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Optical linearity and bandgap analysis of Erythrosine B doped in polyvinyl alcohol films
Optical Materials 100 (2020) 109661
Contents lists available at ScienceDirect
Optical Materials journal homepage: http://www.elsevier.com/locate/optmat
Optical linearity and bandgap analysis of Erythrosine B doped in polyvinyl alcohol films E.F.M. El-Zaidia a, b, H.A.M. Ali b, Taymour A. Hamdalla a, c, A.A.A. Darwish a, d, *, T.A. Hanafy a, e a
Department of Physics and Nanotechnology Research Unit, Faculty of Science University of Tabuk, Tabuk, 71491, Saudi Arabia Department of Physics, Faculty of Education, Ain Shams University, Rorxy, Cairo, 11757, Egypt c Department of Physics, Faculty of Science, Alexandria University, Alexandria, Egypt d Department of Physics, Faculty of Education at Al-Mahweet, Sana’a University, Al-Mahweet, Yemen e Department of Physics, Faculty of Science, Fayoum University, El Fayoum, 63514, Egypt b
A R T I C L E I N F O
A B S T R A C T
Keywords: PVA Erythrosine Optical properties
Polyvinyl alcohol (PVA) has utilized in various fields of industry. PVA has been chosen as a host matrix and then doped with Erythrosine B dye (EB) with different concentrations of EB by using casting procedure. The linear optical properties have been studied and it found that the refractive index of PVA that contains 4 wt % of EB dye decreased by 18% with respect to that obtained for the pure sample. Also, the energy gap of PVA doped samples was studied and found three kinds of interband. The calculated nonlinear properties for pure and doped PVA samples were investigated. The calculated values of the third-order susceptibility, χ (3), and nonlinear refractive index, n2, are decreased by EB doped and the sample doped by 4 wt % of EB has the lowest value of χ (3) and n2. The obtained values of the refractive index candidate our synthesized materials to participate in light-emitting diodes and images sensor.
1. Introduction Polyvinyl alcohol (PVA) is considered the main polymer that has different potential applications in our daily life [1,2]. PVA is a water-soluble and more appealing polymer because it is a polyhydroxy synthetic polymer. Also, it has many features that are biodegradable, inexpensive, and non-toxic and chemically stable [3]. PVA has outstanding UV-IR radiation stability, expensive heat resistance and oxygen barrier properties [4]. Organic materials are of specific attention because they have prosperous electrical, optoelectronic, and storage properties for electronic device development and manufacturing [5]. Erythrosine B (EB) is a dye related to the xanthene family [6], and the chemical structure of EB is displayed in Scheme 1. It absorbs light in the optical range of 500–530 nm and it has a maximum absorbance at 530 nm in an aqueous solution [7]. Meanwhile, the doping of fluores cence organic dyes within the polymeric main chain is a major way for improving the optical and electrical properties of different types of polymers [8,9]. The doping of fluorescence organic materials into PVA is a vital way to improve the structural and various characters of the PVA composites [10,11].In the last decade, rear-Erath elements doped PVA has been
studied by several research groups for improving the structural, optical and electrical properties [12–15]. Balan et al. synthesized and charac terized PVA doped by a laser dye Rhodamine [16]. Significant nonlinear optical properties for PVA doped by azo dyes and Rhodamine have been obtained by Lessard et al. [17]. Qashou et al. [18] studied PVA film doped with different concentrations of Methylsilicon hydroxide phtha locyanine. Red-green-blue laser emissions from dye-doped PVA films are reported by Yap et al. [19]. According to our PVA doping survey, there is no related literature dealing with the optical properties of PVA doped with EB dye. This article is therefore intended to examine the optical characteristics of PVA-EB films in detail. In the present work, we have synthesized films of vinyl alcohol (PVA) doped with different percentage of % 1, 2, 3, and 4 wt % of EB. The structural, linear optical properties, band gap and nonlinear properties of PVA-EB polymeric composite films compared with that obtained for the pure PVA to demonstrate the effect of EB dye. The study of the linear optical and nonlinear optical properties especially the energy gap has an essential part mainly in optoelectronics technology.
* Corresponding author. Department of Physics and Nanotechnology Research Unit, Faculty of Science University of Tabuk, Tabuk, 71491, Saudi Arabia. E-mail address: [email protected] (A.A.A. Darwish). https://doi.org/10.1016/j.optmat.2020.109661 Received 9 November 2019; Received in revised form 30 December 2019; Accepted 2 January 2020 Available online 16 January 2020 0925-3467/© 2020 Elsevier B.V. All rights reserved.
