Enhanced linear and nonlinear optical properties of poly(vinyl alcohol) films with manganese(III) tetraphenylporphyrin chloride additive for optoelectronic applications
DOI:
https://doi.org/10.1002/pi.70049Keywords:
PVA composite films , MnTPPCl additive , optical bandgap , nonlinear optical properties , ATR-FTIR spectroscopy , optical conductivityAbstract
Polymer-based composite materials with tunable optical properties have garnered significant attention due to their potential applications in optoelectronics and photonics. Among them, poly(vinyl alcohol) (PVA) has been extensively investigated owing to its excellent film-forming ability, optical transparency and compatibility with functional additives. In this study, composite films were fabricated by incorporating manganese(III) tetraphenylporphyrin chloride (MnTPPCl: a metalloporphyrin complex that absorbs visible light) into a PVA matrix at concentrations of 0.05, 0.1 and 0.25 wt% via the conventional solution casting method. The films were characterized using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, SEM and UV–visible–near infrared (NIR) spectrophotometry to examine their structural, morphological and optical properties, respectively. ATR-FTIR analysis confirmed the successful formation of molecular interactions between MnTPPCl and PVA, facilitated by hydrogen bonding and coordination. SEM micrographs revealed a smooth surface for pure PVA, whereas the incorporation of MnTPPCl introduced uniformly distributed spherical domains whose size and density increased with the dopant concentration. Optical studies revealed a redshift in the absorption edge, accompanied by the emergence of MnTPPCl-specific absorption bands. A decrease in the indirect optical bandgap (from 4.98 to 4.37 eV) and an increase in the absorption coefficient (up to 10−13 cm−1) were observed. Furthermore, enhancements in both optical conductivity and dielectric response were recorded. Nonlinear optical measurements demonstrated a pronounced improvement, with the third-order nonlinear susceptibility (χ(3)) increasing from 1 × 10−13 to 1.2 × 10−13 esu, and the nonlinear refractive index (n2) exhibiting a tenfold enhancement. These results demonstrate that MnTPPCl can effectively tune the structural and optical properties of PVA, making these composites promising materials for advanced optoelectronic, nonlinear optical and photonic device applications. © 2025 Society of Chemical Industry.
References
A
Abdullah, O. G., Salh, D. M., Mohamad, A. H., Jamal, G. M., Ahmed, H. T., Mustafa, B. S., & Ahmed, K. M. (2022). Structural, optical and electrical characteristics of PVA-based polymer electrolytes incorporated with metal complexes. Journal of Electronic Materials, 51(2), 675–683. https://doi.org/10.1007/s11664-021-09341-z
Abomostafa, H. (2021). Influence of nano-silica on the structural, thermal, and optical properties of PMMA/PVC blend polymer nanocomposites. Journal of Molecular Structure, 1225, Article 129126. https://doi.org/10.1016/j.molstruc.2020.129126
Ahmed, A., Abed, R. N., Kadhom, M., Hashim, H., Akram, E., Jawad, A., & Yousif, E. (2023). Synthesis, characterization, and optical properties of polyvinyl chloride-doped nickel nanoparticles. Journal of Polymer Research, 30(7), Article 274. https://doi.org/10.1007/s10965-023-03639-6
Aithal, S., & Aithal, P. (2017). Phase change materials and their applications in thermal energy storage: A review. International Journal of Engineering Research and Modern Education, 2(1), 90–97.
