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Investigation of photocatalytic activity (under visible light) of ultrathin CZTS films produced in different thicknesses by PLD method

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Abstract

Cu2ZnSnS4 (CZTS) thin films in 61 nm, 112 nm, 242 nm and 313 nm thickness which have been produced by Pulsed Laser Deposition (PLD) on Soda Lime Glass substrates as a function of the number of laser pulses. As the deposition of ablated material has been augmented with increasing number of laser pulses, it has been noticed that CZTS-ultrathin film’s thicknesses and particle sizes have been increased, their crystalline structures have been improved. Larger particles limit the transmission of light and cause thin films to absorb photons. The band gaps of CZTS (61 nm), CZTS (112 nm), CZTS (242 nm) and CZTS (313 nm) thin film which have been determined to be 1.95 eV, 1.90 eV, 1.50 eV and 1.45 eV, respectively. CZTS (61 nm) ultrathin film with the thinnest one among the thin films produced in this work, which is Cu and S poor but Sn and Zn rich. By increasing the thickness of the film, it has been observed that the amount of Cu and S were increased, and the ratio of Sn and Zn were decreased. In addition, it has been systematically investigated that the photocatalytic activity of the ultra-thin CZTS films coated in different thicknesses by PLD method. Among all the photocatalysts, the CZTS (in 242 nm thickness) photocatalyst has exhibited the highest photocatalytic performance, managing to remove 96.1% of methylene blue (MB) in 240 min. Furthermore, the mechanism that performs photocatalysis has been investigated by scavenger experiments, and it was observed that \({}^{ \cdot }O_{2}^{ - }\) radical ions have an important role in the reaction, while holes have little effect.

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References

  • Amakiri, K.T., Angelis-Dimakis, A., Ramirez Canon, A.: Recent advances, influencing factors, and future research prospects using photocatalytic process for produced water treatment. Water Sci. Technol. 85(3), 769–788 (2022)

    Google Scholar 

  • Apostolopoulou, A., et al.: Novel development of nanocrystalline kesterite Cu2ZnSnS4 thin film with high photocatalytic activity under visible light illumination. J. Phys. Chem. Solids 112, 37–42 (2018)

    ADS  Google Scholar 

  • Atwee, T., et al.: Effect of film thickness on structural, morphological, and optical properties of Cu2ZnSnS4 thin films prepared by sol–gel spin coating. Appl. Phys. A 125(4), 1–10 (2019)

    ADS  Google Scholar 

  • Azeez, F., et al.: The effect of surface charge on photocatalytic degradation of methylene blue dye using chargeable titania nanoparticles. Sci. Rep. 8(1), 1–9 (2018)

    MathSciNet  ADS  Google Scholar 

  • Baaloudj, O., et al.: Simultaneous removal of antibiotics and inactivation of antibiotic-resistant bacteria by photocatalysis: a review. J. Water Process Eng. 42, 1–11 (2021)

    Google Scholar 

  • Beres, M., et al.: Stoichiometry control in Cu2ZnSnS4 thin films grown by pulsed laser deposition. Mater. Chem. Phys. 205, 90–96 (2018)

    Google Scholar 

  • Camara, S.M., Wang, L., Zhang, X.: Easy hydrothermal preparation of Cu2ZnSnS4 (CZTS) nanoparticles for solar cell application. Nanotechnology 24(49), 495401 (2013)

    Google Scholar 

  • Đekić, M., et al.: Influence of deposition parameters on pulsed laser deposition of K0. 3MoO3 thin films. Bull. Chem. Technol. Bosnia Herzeg. 48(1), 1–4 (2017)

    Google Scholar 

  • Dong, H., et al.: An overview on limitations of TiO2-based particles for photocatalytic degradation of organic pollutants and the corresponding countermeasures. Water Res. 79, 128–146 (2015)

    Google Scholar 

  • Dundar, I., et al.: Thickness effect on photocatalytic activity of TiO2 thin films fabricated by ultrasonic spray pyrolysis. Catalysts 10(9), 1–13 (2020)

    Google Scholar 

  • Dursun, S., et al.: UV/visible light active CuCrO 2 nanoparticle–SnO 2 nanofiber p–n heterostructured photocatalysts for photocatalytic applications. Dalton Trans. 47(41), 14662–14678 (2018)

    Google Scholar 

  • Dursun, S., et al.: Production of CuO–WO3 hybrids and their dye removal capacity/performance from wastewater by adsorption/photocatalysis. J. Water Process Eng. 36, 1–10 (2020)