E.F.M. El-Zaidia et al.
Optical Materials 100 (2020) 109661
Scheme 1. The chemical structure of the Erythrosine B compound.
2. Experimental setup PVA and EB are obtained from Sigma-Aldrich. For preparing the pure solution of PVA, the powder of PVA was dissolved in 30 ml of triply distilled water and the solution maintained at 80 � C for 1 h on hot plate magnetic stirrer at speed of 1000 rpm. An aqueous solution of EB with different concentrations (1, 2, 3, or 4 wt %) was obtained by added proper weight of EB in 50 ml of triply distilled water maintained at 80 � C and 1000 rpm. The mass fraction of EB (wt. %) was calculated according to the following equation: Wðwt:%Þ ¼
WEB WEB þ WPVA
(1)
where WEB and WPVA represent the weights of EB and PVA, respectively. Then, the required solutions of PVA and EB were dissolved in triply distilled water under a magnetic stirring then they were mixed and maintained at 50 � C and 1000 rpm for 6 h. The mixed solutions cast into Petri dishes and placed in an oven to dry and it will keep at 35 � C for 7 days until the solvent was completely evaporated. The thickness of the obtained polymer film can be measured by using a micrometer and it was found in the order of 0.08 mm. The optical transmission and reflection of the PVA-EB samples have been measured by using a UV-VIS spectrophotometer model V-670 JASCO in the wavelength range of 200–2500 nm at the room tempera ture for the normal light incidence.
Fig. 1. The optical (a) transmission (T) and (b) reflection (R) against wave length for pure PVA and that doped with EB in different concentrations.
3. Results and discussions 3.1. Optical properties studies for pure PVA and PVA-EB films In the spectral range from 200 to 2500 nm, the optical transmission (T) and reflection (R) for pure PVA and PVA doped by 1, 2, 3, and 4 wt % of EB are shown in Fig. 1(a and b). Fig. 1a displays that the transmittance spectrum for all films decreased with that incident shorter wavelength that clear the layer generated by intermolecular hydrogen interaction between the PVA matrix chains and the BE molecules. At the longer wavelength region, the synthesized films are transparent; the addition of T and R is 100%. The optical absorption of light happens at a shorter wavelength region. In the absorption region, PVA doped by 4 wt % of EB has the lowest values of optical transmission. This can be assigned to a high electronegative of EB that has been doped into PVA samples. The increase in electro-negativity acts to increase the absorption of our samples [20]. The absorption coefficient (α) of pure PVA and PVA doped by EB with different concentrations can be calculated using [21]: � �rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi2ffiffi 1 1 R2 1 R (2) α ¼ ln R2 þ d 2T 4T 2
Fig. 2. Variation of absorption coefficient (α) for pure PVA and that doped with EB in different concentrations.
The variation of α against the photon energy (hν) for PVA and PVA with different concentrations of EB dopant was represented in Fig. 2. It is 2
E.F.M. El-Zaidia et al.
Optical Materials 100 (2020) 109661
notified that new bands appeared when PVA doped with EB additives. Further, this behavior reveals the degradation of the PVA main chain and free radicals creation within our prepared samples. It could conclude from this figure, that the optical band gap will be decreased by the doping of EB increase because of the shift of α edge towards the UV spectrum. The forbidden band gap, Eg, can be obtained by using [21]: � ðαhνÞ0:5 ¼ C hυ Eg ; (3)
Table 1 The energy gap for pure PVA and PVA doped by EB up to 4 wt%.
where C is a constant. The relation between (αhν)0.5 and hν is shown in Fig. 3. Eq. (2) shows a straight line partition with a slope is representing the value of C. The straight-line intersection to the x-axis identified the values of Eg, which are introduced in Table 1. These values are found to be consistent with previously published research [13,18]. The onset energy gap (Eg1) is 2.13 eV for films of PVA doped with EB. The energy gap (Eg2 and Eg3) decreased depends on the EB doping. This could be related to the electro-negativity change that had been existed due to the interaction between the PVA main chain and the EB molecules. The electro-negativity increase will enhance the energies of lone-pair elec trons that will act to extend the valence band toward the bandgap [20]. So, a reduction in the energy gap had occurred within our synthesized samples can be expected. The values of Eg3 vary between 4.9 and 3.57 eV which is in good agreement with previous research work is done by Esfhanai et al. [22]. Also, Qashou et al. were found that Eg3 is decreased from 5.09 to 4.18 eV [18]. The refractive index, n, of pure PVA and PVA doped with EB has been introduced in Fig. 4. It is observed that the refractive index decreased with the increased in the doped content. This is related to the additive dye chemical structure and due to organic dye large-size structure. The higher n values of EB could be interpreted to the formation of dye-legend complexes within the main chain of PVA that has been pre-explained. The relation between n and the incident light photon energy, hν, is [23]: n2
� 1
1
¼
Eo Ed
ðhνÞ2 Eo Ed
Sample
Eg1 (eV)
Eg2 (eV)
Eg3 (eV)
Pure PVA 1 wt% EB 2 wt% EB 3 wt% EB 4 wt% EB
– 2.13 2.13 2.13 2.13
– 3.34 3.30 3.28 3.22
4.90 – 4.02 3.95 3.57
Fig. 4. The refractive index, n, variation against wavelength for pure PVA and that doped with EB in different concentrations.