Albu, R. M., Stoica, I., Nica, S. L., Soroceanu, M., & Barzic, A. I. (2024). Tuning surface morphology and optical characteristics of polyimide/zinc oxide nanocomposites. Polymers, 16(22), Article 3288. https://doi.org/10.3390/polym16223288
Alameer, O., Timoumi, A., El Guesmi, N., Alamri, S., Belhadj, W., Althagafi, K., & Bouraoui, A. (2022). Probing the electrical conductivity and dielectric properties of PVC/PMMA blends doped with metallic nanoparticles. The European Physical Journal Plus, 137(10), Article 1160. https://doi.org/10.1140/epjp/s13360-022-03362-w
Algidsawi, A. J. K., Hashim, A., Hadi, A., Habeeb, M. A., & Abed, H. H. (2022). Structural and optical features of PVA/PEG blend reinforced with metal oxide nanoparticles for optoelectronic devices. Physics and Chemistry of Solid State, 23(2), 353–360. https://doi.org/10.15330/pcss.23.2.353-360
Alharthi, S. S., Algethami, G. M., & Badawi, A. (2024). Tuning optical, dielectric, and electrical properties of PEO/CMC doped with mixed metal oxide nanoparticles. Optical Materials, 152Trace, Article 115439. https://doi.org/10.1016/j.optmat.2024.115439
Alharshan, G. A., Zakaly, H. M., Issa, S. A., Uosif, M., & Henaish, A. (2022). Mechanical and radiation shielding features of polymer nanocomposites modified with heavy metal oxides. Optical Materials, 125, Article 112142. https://doi.org/10.1016/j.optmat.2022.112142
Al-Muntaser, A., El-Nahass, M., Oraby, A., & Meikhail, M. (2019). Structural, optical, and electrical properties of thermally evaporated organic semiconductor thin films. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 220, Article 117112. https://doi.org/10.1016/j.saa.2019.05.027
Al-Muntaser, A. A., El-Nahass, M. M., Oraby, A. H., Meikhail, MS., & Zeyada, H. M. (2018). Optical properties and dispersion parameters of organic nanocomposite thin films. Optik, 167, 204–217. https://doi.org/10.1016/j.ijleo.2018.04.025
Al-Muntaser, A., Nasher, M., & Makhlouf, M. (2022). Enhancement of optical and electrical properties of PVC/PMMA blend films doped with Li4Ti5O12 nanoparticles. Ceramics International, 48(6), 8069–8080. https://doi.org/10.1016/j.ceramint.2021.12.008
Al-Muntaser, A., Pashameah, R. A., Alzahrani, E., AlSubhi, S. A., & Tarabiah, A. (2023). Tuning the structural, optical, electrical, and dielectric properties of PVA/PVP/CMC ternary polymer blend using ZnO nanoparticles for nanodielectric and optoelectronic devices. Optical Materials, 135, Article 113333. https://doi.org/10.1016/j.optmat.2022.113333
Al-Muntaser, A. A., Alamri, HR., Sharma, K., Eltahir, S., & Makhlouf, M. M. (2022). Probing the linear and nonlinear optical parameters of polymer nanocomposite films for optoelectronics. Optical Materials, 128, Article 112465. https://doi.org/10.1016/j.optmat.2022.112465
Al-Muntaser, A. A., Al-Ghamdi, S. A., Alzahrani, E., Rajeh, A., Asnag, G. M., Al-Harthi, A. M., & Saeed, A. (2024). Investigation of structural and optical characteristics of PVA/crystal violet dye composites. Journal of Polymer Research, 31(10), Article 311. https://doi.org/10.1007/s10965-024-04160-8
Al-Muntaser, A. A., Alzahrani, E., Saeed, A., Al-Ghamdi, S. A., Alwafi, R., Abo-Dief, H. M., & Morsi, M. A. (2024). An insight into the role of titanium oxide nanofiller on the structural, optical, electrical, and dielectric characteristics of PS/PVK composite. Physica Scripta, 99(10), Article 105991. https://doi.org/10.1088/1402-4896/ad732b
Al-Muntaser, A. A., Alzahrani, E., Al-Ghamdi, S. A., Al-Harthi, A. M., Aldwais, S., & Saeed, A. (2024). Tailoring structural, optical, and dielectric properties of PVC/PMMA/PS/ZnO nanocomposites for capacitive energy storage applications. ECS Journal of Solid State Science and Technology, 13(12), Article 124001. https://doi.org/10.1149/2162-8777/adb992