    Google Scholar 

  • Dursun, S., Akyildiz, H., Kalem, V.: PMN-PT nanoparticle/SnO2 nanofiber heterostructures: enhanced photocatalytic degradation performance by ultrasonic wave induced piezoelectric field. J. Alloy. Compd. 889, 161769 (2021)

    Google Scholar 

  • Elhmaidi, Z., et al.: In-situ tuning of the zinc content of pulsed-laser-deposited CZTS films and its effect on the photoconversion efficiency of p-CZTS/n-Si heterojunction photovoltaic devices. Appl. Surf. Sci. 507, 1–10 (2020)

    Google Scholar 

  • Fateh, R., Dillert, R., Bahnemann, D.: Preparation and characterization of transparent hydrophilic photocatalytic TiO2/SiO2 thin films on polycarbonate. Langmuir 29(11), 3730–3739 (2013)

    Google Scholar 

  • Feng, Y., et al.: In-situ ion exchange electrocatalysis biological coupling (i-IEEBC) for simultaneously enhanced degradation of organic pollutants and heavy metals in electroplating wastewater. J. Hazard. Mater. 364, 562–570 (2019)

    Google Scholar 

  • Ferreira, M.A., et al.: Fabrication of SrTiO3/g-C3N4 heterostructures for visible light-induced photocatalysis. Mater. Sci. Semicond. Process. 108, 1–10 (2020)

    Google Scholar 

  • Fujishima, A., Honda, K.: Electrochemical photolysis of water at a semiconductor electrode. Nature 238(5358), 37–38 (1972)

    ADS  Google Scholar 

  • Gezgin, S.Y., Kiliç, H.Ş: The electrical characteristics of ITO/CZTS/ZnO/Al and ITO/ZnO/CZTS/Al heterojunction diodes. Optik 182, 356–371 (2019)

    ADS  Google Scholar 

  • Gezgin, S.Y., Kılıç, H.Ş: The electrical characteristics of ITO/CZTS/ZnO/Al and ITO/ZnO/CZTS/Al heterojunction diodes. Optik 182, 356–371 (2019)

    ADS  Google Scholar 

  • Gezgin, S.Y., Houimi, A., Kılıç, H.Ş: Production and photovoltaic characterisation of n-Si/p-CZTS heterojunction solar cells based on a CZTS ultrathin active layers. Optik 199, 1–11 (2019)

    ADS  Google Scholar 

  • Gezgin, S.Y., et al.: The effect of CZTS ultrathin film thickness on the electrical characteristic of CZTS/Si heterojunction solar cells in the darkness and under the illumination conditions. SILICON 13(10), 3555–3567 (2021a)

    Google Scholar 

  • Gezgin, S.Y., et al.: Determination of photovoltaic parameters of CIGS hetero junction solar cells produced by PLD technique, using SCAPS simulation program. Vacuum 192, 1–9 (2021b)

    ADS  Google Scholar 

  • Gupta, G.K., Reddy, V., Dixit, A.: Impact of excess and disordered Sn sites on Cu2ZnSnS4 absorber material and device performance: a 119Sn Mössbauer study. Mater. Chem. Phys. 225, 410–416 (2019)

    Google Scholar 

  • Han, S., et al.: Construction of ZnIn2S4-CdIn2S4 microspheres for efficient photo-catalytic reduction of CO2 with visible light. CHIN. J. STRUCT. CHEM., 41(1), (2022)

  • Hu, J., et al.: High-efficiency removal of phenol and coking wastewater via photocatalysis-Fenton synergy over a Fe-g-C3N4 graphene hydrogel 3D structure. J. Ind. Eng. Chem. 84, 305–314 (2020)

    Google Scholar 

  • Inamdar, A., et al.: Optimized fabrication of sputter deposited Cu2ZnSnS4 (CZTS) thin films. Sol. Energy 91, 196–203 (2013)

    ADS  Google Scholar 

  • Khan, I., et al.: Review on methylene blue: its properties, uses, toxicity and photodegradation. Water 14(2), 1–30 (2022)

    Google Scholar 

  • Kılıç, H.Ş, et al.: Nonlinear optical properties of Cu 2 ZnSnS 4 nanocrystal thin films and its constituents thin films. Opt. Quant. Electron. 53(1), 1–11 (2021)

    Google Scholar 

  • Kumar, K.J., Raju, N.R.C., Subrahmanyam, A.: Thickness dependent physical and photocatalytic properties of ITO thin films prepared by reactive DC magnetron sputtering. Appl. Surf. Sci. 257(7), 3075–3080 (2011)