(4)
Fig. 5 introduced the relation between (n2-1) 1 versus (hν)2. The straight lines intercepts are equal ration between oscillator energy, Eo, and dispersion energy, Ed, the slopes of the straight lines are equal to (1/ EoEd). The calculated dispersion parameters data are listed in Table 2. It is well known that Ed is related to the effective coordination number and the chemical structure of the sample under test. It is increased as the filler concentration increases [24]. The high frequency dielectric constant, εL, could be calculated using
Fig. 5. The relation between (n2-1) 1 and the (hν)2 for pure PVA and that doped with EB in different concentrations. Table 2 The optical parameters for pure PVA and PVA doped by EB.
Fig. 3. The relation between (αhν)0.5 and hν for pure PVA and that doped with EB in different concentrations. 3
Sample
Eo (eV)
Ed (eV)
ε∞
εL
N/m* (1046 g 1cm
Pure PVA 1 wt% EB 2 wt% EB 3 wt% EB 4 wt% EB
2.38 2.16 217 2.29 2.44
3.62 2.67 2.34 2.76 2.20
2.52 2.25 2.13 2.06 1.90
2.98 2.72 2.50 2.6 2.18
13.3 13.5 10.3 8.59 7.97
3
)
E.F.M. El-Zaidia et al.
Optical Materials 100 (2020) 109661
[18]: � e2 N λ2 4π 2 εo m* c2
� n2 ¼ εL
(5)
Fig. 6 shows the relation between n2 and λ2 of Pure PVA and PVA doped by different concentrations. The values of εL and N/m* were given in Table 2. As notified from this table that εL values decrease with increasing EB dopant concentration. This could be related to the lattice vibrations decrease and the decrease in the bonded carrier of PVA in the visible region as the dopant EB concentration rises. 3.2. The nonlinear optical properties studies for pure PVA and PVA-ER The non-linear optical properties of polymer composites depend primarily on the composition of the composite and the features of the parent polymers. Nonlinear optics has a big number of large photonics, communications, data, and optical calculation and capability planning applications [25]. PVA is widely used in a different component of nonlinear optical applications. PVA doped by EB is expected to have high nonlinear constants. From the following relationship can be determined the linear optic susceptibility χ (1) of a non-linear media [26]:
χ ð1Þ ¼
n2 1 4π
Fig. 7. Linear optical susceptibility variation against wavelength for pure PVA and that doped with EB in different concentrations.
(6)
According to equation (6), the spectral dependence of the χ (1) is calculated and illustrated in Fig. 7. There has been a peak in the spectra of the linear optical susceptibility which does not alter its location for all the investigated EB-PVA sample. The spectra of χ (1) follow a linear index refractive pattern, and its values are found to be in the range of 0.05 and 0.7. The third-order susceptibility, χ (3), can be calculated using [27]: �4 A n2o 1 χ ð3Þ ¼ (7) ð4πÞ4 where A is a constant (1.7 � 10 10 esu [26]). The calculated χ (3) for PVA doped by EB up to 4 wt % has been displayed in Fig. 8. It is observed that χ (3) values affected by the doping of EB within PVA samples. The lowest value of χ (3) for PVA film doped by 4 wt % of EB this could be related to the change of the degree of crystallinity. The nonlinear refractive index, n2, of pure PVA and PVA doped by EB up to 4 wt % is given by Ref. [26]: n2 ¼ 12π χ(3)/no
Fig. 8. The third-order susceptibility, χ (3) and the nonlinear refractive index, n2, variation against wavelength for pure PVA and that doped with EB in different concentrations.