Al-Muntaser, A., Althobiti, R. A., Al Naim, A. F., Alzahrani, E., & Tarabiah, A. (2024). Structural, morphological, optical, electrical and dielectric features based on nanoceramic Li4Ti5O12 filler reinforced PEO/PVP blend. Physica Scripta, 99(6), Article 065932. https://doi.org/10.1088/1402-4896/ad42eb
Alrowaili, Z., Ezzeldien, M., Mohammed, M., & Yahia, I. (2020). Synthesis, linear and nonlinear optical properties of organic semiconductor thin films for optoelectronics. Results in Physics, 18, Article 103203. https://doi.org/10.1016/j.rinp.2020.103203
Alsaif, N. A., Atta, A., Abdeltwab, E., & Abdel-Hamid, M. (2024). Structural characteristics, dielectric dispersion, and optical parameters of PVA/ZnO nanocomposite films. Macromolecular Research, 32(1), 35–44. https://doi.org/10.1007/s13203-023-00311-2
AlSaidi, R. A., Alamri, H. R., Sharma, K., & Al-Muntaser, A. (2022). Flexible polymer nanocomposites with enhanced dielectric and optical properties for energy storage devices. Materials Today Communications, 32, Article 103874. https://doi.org/10.1016/j.mtcomm.2022.103874
Ang, P. Y., Čehovski, M., Lompa, F., Hänisch, C., Samigullina, D., Reineke, S., & Formanek, P. (2021). Matrix-dependent emission and optical characterization of organic light-emitting materials in polymer blends. Polymers, 13(20), Article 3566. https://doi.org/10.3390/polym13203566
B
Bhatti, M. R. A., Kernin, A., Tausif, M., Zhang, H., Papageorgiou, D., Bilotti, E., & Peijs, T. (2022). Smart and stretchable polymer nanocomposites with high optical and electrical responsiveness. Advanced Optical Materials, 10(4), Article 2102186. https://doi.org/10.1002/adom.20102186
Bouzidi, A., Omri, K., Jilani, W., Guermazi, H., & Yahia, I. (2018). Electrical transport mechanism and dielectric relaxation behavior of polymer/ZnO nanocomposite films. Journal of Inorganic and Organometallic Polymers and Materials, 28(4), 1114–1126. https://doi.org/10.1007/s10904-018-0810-6
Brza, M., Aziz, S. B., Anuar, H., Ali, F., Dannoun, E. M., Mohammed, S. J., & Abdulwahid, R. T. (2020). Structural, morphological and electrical impedance analysis of PVA-based solid polymer electrolytes. Scientific Reports, 10(1), Article 18108. https://doi.org/10.1038/s41598-020-75112-9
Bulinski, M. (2021). Quantitative analysis of dielectric relaxation and electric modulus in multiphase polymer blends. Molecules, 26(10), Article 2886. https://doi.org/10.3390/molecules26102886
D
Darwesh, A. H., Aziz, S. B., & Hussen, S. A. (2022). Probing the linear and nonlinear optical parameters of chitosan-based polymer composites for optoelectronics. Optical Materials, 133, Article 113007. https://doi.org/10.1016/j.optmat.2022.113007
Devadiga, D., Selvakumar, M., Shetty, P., Mahesha, M., Devadiga, D., Ahipa, T., & Santhosh, A. S. (2021). Recent progress in polymer-based solid polymer electrolytes for lithium-ion batteries. Journal of Solid State Electrochemistry, 25(5), 1461–1478. https://doi.org/10.1007/s10008-021-04910-z
E
Elgharbawy, A. S., El Demerdash, A. .-G. M., Sadik, W. A., Kasaby, M. A., Lotfy, A. H., & Osman, A. I. (2024). Synthesis and characterization of multifunctional polymer nanocomposites for capacitive energy storage. Polymers, 16(15), Article 2141. https://doi.org/10.3390/polym16152141
El-Naggar, A., Heiba, Z. K., Mohamed, M. B., Kamal, A., Lakshminarayana, G., & Abd-Elkader, O. H. (2022). Probing the influence of metal oxide doping on the optical and dielectric characteristics of PMMA matrices. Optical Materials, 128Trace, Article 112379. https://doi.org/10.1016/j.optmat.2022.112379
