Writing—Review & Editing, formal analysis, Conceptualization, Methodology, Investigation.

Corresponding authors

Correspondence to Sadiq H. Khoreem .

Funding

This research received no external funding.

Data availability

All necessary data generated or analyzed during this study are included in this published article as figurs, and other auxiliary data are available from the corresponding author on a reasonable request. Sadiq H. Khoreem [email protected]

Supplementary information: ‘Not Applicable’.

Conflict of interest The authors declare that they have no known competing fnancial interests or personal relationships that could have appeared to infuence the work reported in this paper.

Ethical approval: ‘Not Applicable’.

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Studies on the electrical and optical conductivity of Barium-Nickel ferrite nanoparticles doped with Zn

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Abstract

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1. Introduction

2. Materials and Methods

3. Results and Discussion

3.1. XRD analysis

Conclusion

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References

Additional Declarations

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Version 1