The valued n2 of PVA and PVA-ER films are represented in Fig. 8. It is clear that n2 has high values that candidate our studied sample materials for the design of nonlinear electronic or optoelectronic devices. As we can conclude that PVA doped with 4 wt % of EB dye has the lowest value of χ (3) and n2. The data show that values of χ (3) and n2 are smaller that published by Shanshool et al. when they added nanoparticles to PMMA polymer as a host material [28].
(8)
4. Conclusions Linear and nonlinear optical studies were performed for pure PVA and PVA doped by EB with concentrations from 1 wt % up to 4 wt % utilizing the casting techniques. The optical properties have investi gated. The refractive index decreased with the increased in the EB doped concentration. The observed decrease in the optical band gap has been interpreted as a result of the changing of the crystalline disorder and deformation in the structural bonding between the PVA main chains. This was assigned to the interaction between EB molecules and func tional groups of PVA structure. The third-order susceptibility, χ (3), was calculated using Miller’s rule and its values were affected by the doping of EB within PVA samples. Fig. 6. The relation between n2and the λ2for pure PVA and that doped with EB in different concentrations. 4
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Optical Materials 100 (2020) 109661
Author contributions section
[12] T.A. Hamdalla, T.A. Hanafy, A.E. Bekheet, Influence of erbium ions on the optical and structural properties of polyvinyl alcohol, J. Spectrosc. 2015 (2015). [13] T.A. Hamdalla, T.A. Hanafy, Optical properties studies for PVA/Gd, La, Er or Y chlorides based on structural modification, Optik 127 (2016) 878. [14] T.A. Hanafy, Dielectric relaxation and alternating current conductivity of lanthanum, gadolinium, and erbium-polyvinyl alcohol doped films, J. Appl. Phys. 112 (2012), 034102. [15] E.F.M. El-Zaidia, Saleem I. Qashou, A.A.A. Darwish, T.A. Hanafy, Structural, optical, electrical conductivity and dielectric properties of PVA-10%YCl3 films, Surf. Rev. Lett. 26 (2019), 1850149. [16] N. Balan, M. Hari, V.P.N. Nampoori, Selective mode excitation in dye-doped DNA polyvinyl alcohol thin film, Appl. Opt. 48 (2009) 3521–3525. [17] R.A. Lessard, C. Malouin, R. Changkakoti, G. Manivannan, Dye-doped polyvinyl alcohol recording materials for holography and nonlinear optics, Opt. Eng. 32 (1993) 665. [18] Saleem I. Qashou, E.F.M. El-Zaidia, A.A.A. Darwish, T.A. Hanafy, Methylsiliconphthalocyanine hydroxide doped PVA films for optoelectronic applications: FTIR spectroscopy, electrical conductivity, linear and nonlinear optical studies, Physica B 571 (2019) 93–100. [19] S.-S. Yap, W.-O. Siew, T.-Y. Tou, S.-W. Ng, Red-green-blue laser emissions from dye-doped poly(vinyl alcohol) films, Appl. Opt. 41 (2002) 1725–1728. [20] R.G. Pearson, Absolute electronegativity and hardness: application to inorganic chemistry, Inorg. Chem. 27 (1988) 734–740. [21] Saleem I. Qashou, M. Rashad, A.A.A. Darwish, T.A. Hanafy, Thermal annealing effect on structural and optical properties of 2,9-Bis [2-(4-chlorophenyl)ethyl] anthrax [2,1,9-def:6,5,10-d0 e0 f0 ] diisoquinoline-1,3,8,10 (2H,9H) tetrone (ChdiisoQ) thin films, Opt. Quant. Electron. 49 (2017) 240. [22] Z.H. Esfahani, M. Ghanipour, D. Dorranian, Effect of dye concentration on the optical properties of red-BS dye-doped PVA film, J. Theor. Appl. Phys. 8 (2014) 117–121. [23] A.A.A. Darwish, H.A.M. Ali, On annealing induced effect in optical properties of amorphous GeSeSn chalcogenide films, J. Alloy. Comp. 710 (2017) 431–435. [24] T.A. Hamdalla, S.M. Seleim, A.K. Mohamed, M.E. Mahmoud, Design, characterization and optical properties of assembled nanoscale thin films of copper (II) complex with 5-azo-Phenol-8-Hydroxyquinoline, Opt. Mater. 95 (2019), 109215. [25] M. Frumar, J. Jedelsky, B. Frumarova, T. Wagner, M. Hrdlicka, J. Non-Cryst. Solids 326&327 (2003) 399–404. [26] L. Tichy, H. Tich� a, P. Nagels, R. Callaerts, R. Mertens, M. Vlcek, Optical properties of amorphous As-Se and Ge-As-Se thin films, Mater. Lett. 39 (1999) 122–128. [27] M. Rashad, Taymour A. Hamdalla, S.E. Al Garni, A.A.A. Darwish, S.M. Seleim, Optical and electrical behaviors in NiO/xFe2O3 nanoparticles synthesized by microwave irradiation method, Opt. Mater. 75 (2018) 869–874. [28] Haider Mohammed Shanshool, Muhammad Yahaya, Wan Mahmood Mat Yunus, Ibtisam Yahya Abdullah, Influence of CuO nanoparticles on third-order nonlinearity and optical limiting threshold of polymer/ZnO nanocomposites, Opt. Quant. Electron. 49 (2017) 18.
