Abstract
In this study, WO3:Ni (0 at.%, 10 at.%, 20 at.%, and 30 at.%) and WO3:Co20 at.%: Ni (0%, 5%, 10%, 20%, and 30%) thin films were deposited on glass substrates by pyrolysis spray technique and then annealed at T = 500 °C. For the preparation of thin films, the initial solution of 0.1 M tungsten oxide and the precursors of nickel sulfate and 6-hydrate cobalt chloride were used. After preparing thin films, the effect of the presence of Ni impurities on the structural, morphology, optical and electrochromic properties of WO3:Ni and WO3:Co 20 at.%–Ni thin films was studied. The results of the X-ray diffraction showed that the structure of thin films after annealing has a polycrystalline structure with the combined phases of CoWO4, NiWO4, and W17O49 with monoclinic and hexagonal structures. As the amount of Ni impurities increases, the grain size of the WO3:Ni thin films increases and ranges from 8 to 36 nm. Also, for WO3 thin films:Co20 at.%:Ni, the CoWO4 and NiWO4 phases have been seen and the grain size was in the range from 35 to 39 nm. The voltametric cycle diagrams of WO3:Ni and WO3:Co20 at.%:Ni thin films showed that the electrochromic behavior improves with increasing nickel impurity. The morphology of the thin films was studied by field emission electron microscopy (FESEM). Also, the energy band gap of thin films with the addition of nickel and cobalt impurities was calculated using UV–Vis diagrams. The energy gap is decreased for both WO3:Ni and WO3:Co (20%):Ni thin films.
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References
Bandi, S., Srivastav, A.K.: Review: oxygen-deficient tungsten oxides. J. Mater. Sci. 56, 6615–6644 (2021)
Bathe, S.R., Patil, P.S.: Electrochromic characteristics of fibrous reticulated WO3 thin films prepared by pulsed spray pyrolysis technique. Sol. Energy Mater. Sol. Cells 91(12), 1097–1101 (2007)
Bonomo, M., Dini, D., Decker, F.: Electrochemical and photoelectrochemical properties of nickel oxide (NiO) with nanostructured morphology for photoconversion applications. Front. Chem. 6, 601 (2018). https://doi.org/10.3389/fchem.2018.00601
Chang, ChCh., Chi, P.W., Chandan, P., Lin, Ch.K.: Electrochemistry and rapid electrochromism control of MoO3/V2O5 hybrid nanobilayers. Materials 12, 2475–2483 (2019)
Dai, J., Li, Y., Ruan, H., Ye, Z., Chai, N., Wang, X., Qiu, S., Bai, W., Yang, M.: Fiber optical hydrogen sensor based on WO3-Pd2Pt-Pt nanocomposite films. Nanomaterials 11, 128–136 (2021)
Deb, S.K.: Opportunities and challenges in science and technology of WO3 for electrochromic and related applications. Sol. Energy Mater. Sol. 92, 245–258 (2008)
Deshpande, M.P., Patel, K.N., Gujarati, V.P., Patel, K., Chaki, S.H.: Structural, thermal and optical properties of nickel oxide (NiO) nanoparticles synthesized by chemical precipitation method. Adv. Mater. Res. 1141, 65–71 (2016)
Dong, C., Zhao, R., Yao, L., Ran, Y., Zhang, X., Wang, Y.: A review on WO3 based gas sensors: morphology control and enhanced sensing properties. J. Alloy. Compd. 820, 153194–153217 (2020)
Fularz, A., Almohammed, S., Rice, J.H.: Controlling plasmon-induced photocatalytic redox reactions on WO3 nanowire/AgNPs substrates via defect engineering. J. Phys. Chem. C 124, 25351–25360 (2020)
Gaewdang, T., Wongcharoen, N.: Temperature-dependent electrical transport characteristics of p-SnS/n-WO3: Sb heterojunction diode. Mater. Sci. Eng. 383, 012006–0122011 (2018)
Gesheva, K.A., Cziraki, A., Ivanova, T., Szekeres, A.: Crystallization of chemically vapor deposited molybdenum and mixed tungsten/molybdenum oxide films for electrochromic application. Thin Solid Films 515(11), 4609–4613 (2007)
Huang, J.-J., Huang, C.-S., Ho, Y.-R., Yu-Qi, Wu.: Electrochromic property improvement of WO3 films by using PEDOT:PSS-AgNWs/ITO counter electrode. Mater. Lett. 303, 130479–130481 (2021). https://doi.org/10.1016/j.matlet.2021.130479
