Karaelmas Fen ve Mühendislik Dergisi 2146-7277 Zonguldak Bülent Ecevit Üniversitesi 10.7212/karaelmasfen.902067 Deposition of TiO2-Doped Diamond-Like Carbon Films From a New Solution and Their Characterizations TiO2 Katkılı Elmas-Benzeri Karbon Filmlerin Yeni Bir Çözeltiden Üretilmesi ve Karakterizasyonları https://orcid.org/0000-0002-8421-641X Başman Necati İSKENDERUN TEKNİK ÜNİVERSİTESİ https://orcid.org/0000-0003-3900-4626 Gökçen Mehmet Zonguldak Bülent Ecevit Üniversitesi https://orcid.org/0000-0002-9265-7485 Temiz Cengiz Zonguldak Bülent Ecevit Üniversitesi 06 01 2022 12 1 1 8 03 23 2021 04 12 2021 Copyright © 2011, Karaelmas Fen ve Mühendislik Dergisi 2011 Karaelmas Fen ve Mühendislik Dergisi

Diamond-like carbon (DLC) films are the most studied coating materials due to their mechanical and physical properties. Manystudies have been conducted on the deposition methods and doping to improve the properties of these films. Among the depositionmethods, the electrochemical deposition has advantages such as convenience and inexpensive equipment. In our previous study, wewere able to produce a titanium dioxide (TiO2) doped DLC film by electrochemical method from a mixture of methanol (CH3OH)and titanium solution obtained by dissolving titanium metal in hydrogen peroxide (H2O2). In this study, TiO2 doped DLC films weredeposited by electrolysis of solutions formed from a mixture of titanium isopropoxide (TTIP) and methanol. The films deposited attwo different TTIP concentrations were characterized morphologically, structurally and elementally. Scanning electron micrographswere shown that the films are homogeneous and compact. No change was observed in the morphology of the films after annealingthe films at 600 0C. Chemical analyses showed that titanium was in the form of TiO2 and the amount of titanium increased withincreasing TTIP concentration. X-ray diffraction analysis revealed that TiO2 was amorphous in the DLC matrix and the film preparedwith lower TTIP concentration had diamond content. After annealing at 600 0C, it was seen that this film was graphitized. Theobtained findings showed that TiO2 doped DLC nanocomposite films can be easily deposited with the solution proposed in this study.

Elmas-benzeri karbon (EBK) filmler gösterdikleri mekanik ve fiziksel özelliklerinden dolayı en çok çalışılan kaplama malzemeleridir.Bu filmlerin özelliklerinin iyileştirilmesi için üretim yöntemleri ve katkılanmaları üzerine pek çok çalışma yapılmıştır. Üretim yöntemleriarasında elektrokimyasal biriktirme yöntemi, kolaylık ve ucuz ekipman gibi avantajlara sahiptir. Daha önceki bir çalışmamızda,titanyum metalini hidrojen peroksit (H2O2) içerisinde çözündürerek elde ettiğimiz titanyum çözeltisi ile metanol (CH3OH)karışımından, elektrokimyasal yöntemle titanyum dioxide (TiO2) katkılı EBK film üretmeyi başarmıştık. Bu çalışmada ise TiO2 katkılıEBK filmler titanyum isopropoxide (TTIP) ve metanol karışımından oluşturulan çözeltilerin elektrolizi ile biriktirildi. İki farklıTTIP konsantrasyonunda üretilen filmler, morfolojik, yapısal ve elementel olarak karakterize edildi. Taramalı elektron mikroskobufotoğrafları filmlerin homojen ve kompakt olduğunu göstermiştir. Filmlerin 600 0C ‘de tavlanmasıyla filmlerin morfolojisinde birdeğişiklik gözlenmemiştir. X-ışınları fotoelektron spektroskopisi analizleri, titanyumun film içerisinde TiO2 formunda olduğunuve TTIP konsantrasyonunun artmasıyla filmdeki titanyum miktarının arttığını göstermiştir. X-ışınları kırınımı analizleri, TiO2’ninEBK matriste amorf olarak bulunduğunu ve daha düşük TTIP konsantrasyonuyla hazırlanan filmin elmas içeriğe sahip olduğunuortaya koymuştur. 600 0C de tavlandıktan sonra ise bu filmin grafitize olduğu görülmüştür. Elde edilen bulgular, TiO2 katkılı EBKnanokompozit filmlerin bu çalışmada önerilen çözeltiyle kolaylıkla üretilebileceğini göstermiştir.