This article was produced with the participation of all authors. Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. References [1] Tayser Sumer Gaaz, Abu Bakar Sulong, Majid Niaz Akhtar, Abdul Amir H. Kadhum, Abu Bakar Mohamad, Ahmed A. Al-Amiery, Properties and applications of polyvinyl alcohol, halloysite nanotubes and their nanocomposites, Molecules 20 (2015) 22833–22847. [2] A.K. Kulshreshtha, C. Vasile, Handbook of Polymer Blends and Composites, iSmithersRapra Publishing, 2002. [3] I.S. Yahia, A. Bouzidi, H.Y. Zahran, W. Jilani, S. AlFaify, H. Algarni, H. Guermazi, Design of smart optical sensor using polyvinyl alcohol Fluoresce in sodium salt: laser filters and optical limiting effect, J. Mol. Struct. 1156 (2018) 492–500. [4] L. Li, Z. Wang, P. Ma, H. Bai, W. Dong, M. Chen, Preparation of polyvinyl alcohol/ chitosan hydrogel compounded with graphene oxide to enhance the adsorption properties for Cu(II) in aqueous solution, J. Polym. Res. 150 (2015) 1–10. [5] M.M. El-Nahass, H.S. Soliman, B.A. Khalifa, I.M. Soliman, Structural and optical properties of nanocrystalline aluminum phthalocyanine chloride thin films, Mater. Sci. Semicond. Process. 38 (2015) 177–183. [6] Laura Carmen Apostol, Cristina Ghinea, Madalena Alves, Maria Gavrilescu, Removal of Erythrosine B dye from water effluents using crop waste pumpkin seed hulls as adsorbent, Desalin. Water Treat. 57 (2016) 22585–22608. [7] P.A. Lyday, T. Kaiho, Ullmann’s Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, Germany, 2000. [8] R. Chib, S. Raut, S. Shah, B. Grobelna, I. Akopova, R. Rich, T.J. Sørensen, B. W. Laursen, H. Grajek, Z. Gryczynski, Steady-state and time-resolved fluorescence studies of azadioxatriangulenium (ADOTA) fluorophore in silica and PVA thin films, Dyes Pigments 117 (2015) 16–23. [9] H. Tan, S. Xie, N. Li, C. Tong, L. Xu, J. Xu, C. Zhang, Synthesis and characterization of NaYF4:Yb, Er up-conversion phosphors/poly(vinyl alcohol) composite fluorescent films, Mater. Exp. 8 (2018) 141. [10] D. Wr� obel, I. Hany_z, R. Bartkowiak, R.M. Ion, Fluorescence and time-resolved delayed luminescence of porphyrins in organic solvents and polymer matrices, J. Fluoresc. 8 (1998) 191–198. [11] R. Marangoni, A. Mikowski, F. Wypych, Effect of adsorbed/intercalated anionic dyes into the mechanical properties of PVA: layered zinc hydroxide nitrate nanocomposites, J. Colloid Interface Sci. 351 (2010) 384–391.