Ivanova, T., Gesheva, K.A., Szekeres, A.: Structure and optical properties of CVD molybdenum oxide films for electrochromic application. J. Solid State Electrochem. 7(1), 21–24 (2002)
Janssen, G.J.M., Nieuwpoort, W.C.: Band gap in NiO: a cluster study. Phys. Rev. B 38(5), 3449–3458 (1988)
Ji, Y., Yang, Y., Lee, S.K., Ruan, G., Kim, T.W., Fei, H., Lee, S.H., Kim, D.Y., Yoon, J., Tour, J.M.: Flexible nanoporous WO3-x nonvolatile memory device. ACS Nano 10, 7598–7603 (2016)
Karaca, G.Y., Eren, E., Cogal, G.C., Uygun, E., Oksuz, L.: Enhanced electrochromic characteristics induced by Au/PEDOT/Pt microtubes in WO3 based electrochromic devices. Opt. Mater. 88, 472–478 (2019)
Karthik, Y.P.V., Ajitha, B., Kumar Reddy, Y.A., Minnam Reddy, V.R., Reddeppad, M., Kim, M.D.: Effect of sputter pressure on UV photodetector performance of WO3 thin films. Appl. Surf. Sci. 536, 147947–147955 (2021)
Kharade, R.R., Mali, S.S., Mohite, S.S., Kondalkar, V.V., Patil, P.S., Bhosalel, P.N.: Hybrid physicochemical synthesis and electrochromic performance of WO3/MoO3 thin films. Electroanalysis 26, 2388–2397 (2014)
Kim, D.G., Kim, S.H., Kim, Y.D.: Electrochromic property of MoO3 thin films deposited by chemical vapor transport synthesis. Jpn. J. Appl. Phys. 50, 102601 (2011)
Kim, Y.H., Lee, S.Y., Umh, H.N., Song, H.D., Han, J.W., Choi, J.W., Yi, J.: Directional change of interfacial electric field by carbon insertion in heterojunction system TiO2/WO3. ACS Appl. Mater. Interfaces 12, 15239–15245 (2020)
Li, S., Li, X., Li, Y., Yan, B., Song, X., Li, D.: Superior sodium storage of vanadium pentoxide cathode with controllable interlamellar spacing. Electrochim. Acta 244, 77–85 (2017)
Li, N., Fu, S., Wu, J., Li, X., Zhou, J., Wang, Y., Zhang, X., Liu, Y.: WO3/ZnO nanowire heterojunction as hole transport channel for building up persistent holographic fringes. Appl. Phys. Lett. 116, 251606 (2020)
Lin, H., Long, X., An, Y., Yang, S.: In situ growth of Fe2WO6 on WO3 nanosheets to fabricate heterojunction arrays for boosting solar water splitting. J. Chem. Phys. 152, 214704 (2020)
Ling, Z., Leach, C., Freer, R.: NO2 sensitivity of a heterojunction sensor based on WO3 and doped SnO2. J. Eur. Ceram. Soc. 23(11), 1881–1891 (2003)
Liu, S., Qu, X.: Construction of nanocomposite film of Dawson-type polyoxometalate and TiO2 nanowires for electrochromic applications. Appl. Surf. Sci. 412, 189–195 (2017)
Lu, H.H.: Effects of oxygen contents on the electrochromic properties of tungsten oxide films prepared by reactive magnetron sputtering. J. Alloys Compd. 465(1–2), 429–435 (2008)
Meenakshi, M., Sivakumar, R., Perumal, P., Sanjeeviraja, C.: Studies on electrochromic properties of RF sputtered vanadium oxide: tungsten oxide thin films. Mater. Today Proc. 3S, S30–S39 (2016)
Nandapure, B.I., Kondawar, S.B., Salunkhe, M.Y., Nandapure, A.I.: Magnetic and transport properties of conducting polyaniline/nickel oxide nanocomposites. Adv. Mater. Lett. 4(2), 134–140 (2013)
Patterson, A.: The Scherrer formula for X-ray particle size determination. Phys. Rev. 56(10), 978–982 (1939)
Pereira, S., Gonçalves, A., Correia, N., Pinto, J., Pereira, L., Martins, R., Fortunato, E.: Electrochromic behavior of NiO thin films deposited by e-beam evaporation at room temperature. Sol. Energy Mater. Sol. Cells 1(120), 109–115 (2014)
Poongodi, S., Kumar, P.S., Masuda, Y., Mangalaraj, D., Ponpandian, N., Viswanathan, C., Ramakrishna, S.: Synthesis of hierarchical WO3 nanostructured thin films with enhanced electrochromic performance for switchable smart windows. RSC Adv. 5(117), 96416–96427 (2015)
Qiongling, D., Yanrong, W., Pengqian, G., Li, J., Chen, C., Ting, W., Sn, K., Deyan, H.: Cr-doped urchin-like WO3 hollow spheres: the cooperative modulation of crystal growth and energy-band structure for high-sensitive acetone detection. Sensors 20, 3473–3481 (2020)