G
Ghoshal, D., Bhattacharya, D., Mondal, D., Das, S., Bose, N., & Basu, M. (2020). Tailoring the optical band gap and electrical conductivity of polyvinyl alcohol composite films. Applied Physics A, 126(1), Article 28. https://doi.org/10.1007/s00339-019-3211-8
H
Habeeb, M. A., Hamza, R. S. A., Oreibi, I., & Sabur, D. A. (2024). Structural, optical and electrical characteristics of PVA/PVP blend reinforced with hybrid metal chloride complexes. Silicon, 16(7), 2839–2851. https://doi.org/10.1007/s12633-024-02891-3
Habeeb, M. A., Mahdi, S. M., & Mamoun, F. (2024). Synthesis and characterization of polymer blend electrolytes filled with semiconductor nanoparticles for optoelectronic devices. Silicon, 16(9), 3917–3928. https://doi.org/10.1007/s12633-024-02988-9
Habeeb, M. A., Oreibi, I., Hamza, R. S. A., & Mamoun, F. (2024). Broadband dielectric spectroscopy and transport properties of multiphase semicrystalline polymer nanocomposites. Silicon, 16(13), 5947–5960. https://doi.org/10.1007/s12633-024-03112-7
Hassanien, A. S., & Sharma, I. (2020). Optical band gap, dispersion parameters and electronic properties of amorphous chalcogenide thin films. Optik, 200, Article 163415. https://doi.org/10.1016/j.ijleo.2019.163415
J
Jahan, Z., Niazi, M. B. K., & Gregersen, Ø. W. (2018). Mechanical, thermal and optical properties of PVA/cellulose nanocomposite membranes for industrial separations. Journal of Industrial and Engineering Chemistry, 57, 113–124. https://doi.org/10.1016/j.jiec.2017.08.014
Jilani, W., Bouzidi, A., Yahia, I., Guermazi, H., Zahran, H., & Saker, G. (2018). AC conductivity and dielectric relaxation behavior of polyvinyl alcohol/copper oxide nanocomposites. Journal of Materials Science: Materials in Electronics, 29(19), 16446–16453. https://doi.org/10.1007/s10854-018-9736-2
Jin, Z. H., & Gao, H. J. (2013). Finite element analysis of mechanical characteristics in multiphase hybrid polymer nanocomposites. Advanced Materials Research, 634, 2432–2435. https://doi.org/10.4028/www.scientific.net/AMR.634-638.2432
K
Kadim, A. M., Abass, K. H., Abdali, K., & Musa, S. J. (2024). Investigation of linear and non-linear optical parameters of plasticized solid polymer electrolytes. Nano Biomedicine and Engineering, 16(2), 119–127. https://doi.org/10.26599/NBE.2024.9300114
Kharazmi, A., Faraji, N., Hussin, R. M., Saion, E., Yunus, W. M. M., & Behzad, K. (2015). Structural, optical, and thermal characteristics of laser-ablated metal nanoparticles in polymer matrices. Beilstein Journal of Nanotechnology, 6, 529–536. https://doi.org/10.3762/bjnano.6.55
L
Liu, B., Zhang, J., & Guo, H. (2022). Composite electrospun membranes based on PVC/PMMA blends as polymer electrolytes for lithium batteries. Membranes, 12(4), Article 347. https://doi.org/10.3390/membranes12040347
Liu, T., Peng, X., Chen, Y. N., Bai, Q. W., Shang, C., Zhang, L., & Wang, H. (2018). Highly transparent, stable and conducting silver nanowire networks buried at the surface of flexible polymers. Macromolecular Rapid Communications, 39(12), Article 1800050. https://doi.org/10.1002/marc.201800050
M
Makhlouf, M. (2021). Probing the linear and non-linear optical parameters of copper chloride doped polyvinyl alcohol freestanding films. Optical Materials, 111, Article 110663. https://doi.org/10.1016/j.optmat.2020.110663
Mohammed, M., Yahia, I., & Salem, G. (2022). Optical and dielectric features of PVC/ZnCo2O4/MWCNTs ternary hybrid nanocomposite polymer electrolytes. Optics & Laser Technology, 156, Article 108629. https://doi.org/10.1016/j.optlastec.2022.108629