5
Contents lists available at ScienceDirect
Optical Materials journal homepage: http://www.elsevier.com/locate/optmat
Optical linearity and bandgap analysis of Erythrosine B doped in polyvinyl alcohol films E.F.M. El-Zaidia a, b, H.A.M. Ali b, Taymour A. Hamdalla a, c, A.A.A. Darwish a, d, *, T.A. Hanafy a, e a
Department of Physics and Nanotechnology Research Unit, Faculty of Science University of Tabuk, Tabuk, 71491, Saudi Arabia Department of Physics, Faculty of Education, Ain Shams University, Rorxy, Cairo, 11757, Egypt c Department of Physics, Faculty of Science, Alexandria University, Alexandria, Egypt d Department of Physics, Faculty of Education at Al-Mahweet, Sana’a University, Al-Mahweet, Yemen e Department of Physics, Faculty of Science, Fayoum University, El Fayoum, 63514, Egypt b
A R T I C L E I N F O
A B S T R A C T
Keywords: PVA Erythrosine Optical properties
Polyvinyl alcohol (PVA) has utilized in various fields of industry. PVA has been chosen as a host matrix and then doped with Erythrosine B dye (EB) with different concentrations of EB by using casting procedure. The linear optical properties have been studied and it found that the refractive index of PVA that contains 4 wt % of EB dye decreased by 18% with respect to that obtained for the pure sample. Also, the energy gap of PVA doped samples was studied and found three kinds of interband. The calculated nonlinear properties for pure and doped PVA samples were investigated. The calculated values of the third-order susceptibility, χ (3), and nonlinear refractive index, n2, are decreased by EB doped and the sample doped by 4 wt % of EB has the lowest value of χ (3) and n2. The obtained values of the refractive index candidate our synthesized materials to participate in light-emitting diodes and images sensor.
1. Introduction Polyvinyl alcohol (PVA) is considered the main polymer that has different potential applications in our daily life [1,2]. PVA is a water-soluble and more appealing polymer because it is a polyhydroxy synthetic polymer. Also, it has many features that are biodegradable, inexpensive, and non-toxic and chemically stable [3]. PVA has outstanding UV-IR radiation stability, expensive heat resistance and oxygen barrier properties [4]. Organic materials are of specific attention because they have prosperous electrical, optoelectronic, and storage properties for electronic device development and manufacturing [5]. Erythrosine B (EB) is a dye related to the xanthene family [6], and the chemical structure of EB is displayed in Scheme 1. It absorbs light in the optical range of 500–530 nm and it has a maximum absorbance at 530 nm in an aqueous solution [7]. Meanwhile, the doping of fluores cence organic dyes within the polymeric main chain is a major way for improving the optical and electrical properties of different types of polymers [8,9]. The doping of fluorescence organic materials into PVA is a vital way to improve the structural and various characters of the PVA composites [10,11].In the last decade, rear-Erath elements doped PVA has been
studied by several research groups for improving the structural, optical and electrical properties [12–15]. Balan et al. synthesized and charac terized PVA doped by a laser dye Rhodamine [16]. Significant nonlinear optical properties for PVA doped by azo dyes and Rhodamine have been obtained by Lessard et al. [17]. Qashou et al. [18] studied PVA film doped with different concentrations of Methylsilicon hydroxide phtha locyanine. Red-green-blue laser emissions from dye-doped PVA films are reported by Yap et al. [19]. According to our PVA doping survey, there is no related literature dealing with the optical properties of PVA doped with EB dye. This article is therefore intended to examine the optical characteristics of PVA-EB films in detail. In the present work, we have synthesized films of vinyl alcohol (PVA) doped with different percentage of % 1, 2, 3, and 4 wt % of EB. The structural, linear optical properties, band gap and nonlinear properties of PVA-EB polymeric composite films compared with that obtained for the pure PVA to demonstrate the effect of EB dye. The study of the linear optical and nonlinear optical properties especially the energy gap has an essential part mainly in optoelectronics technology.
* Corresponding author. Department of Physics and Nanotechnology Research Unit, Faculty of Science University of Tabuk, Tabuk, 71491, Saudi Arabia. E-mail address: [email protected] (A.A.A. Darwish). https://doi.org/10.1016/j.optmat.2020.109661 Received 9 November 2019; Received in revised form 30 December 2019; Accepted 2 January 2020 Available online 16 January 2020 0925-3467/© 2020 Elsevier B.V. All rights reserved.
E.F.M. El-Zaidia et al.
Optical Materials 100 (2020) 109661
Scheme 1. The chemical structure of the Erythrosine B compound.
2. Experimental setup PVA and EB are obtained from Sigma-Aldrich. For preparing the pure solution of PVA, the powder of PVA was dissolved in 30 ml of triply distilled water and the solution maintained at 80 � C for 1 h on hot plate magnetic stirrer at speed of 1000 rpm. An aqueous solution of EB with different concentrations (1, 2, 3, or 4 wt %) was obtained by added proper weight of EB in 50 ml of triply distilled water maintained at 80 � C and 1000 rpm. The mass fraction of EB (wt. %) was calculated according to the following equation: Wðwt:%Þ ¼
WEB WEB þ WPVA
(1)
where WEB and WPVA represent the weights of EB and PVA, respectively. Then, the required solutions of PVA and EB were dissolved in triply distilled water under a magnetic stirring then they were mixed and maintained at 50 � C and 1000 rpm for 6 h. The mixed solutions cast into Petri dishes and placed in an oven to dry and it will keep at 35 � C for 7 days until the solvent was completely evaporated. The thickness of the obtained polymer film can be measured by using a micrometer and it was found in the order of 0.08 mm. The optical transmission and reflection of the PVA-EB samples have been measured by using a UV-VIS spectrophotometer model V-670 JASCO in the wavelength range of 200–2500 nm at the room tempera ture for the normal light incidence.