Rao, M.C.: Structure and properties of WO3 thin films for electrochromic device application. J. Non-Oxide Glasses 5, 1–8 (2013)
Sasi, B., Gopchandran, K.G.: Preparation and characterization of nanostructured NiO thin films by reactive-pulsed laser ablation technique. Sol. Energy Mater. Sol. Cells 91(15–16), 1505–1509 (2007)
Sasi, B., Gopchandran, K.G., Manoj, P.K., Koshy, P., Rao, P.P., Vaidyan, V.K.: Preparation of transparent and semiconducting NiO films. Vacuum 68(2), 149–154 (2002)
Seike, T., Nagai, J.: Electrochromism of 3d transition metal oxides. Sol. Energy Mater. 22(2–3), 107–117 (1991)
Shirpay, A., Bagheri-Mohagheghi, M.M.: Investigation of structural, optical and thermoelectric properties of 2H–MoTe2 and MoO3–TeO2 thin films. Physica B 587, 412141–412153 (2020). https://doi.org/10.1016/j.physb.2020.412141
Shirpay, A., Mohagheghi, M.M.B.: The effect of H2Te2O6 and TeO2 phases on structural and electrochromic properties of WO3–TeO2 nanostructured binary thin films. J. Mater. Sci. 56, 14644–14658 (2021). https://doi.org/10.1007/s10853-021-06233-1
Sivakarthik, P., Thangaraj, V., Parthibavarman, M.: A facile and one-pot synthesis of pure and transition metals (M = Co & Ni) doped WO3 nanoparticles for enhanced photocatalytic performance. J. Mater. Sci. Mater. Electron. 28(8), 5990–5996 (2017)
Sun, J., Zhang, S., Zhan, T., Liu, Z., Wang, J., Yi, X., Li, J., Sarro, P.M., Zhang, G.: A high responsivity and controllable recovery ultraviolet detector based on a WO3 gate AlGaN/GaN heterostructure with an integrated micro-heater. J. Mater. Chem. C 8, 5409–5416 (2020)
Varkey, A.J., Fort, A.F.: Solution growth technique for deposition of nickel oxide thin films. Thin Solid Films 235(1–2), 47–50 (1993)
Wang, L., Cheng, S., Wu, C., Pei, K., Song, Y., Li, H., Wang, Q., Sang, D.: Fabrication and high temperature electronic behaviors of n-WO3 nanorods/p-diamond heterojunction. Appl. Phys. Lett. 110(15), 052106–052110 (2017)
**a, X.H., Tu, J.P., Zhang, J., Wang, X.L., Zhang, W.K., Huang, H.: Electrochromic properties of porous NiO thin films prepared by a chemical bath deposition. Sol. Energy Mater. Sol. Cells 92(6), 628–633 (2008)
Yano, M., Kuwagata, W., Mito, H., Koike, K., Kobayashi, S., Inaba, K.: Electrochromic properties of epitaxial WO3 thin films grown on sapphire substrates. Jpn. J. Appl. Phys. 57, 100309 (2018)
Yin, C., Zhu, S., Zhang, D.: 3D nanostructured WO3/BiVO4 heterojunction derived from Papilio paris for efficient water splitting. RSC Adv. 7, 27354–27360 (2017)
Yoshimura, K., Miki, T., Tanemura, S.: Nickel oxide electrochromic thin films prepared by reactive DC magnetron sputtering. Jpn. J. Appl. Phys. 34(5R), 2440–2446 (1995)
Yu, P., Yang, H., Chen, X., Yi, Z., Yao, W., Chen, J., Yi, Y., Wu, P.: Ultra-wideband solar absorber based on refractory titanium metal. Renew. Energy 158, 227–235 (2020)
Zhang, J., Lu, H., Liu, C., Chen, C., **n, X.: Porous NiO-WO3 heterojunction nanofibers fabricated by electrospinning with enhanced gas sensing properties. RSC Adv. 7, 40499–40509 (2017)
Zhao, F., Chen, X., Yi, Z., Qin, F., Tang, Y., Yao, W., Zhou, Z., Yi, Y.: Study on the solar energy absorption of hybrid solar cells with trapezoid-pyramidal structure based PEDOT:PSS/c-Ge. Sol. Energy 204, 635–643 (2020)
Zhong, X., Liu, X., Diao, X.: Electrochromic devices based on tungsten oxide and nickel oxide: a review. J. Inorg. Mater. 36, 128–139 (2021)
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Dalenjan, F.A., Bagheri-Mohagheghi, M.M. & Shirpay, A. The study of structural, optical and electrochromic properties of WO3:Co:Ni thin films deposited by spray pyrolysis. Opt Quant Electron 54, 711 (2022). https://doi.org/10.1007/s11082-022-04113-9
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DOI: https://doi.org/10.1007/s11082-022-04113-9