Morad, I., Ali, H. E., Khairy, Y., Algarni, H., Qasim, K., Ismail, A., & Abdel-Wahab, M. S. (2023). Tuning the structure, optical band gap and dispersion parameters of polymer matrices using laser combustion derived nano-fillers. Journal of Inorganic and Organometallic Polymers and Materials, 33(10), 3060–3075. https://doi.org/10.1007/s10904-023-02684-y
Mostafa, My., Zakaly, H. M., Issa, S. A., Saudi, H., & Henaish, A. (2022). Structural, optical, and gamma-ray shielding features of PVA/PEG blend containing metal oxide nanoparticle composites. Applied Physics A: Materials Science & Processing, 128(3), Article 199. https://doi.org/10.1007/s00339-022-05332-9
Muhammad, S. D., Aziz, D. M., & Aziz, S. B. (2024). Overview of broadband dielectric spectroscopy and electrical conductivity of biopolymer blend electrolytes for energy storage. RSC Advances, 14(37), 26362–26387. https://doi.org/10.1039/D4RA04112E
N
Namsheer, K., & Rout, C. S. (2021). Conducting polymers and their composites for high-performance supercapacitors: A review on recent progress, challenges and perspectives. RSC Advances, 11(10), 5659–5697. https://doi.org/10.1039/D0RA08712E
O
Oreibi, I., Habeeb, M. A., & Hamza, R. S. A. (2024). Impedance and modulus spectroscopy of polyvinyl alcohol/polyvinyl pyrrolidone salt hybrid electrolyte thin films. Silicon, 16(4), 1407–1419. https://doi.org/10.1007/s12140-023-02844-4
P
Paz, L. F., Caño-García, M., Geday, M., Otón, J., & Quintana, X. (2022). Optical characterization of molecular dynamics and relaxation processes in flexible organic thin-film configurations. Scientific Reports, 12(1), Article 6142. https://doi.org/10.1038/s41598-022-10111-y
Plouzeau, M., Piogé, S., Peilleron, F., Fontaine, L., & Pascual, S. (2022). Synthesis and performance of block copolymer based solid polymer electrolytes via computational chemistry and experiments. Journal of Applied Polymer Science, 139(22), Article e52861. https://doi.org/10.1002/app.52861
Q
Qadir, A., Shafique, S., Iqbal, T., Ali, H., Xin, L., Ruibing, S., & Ahmad, I. (2024). Roll-to-roll processed silver nanowire/silicon dioxide microsphere hybrid conductive electrode for touch sensing application. Sensors and Actuators A: Physical, 370, Article 115267. https://doi.org/10.1016/j.sna.2024.115267
Qashou, S. I., El-Zaidia, E., Darwish, A., & Hanafy, T. (2019). Dielectric relaxations and transport properties parameter analysis of novel blended solid polymer electrolyte. Physica B: Condensed Matter, 571, 93–100. https://doi.org/10.1016/j.physb.2019.06.052
R
Rajesh, K., Krishnan, P., Mani, A., Anandan, K., Gayathri, K., & Devendran, P. (2020). Pure and Mn2+ doped PVP freestanding films: Structural, thermal, and optical studies. Materials Research Innovations, 24(5), 295–300. https://doi.org/10.1080/14328917.2019.1644312
Rehman, W. U., Khattak, M. N. T., Saeed, A., Shaheen, K., Shah, Z., Hussain, S., & Khan, S. A. (2023). Co3O4/NiO nanocomposite as a thermocatalytic and photocatalytic material for the degradation of organic dyes. Journal of Materials Science: Materials in Electronics, 34(1), Article 15. https://doi.org/10.1007/s10854-022-09419-4
S
Saeed, A., & Abdulwahed, J. A. M. (2024). Synergistic enhancement of electrical and ionic conductivity in PVA/PVP copper/لإثيوم تيتانات أكسيد إلكتروليت نانوية. Journal of Energy Storage, 98, Article 113138. https://doi.org/10.1016/j.est.2024.113138