Fig. 1. The optical (a) transmission (T) and (b) reflection (R) against wave length for pure PVA and that doped with EB in different concentrations.
3. Results and discussions 3.1. Optical properties studies for pure PVA and PVA-EB films In the spectral range from 200 to 2500 nm, the optical transmission (T) and reflection (R) for pure PVA and PVA doped by 1, 2, 3, and 4 wt % of EB are shown in Fig. 1(a and b). Fig. 1a displays that the transmittance spectrum for all films decreased with that incident shorter wavelength that clear the layer generated by intermolecular hydrogen interaction between the PVA matrix chains and the BE molecules. At the longer wavelength region, the synthesized films are transparent; the addition of T and R is 100%. The optical absorption of light happens at a shorter wavelength region. In the absorption region, PVA doped by 4 wt % of EB has the lowest values of optical transmission. This can be assigned to a high electronegative of EB that has been doped into PVA samples. The increase in electro-negativity acts to increase the absorption of our samples [20]. The absorption coefficient (α) of pure PVA and PVA doped by EB with different concentrations can be calculated using [21]: � �rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi2ffiffi 1 1 R2 1 R (2) α ¼ ln R2 þ d 2T 4T 2
Fig. 2. Variation of absorption coefficient (α) for pure PVA and that doped with EB in different concentrations.
The variation of α against the photon energy (hν) for PVA and PVA with different concentrations of EB dopant was represented in Fig. 2. It is 2
E.F.M. El-Zaidia et al.
Optical Materials 100 (2020) 109661
notified that new bands appeared when PVA doped with EB additives. Further, this behavior reveals the degradation of the PVA main chain and free radicals creation within our prepared samples. It could conclude from this figure, that the optical band gap will be decreased by the doping of EB increase because of the shift of α edge towards the UV spectrum. The forbidden band gap, Eg, can be obtained by using [21]: � ðαhνÞ0:5 ¼ C hυ Eg ; (3)
Table 1 The energy gap for pure PVA and PVA doped by EB up to 4 wt%.
where C is a constant. The relation between (αhν)0.5 and hν is shown in Fig. 3. Eq. (2) shows a straight line partition with a slope is representing the value of C. The straight-line intersection to the x-axis identified the values of Eg, which are introduced in Table 1. These values are found to be consistent with previously published research [13,18]. The onset energy gap (Eg1) is 2.13 eV for films of PVA doped with EB. The energy gap (Eg2 and Eg3) decreased depends on the EB doping. This could be related to the electro-negativity change that had been existed due to the interaction between the PVA main chain and the EB molecules. The electro-negativity increase will enhance the energies of lone-pair elec trons that will act to extend the valence band toward the bandgap [20]. So, a reduction in the energy gap had occurred within our synthesized samples can be expected. The values of Eg3 vary between 4.9 and 3.57 eV which is in good agreement with previous research work is done by Esfhanai et al. [22]. Also, Qashou et al. were found that Eg3 is decreased from 5.09 to 4.18 eV [18]. The refractive index, n, of pure PVA and PVA doped with EB has been introduced in Fig. 4. It is observed that the refractive index decreased with the increased in the doped content. This is related to the additive dye chemical structure and due to organic dye large-size structure. The higher n values of EB could be interpreted to the formation of dye-legend complexes within the main chain of PVA that has been pre-explained. The relation between n and the incident light photon energy, hν, is [23]: n2
� 1
1
¼
Eo Ed
ðhνÞ2 Eo Ed
Sample
Eg1 (eV)
Eg2 (eV)
Eg3 (eV)
Pure PVA 1 wt% EB 2 wt% EB 3 wt% EB 4 wt% EB
– 2.13 2.13 2.13 2.13
– 3.34 3.30 3.28 3.22
4.90 – 4.02 3.95 3.57
Fig. 4. The refractive index, n, variation against wavelength for pure PVA and that doped with EB in different concentrations.