    ADS  Google Scholar 

  • Madiraju, V.A., et al.: CZTS synthesis in aqueous media by microwave irradiation. J. Mater. Sci. Mater. Electron. 27(4), 3152–3157 (2016)

    Google Scholar 

  • Marcelino, R.B., et al.: Novel and versatile TiO2 thin films on PET for photocatalytic removal of contaminants of emerging concern from water. Chem. Eng. J. 370, 1251–1261 (2019)

    Google Scholar 

  • Ong, C.B., Ng, L.Y., Mohammad, A.W.: A review of ZnO nanoparticles as solar photocatalysts: synthesis, mechanisms and applications. Renew. Sustain. Energy Rev. 81, 536–551 (2018)

    Google Scholar 

  • Pedanekar, R., Shaikh, S., Rajpure, K.: Thin film photocatalysis for environmental remediation: a status review. Curr. Appl. Phys. 20(8), 931–952 (2020)

    ADS  Google Scholar 

  • Peksu, E., Karaagac, H.: Characterization of Cu2ZnSnS4 thin films deposited by one-step thermal evaporation for a third generation solar cell. J. Alloy. Compd. 862, 1–9 (2021)

    Google Scholar 

  • Pérez-González, M., Tomás, S.: Surface chemistry of TiO2-ZnO thin films doped with Ag. Its role on the photocatalytic degradation of methylene blue. Catal. Today 360, 129–137 (2021)

    Google Scholar 

  • Phaltane, S.A., et al.: Photocatalytic degradation of methylene blue by hydrothermally synthesized CZTS nanoparticles. J. Mater. Sci. Mater. Electron. 28(11), 8186–8191 (2017)

    Google Scholar 

  • Rajan, G., et al.: Characterization and analysis of ultrathin CIGS films and solar cells deposited by 3-Stage process. J. Spectrosc. 2018, 1–9 (2018)

    Google Scholar 

  • Rathi, B.S., Kumar, P.S., Vo, D.-V.N.: Critical review on hazardous pollutants in water environment: occurrence, monitoring, fate, removal technologies and risk assessment. Sci. Total Environ. 797, 1–22 (2021)

    ADS  Google Scholar 

  • Saravanan, R., Gracia, F., Stephen, A.: Basic principles, mechanism, and challenges of photocatalysis. In: Nanocomposites for Visible Light-Induced Photocatalysis, pp. 19–40. Springer, Berlin (2017)

    Google Scholar 

  • Sarswat, P.K., Free, M.L.: A study of energy band gap versus temperature for Cu2ZnSnS4 thin films. Physica B 407(1), 108–111 (2012)

    ADS  Google Scholar 

  • Singha, M.K., Patra, A.: Highly efficient and Reusable ZnO microflower photocatalyst on stainless steel mesh under UV–Vis and natural sunlight. Opt. Mater. 107, 1–9 (2020)

    Google Scholar 

  • Tahir, M., Ali, S., Rizwan, M.: A review on remediation of harmful dyes through visible light-driven WO3 photocatalytic nanomaterials. Int. J. Environ. Sci. Technol. 16(8), 4975–4988 (2019)

    Google Scholar 

  • Tamjidi, S., et al.: Improving the surface properties of adsorbents by surfactants and their role in the removal of toxic metals from wastewater: a review study. Process Saf. Environ. Prot. 148, 775–795 (2021)

    Google Scholar 

  • Tao, J., et al.: A sputtered CdS buffer layer for co-electrodeposited Cu 2 ZnSnS 4 solar cells with 6.6% efficiency. Chem. Commun. 51(51), 10337–10340 (2015)

    Google Scholar 

  • Vakulov, Z., et al.: Size effects in LiNbO3 thin films fabricated by pulsed laser deposition. J. Phys. Conf. Series 1124, 022032 (2018)

    Google Scholar 

  • Vaya, D., Surolia, P.K.: Semiconductor based photocatalytic degradation of pesticides: an overview. Environ. Technol. Innov. 20, 1–25 (2020)

    Google Scholar 

  • Wadhene, R., et al.: Electrodeposition of Cu2ZnSnS4 thin films onto TiO2 nanorods for photocatalytic application: effect of deposition time. Inorg. Chem. Commun. 122, 1–11 (2020)

    Google Scholar 

  • Wang, X., et al.: Ag clusters anchored conducting polyaniline as highly efficient cocatalyst for Cu2ZnSnS4 nanocrystals toward enhanced photocatalytic hydrogen generation. ACS Sustain. Chem. Eng. 6(9), 11424–11432 (2018)