Saeed, A., Asnag, G. M., Alghamdi, A. M., Alghamdi, S. A., Alwafi, R., Alanazi, F. K., & Morsi, M. A. (2024). Improving the polyethylene oxide/carboxymethyl cellulose blend's optical and electrical/dielectric performance by incorporating hybrid quantum dots for energy storage. Journal of Energy Storage, 96Trace, Article 112765. https://doi.org/10.1016/j.est.2024.112765
Saeed, A., Razvi, M. A. N., & Salah, N. (2021). Linear and non-linear optical parameters of copper chloride doped poly (vinyl alcohol) thin-film structures. Results in Physics, 24, Article 104162. https://doi.org/10.1016/j.rinp.2021.104162
Sánchez Vergara, M. E., Hernández Méndez, J. A., González Verdugo, D., Giammattei Funes, I. M., & Lozada Flores, O. (2023). Tuning optical and electrical features of PVC based composite films via integration of metal oxide nanoparticles. Polymers, 15(14), Article 3125. https://doi.org/10.3390/polym15143125
Shahid, M. A., Rahman, M. M., Hossain, M. T., Hossain, I., Sheikh, M. S., Rahman, M. S., & Peijs, T. (2025). Novel of (polymer blend-Fe3O4) magnetic nanocomposites: Preparation and characterization for thermal energy storage and release. Journal of Composites Science, 9(2), Article 42. https://doi.org/10.3390/jcs9020042
Stejskal, J. (2020). Polymers based on aniline and related compounds: Progress, challenges, and environmental perspectives. Chemical Papers, 74(1), 1–54. https://doi.org/10.1007/s11696-019-00912-3
Suma, G., Subramani, N. K., Shilpa, K., Sachhidananda, S., Satyanarayana, S., & Siddaramaiah. (2017). Microstructure, optical and broadband dielectric properties of P(VDF-HFP)/PEO/ZnO ternary hybrid nanocomposites. Journal of Materials Science: Materials in Electronics, 28(14), 10707–10714. https://doi.org/10.1007/s10854-017-6846-1
T
Tauc, J. (1974). Amorphous and liquid semiconductors. Plenum Press. https://doi.org/10.1007/978-1-4615–8705-7
Tou, Z., Koh, T., & Chan, C. (2014). Smooth ZnO:Al composite electrodes based on optical fiber layouts for specialized electrochemical sensing. Sensors and Actuators B: Chemical, 202, 185–193. https://doi.org/10.1016/j.snb.2014.05.056
Tuama, A. N., Abass, K. H., & Agam, M. A. B. (2021). Fabrication of core-shell composite nanostructures and testing their refractive index and optical dielectric constants. Optik, 247, Article 167980. https://doi.org/10.1016/j.ijleo.2021.167980
V
Vongsvivut, J., Itoh, T., Ikehata, A., Ekgasit, S., & Ozaki, Y. (2006). An infrared spectroscopy study of polymer matrices, blending dynamics and hydrogen bonding networks. ScienceAsia, 32(3), 261–269. https://doi.org/10.2306/scienceasia1511-2462.2006.32.261
W
Waly, A., Abdelghany, A., & Tarabiah, A. (2022). Optical, thermal, and electrical characterization of polyvinyl pyrrolidone/carboxymethyl cellulose blend scattered by transitional metal complexes. Journal of Materials Science: Materials in Electronics, 33(29), 23174–23186. https://doi.org/10.1007/s10854-022-09062-z
Y
Yuan, H. .-K., Ren, J., Ma, X. .-H., & Xu, Z. .-L. (2011). PVC–PMMA composite electrospun membranes as polymer electrolytes for lithium-ion battery configurations. Desalination, 280(1-3), 252–258. https://doi.org/10.1016/j.desal.2011.07.014
Z
Zidan, H. M., Abdelrazek, E. M., Abdelghany, A. M., & Tarabiah, A. E. (2019). Conductivity, linear and nonlinear optical parameters of gold nanoparticles filled biopolymer composites. Journal of Materials Research and Technology, 8(1), 904–913. https://doi.org/10.1016/j.jmrt.2018.04.020
Zyoud, S. H., AlAbdulaal, T. H., Almoadi, A., Alqahtani, M. S., Harraz, F. A., Al-Assiri, M. S., & Henaish, A. (2023). One-pot pulsed laser ablation route assisted titanium trioxide nano-structures doped in ternary matrix for capacitive energy storage. Crystals, 13(4), Article 608. https://doi.org/10.3390/cryst13040608