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Fig. 5 introduced the relation between (n2-1) 1 versus (hν)2. The straight lines intercepts are equal ration between oscillator energy, Eo, and dispersion energy, Ed, the slopes of the straight lines are equal to (1/ EoEd). The calculated dispersion parameters data are listed in Table 2. It is well known that Ed is related to the effective coordination number and the chemical structure of the sample under test. It is increased as the filler concentration increases [24]. The high frequency dielectric constant, εL, could be calculated using
Fig. 5. The relation between (n2-1) 1 and the (hν)2 for pure PVA and that doped with EB in different concentrations. Table 2 The optical parameters for pure PVA and PVA doped by EB.
Fig. 3. The relation between (αhν)0.5 and hν for pure PVA and that doped with EB in different concentrations. 3
Sample
Eo (eV)
Ed (eV)
ε∞
εL
N/m* (1046 g 1cm
Pure PVA 1 wt% EB 2 wt% EB 3 wt% EB 4 wt% EB
2.38 2.16 217 2.29 2.44
3.62 2.67 2.34 2.76 2.20
2.52 2.25 2.13 2.06 1.90
2.98 2.72 2.50 2.6 2.18
13.3 13.5 10.3 8.59 7.97
3
)
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Optical Materials 100 (2020) 109661
[18]: � e2 N λ2 4π 2 εo m* c2
� n2 ¼ εL
(5)
Fig. 6 shows the relation between n2 and λ2 of Pure PVA and PVA doped by different concentrations. The values of εL and N/m* were given in Table 2. As notified from this table that εL values decrease with increasing EB dopant concentration. This could be related to the lattice vibrations decrease and the decrease in the bonded carrier of PVA in the visible region as the dopant EB concentration rises. 3.2. The nonlinear optical properties studies for pure PVA and PVA-ER The non-linear optical properties of polymer composites depend primarily on the composition of the composite and the features of the parent polymers. Nonlinear optics has a big number of large photonics, communications, data, and optical calculation and capability planning applications [25]. PVA is widely used in a different component of nonlinear optical applications. PVA doped by EB is expected to have high nonlinear constants. From the following relationship can be determined the linear optic susceptibility χ (1) of a non-linear media [26]:
χ ð1Þ ¼
n2 1 4π
Fig. 7. Linear optical susceptibility variation against wavelength for pure PVA and that doped with EB in different concentrations.
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According to equation (6), the spectral dependence of the χ (1) is calculated and illustrated in Fig. 7. There has been a peak in the spectra of the linear optical susceptibility which does not alter its location for all the investigated EB-PVA sample. The spectra of χ (1) follow a linear index refractive pattern, and its values are found to be in the range of 0.05 and 0.7. The third-order susceptibility, χ (3), can be calculated using [27]: �4 A n2o 1 χ ð3Þ ¼ (7) ð4πÞ4 where A is a constant (1.7 � 10 10 esu [26]). The calculated χ (3) for PVA doped by EB up to 4 wt % has been displayed in Fig. 8. It is observed that χ (3) values affected by the doping of EB within PVA samples. The lowest value of χ (3) for PVA film doped by 4 wt % of EB this could be related to the change of the degree of crystallinity. The nonlinear refractive index, n2, of pure PVA and PVA doped by EB up to 4 wt % is given by Ref. [26]: n2 ¼ 12π χ(3)/no
Fig. 8. The third-order susceptibility, χ (3) and the nonlinear refractive index, n2, variation against wavelength for pure PVA and that doped with EB in different concentrations.
The valued n2 of PVA and PVA-ER films are represented in Fig. 8. It is clear that n2 has high values that candidate our studied sample materials for the design of nonlinear electronic or optoelectronic devices. As we can conclude that PVA doped with 4 wt % of EB dye has the lowest value of χ (3) and n2. The data show that values of χ (3) and n2 are smaller that published by Shanshool et al. when they added nanoparticles to PMMA polymer as a host material [28].
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4. Conclusions Linear and nonlinear optical studies were performed for pure PVA and PVA doped by EB with concentrations from 1 wt % up to 4 wt % utilizing the casting techniques. The optical properties have investi gated. The refractive index decreased with the increased in the EB doped concentration. The observed decrease in the optical band gap has been interpreted as a result of the changing of the crystalline disorder and deformation in the structural bonding between the PVA main chains. This was assigned to the interaction between EB molecules and func tional groups of PVA structure. The third-order susceptibility, χ (3), was calculated using Miller’s rule and its values were affected by the doping of EB within PVA samples. Fig. 6. The relation between n2and the λ2for pure PVA and that doped with EB in different concentrations. 4
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Optical Materials 100 (2020) 109661
Author contributions section
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