    Google Scholar 

  • Wang, X.-Q., et al.: Photocatalytic oxidation degradation mechanism study of methylene blue dye waste water with GR/iTO2. In MATEC Web of Conferences. 2018. EDP Sciences

  • Wu, C.-Y., et al.: Thickness-dependent photocatalytic performance of nanocrystalline TiO2 thin films prepared by sol–gel spin coating. Appl. Surf. Sci. 280, 737–744 (2013)

    ADS  Google Scholar 

  • Wu, J., et al.: Catalytic ozonation of organic pollutants from bio-treated dyeing and finishing wastewater using recycled waste iron shavings as a catalyst: removal and pathways. Water Res. 92, 140–148 (2016)

    Google Scholar 

  • Xia, D., et al.: Synthesis and characterization of Cu2ZnSnS4 nanocrystals by hot-injection method. J. Mater. Sci. Mater. Electron. 26(7), 5426–5432 (2015)

    Google Scholar 

  • Xiao-Wei, M., et al.: Dramatically enhanced visible-light-responsive H-2 evolution of Cd1-xZnxS via the synergistic effect of Ni2P and 1T/2H MoS2 cocatalysts. Chin. J. Struct. Chem. 40(1), 7–22 (2021)

    Google Scholar 

  • Yang, J., et al.: Enhanced catalytic activation of photo-Fenton process by Cu0· 5Mn0· 5Fe2O4 for effective removal of organic contaminants. Chemosphere 247, 1–9 (2020)

    ADS  Google Scholar 

  • Yao, L., et al.: Bismuth oxychloride-based materials for the removal of organic pollutants in wastewater. Chemosphere 273, 1–19 (2021)

    ADS  Google Scholar 

  • Zhang, K., et al.: An order/disorder/water junction system for highly efficient co-catalyst-free photocatalytic hydrogen generation. Energy Environ. Sci. 9(2), 499–503 (2016)

    Google Scholar 

  • Zhu, D., Zhou, Q.: Action and mechanism of semiconductor photocatalysis on degradation of organic pollutants in water treatment: a review. Environ. Nanotechnol. Monit. Manag. 12, 1–11 (2019)

    Google Scholar 

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Acknowledgements

Author kindly would like to thank, Selcuk University Scientific Research Project (BAP) Coordination for the support with the number 18401124 and project, Selçuk University, High Technology Research and Application Center (İL-TEK) and SULTAN Center for infrastructures.

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Authors and Affiliations

  1. Department of Metallurgical and Materials Engineering, Konya Technical University, Konya, Turkey

    Sami Dursun

  2. Department of Chemical Engineering, Konya Technical University, Konya, Turkey

    Fatma Bayram Sarıipek

  3. Department of Physics, Faculty of Science, Selcuk University, 42031, Selcuklu, Konya, Turkey

    Serap Yiğit Gezgin & Hamdi Şükür Kılıç

  4. Department of Computer Technologies, Kadınhanı Faik İçil Vocational High School, Selçuk University, 42031, Kadınhanı, Konya, Turkey

    Yasemin Gündoğdu

  5. Laser Induced Proton Therapy Application and Research Center, University of Selçuk, Konya, Turkey

    Yasemin Gündoğdu & Hamdi Şükür Kılıç

  6. Department of Metallurgical and Materials Engineering, Selcuk University, Konya, Turkey

    Sümeyye Kılıç

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  1. Sami Dursun
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Contributions

S.D.: Formal analysis, Software, Visualization, Writing—Original Draft, Writing—Review & Editing, Resources, Methodology; F.B.S.: Conceptualization, Visualization, Writing—Original Draft, Writing—Review& Editing, Resources, Methodology; S.K.: Methodology, Writing—Original Draft, Writing—Review& Editing, Resources; S.Y.G.: Conceptualization, Visualization, Writing—Original Draft, Writing—Review& Editing, Resources, Methodology, Formal analysis, Software; Y.G.: Visualization, Writing—Original Draft, Writing—Review & Editing, Resources, Methodology, Formal analysis, Software; H.Ş.K.: Project administration, Supervision, Visualization. Writing—Original Draft, Writing—Review & Editing, Resources, Conceptualization, Methodology.

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Correspondence to Hamdi Şükür Kılıç.

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Dursun, S., Sarıipek, F.B., Kılıç, S. et al. Investigation of photocatalytic activity (under visible light) of ultrathin CZTS films produced in different thicknesses by PLD method. Opt Quant Electron 55, 166 (2023). https://doi.org/10.1007/s11082-022-04417-w

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