 Elmas-benzeri karbon Titanyum dioksit Nanokompozit Diamond-like carbon Titanium dioxide Nanocomposite Zonguldak Bülent Ecevit Üniversitesi Bilimsel Araştırma Projeleri Koordinatörlüğü 2015-75737790-03 Amin, M. S., Randeniya, L. K., Bendavid, A., Martin, P. J., Preston, E. W. 2009. Diamond & Related Materials Amorphous carbonated apatite formation on diamond-like carbon containing titanium oxide. Diam. Relat. Mater., 18(9): 1139–1144. Doi:10.1016/j.diamond.2009.02.034 Basman, N., Aslan, N., Uzun, O., Cankaya, G., Kolemen, U. 2015. Electrical characterization of metal/diamond-like carbon/inorganic semiconductor MIS Schottky barrier diodes. Microelectron. Eng., 140: 18–22. Doi:10.1016/j.mee.2015.05.001 Basman, N., Uzun, R., Gocer, E., Bacaksiz, E., Kolemen, U. 2018. Electrodeposition of Si–DLC nanocomposite film and its electronic application. Microsyst. Technol., 24(5): 2287–2294. Doi:10.1007/s00542-017-3635-y Basman, N., Varol, S. F. 2019. High Temperature Characterization of a MIS Schottky Diode Based on Diamond-Like Carbon Nanocomposite Film. J. Electron. Mater., 48(12): 7874–7881. Doi:10.1007/s11664-019-07621-9 Basman, N. 2020. TiO2 Katkılı Elmas-Benzeri Karbon Nanokompozit Filmin Elektrokimyasal Yöntemle Biriktirilmesi. Karaelmas Fen ve Müh. Derg., 10: 94-99. Doi: 10.7212/zkufbd.v10i1.1373 Bharti, B., Kumar, S., Lee, H. N., Kumar, R. 2016. Formation of oxygen vacancies and Ti3+ state in TiO2 thin film and enhanced optical properties by air plasma treatment. Scientific Reports., 6: 1–12. Doi:10.1038/srep32355 Bootkul, D., Saenphinit, N., Supsermpol, B., Aramwit, C., Intarasiri, S. 2014. Synthesis of Ti-doped DLC film on SS304 steels by Filtered Cathodic Vacuum Arc (FCVA) technique for tribological improvement. Appl. Surf. Sci., 310: 293–299. Doi:10.1016/j.apsusc.2014.04.053 Bouabibsa, I., Alhussein, A., Lamri, S., Sanchette, F., Rtimi, S. 2020. Biological responses at the interface of Ti-doped diamond-like carbon surfaces for indoor environment application. Environ. Sci. Pollut Res. Int., 27(25): 31120–31129. Doi:10.1007/s11356-020-09376-x Caschera, D., Federici, F., Pandolfi, L., Kaciulis, S., Sebastiani, M., Bemporad, E., Padeletti, G. 2011. Effect of composition on mechanical behaviour of diamond-like carbon coatings modified with titanium. Thin Solid Films, 519(10): 3061–3067. Doi:10.1016/j.tsf.2010.12.031 Chen, S. Y., Ou, K. L., Huang, W. C., Chu, K. T., Ou, S. F. 2013. Phase transformation of diamond-like carbon/silver composite films by sputtering deposition. Ceram. Intern., 39(3): 2575–2580. Doi:10.1016/j.ceramint.2012.09.019 Chen, X., Kuo, D. H., Lu, D. 2017. Visible light response and superior dispersed S-doped TiO2 nanoparticles synthesized via ionic liquid. Adv. Powder Technol., 28(4): 1213–1220. Doi:10.1016/j.apt.2017.02.007 Dai, W., Ke, P., Wang, A. 2013. Influence of bias voltage on microstructure and properties of Al-containing diamond-like carbon films deposited by a hybrid ion beam system. Surf. Coat. Technol., 229: 217–221. Doi:10.1016/j.surfcoat.2012.03.076 Ennaceri, H., Boujnah, M., Taleb, A., Khaldoun, A., Sáez-Araoz, R., Ennaoui, A., El Kenz, A., Benyoussef, A. 2017. Thickness effect on the optical properties of TiO2-anatase thin films prepared by ultrasonic spray pyrolysis: Experimental and ab initio study. Int. J. Hydrog. Energy, 42(30): 19467–19480. Doi:10.1016/j.ijhydene.2017.06.015 Erdemir, A., Donnet, C. 2006. Tribology of diamond-like carbon films: Recent progress and future prospects. J. Phys. D: Appl. Phys., 39(18): 311–327. Doi:10.1088/0022-3727/39/18/R01 He, Z., Que, W., Chen, J., He, Y., Wang, G. 2013. Surface chemical analysis on the carbon-doped mesoporous TiO2 photocatalysts after post-thermal treatment: XPS and FTIR characterization. J. Phys. Chem. Solids 74(7): 924–928. Doi:10.1016/j.jpcs.2013.02.001 Isildak, O., Özbek, O. 2020. Application of potentiometric sensors in real samples. Crit. Rev. Anal. Chem. 1-14. Doi: 10.1080/10408347.2019.1711013 Khun, N. W., Liu, E., Zeng, X. T. 2009. Corrosion behavior of nitrogen doped diamond-like carbon thin films in NaCl solutions. Corros. Sci., 51(9): 2158–2164. Doi:10.1016/j.corsci.2009.05.050 Lin, Y. T., Weng, C. H., Lin, Y. H., Shiesh, C. C., Chen, F. Y. 2013. Effect of C content and calcination temperature on the photocatalytic activity of C-doped TiO2 catalyst. Sep. Purif. Technol., 116: 114–123. Doi:10.1016/j.seppur.2013.05.018 Lopes, F. S., Oliveira, J. R., Milani, J., Oliveira, L. D., Machado, J. P. B., Trava-Airoldi, V. J., Lobo, A. O., Marciano, F. R. 2017. Biomineralized diamond-like carbon films with incorporated titanium dioxide nanoparticles improved bioactivity properties and reduced biofilm formation. Mater. Sci. Eng. C, 81(May): 373–379. Doi:10.1016/j.msec.2017.07.043 Ma, Y., Han, L., Ma, H., Wang, J., Liu, J., Cheng, L., Yang, J., Zhang, Q. 2017. Improving the visible-light photocatalytic activity of interstitial carbon-doped TiO 2 with electron-withdrawing bidentate carboxylate ligands. Catal. Commun., 95: 1–5. Doi:10.1016/j.catcom.2017.02.025 Marciano, F. R., Lima-Oliveira, D. A., Da-Silva, N. S., Diniz, A. V., Corat, E. J., Trava-Airoldi, V. J. 2009. Antibacterial activity of DLC films containing TiO2 nanoparticles. J. Colloid Interface Sci., 340(1): 87–92. Doi:10.1016/j.jcis.2009.08.024 Nezar, S., Saoula, N., Sali, S., Faiz, M., Mekki, M., Laoufi, N. A., Tabet, N. 2017. Properties of TiO2 thin films deposited by rf reactive magnetron sputtering on biased substrates. Appl. Surf. Sci., 395: 172–179. doi:10.1016/j.apsusc.2016.08.125 Park, Y., Kim, W., Park, H., Tachikawa, T., Majima, T., Choi, W. 2009. Carbon-doped TiO2 photocatalyst synthesized without using an external carbon precursor and the visible light activity. Appl. Catal. B . Environ., 91(1–2): 355–361. Doi:10.1016/j.apcatb.2009.06.001 Robertson, J. 2002. Diamond-like amorphous carbon.pdf. Mater. Sci. Eng. R Rep., 37: 129–281. Doi:10.1016/S0927-796X(02)00005-0 Sullivan, J. A., Neville, E. M., Herron, R., Thampi, K. R., Macelroy, J. M. D. 2014. Routes to visible light active C-doped TiO2 photocatalysts using carbon atoms from the Ti precursors. J. Photochem. Photobiol. A, 289: 60–65. Doi:10.1016/j.jphotochem.2014.05.009 Thorwarth, G., Hammerl, C., Kuhn, M., Assmann, W., Schey, B., Stritzker, B. 2005. Investigation of DLC synthesized by plasma immersion ion implantation and deposition. Surf. Coat. Technol., 193(1-3 SPEC. ISS.): 206–212. Doi:10.1016/j.surfcoat.2004.07.061 Wachesk, C. C., Pires, C. A. F., Ramos, B. C., Trava-Airoldi, V. J., Lobo, A. O., Pacheco-Soares, C., Marciano, F. R., Da-Silva, N. S. 2013. Cell viability and adhesion on diamond-like carbon films containing titanium dioxide nanoparticles. Appl. Surf. Sci., 266: 176–181. Doi:10.1016/j.apsusc.2012.11.124 Wachesk, C. C., Trava-Airoldi, V. J., Da-Silva, N. S., Lobo, A. O., Marciano, F. R. 2016. The Influence of Titanium Dioxide on Diamond-Like Carbon Biocompatibility for Dental Applications. J. Nanomater., 2016: 8194516. Doi:10.1155/2016/8194516 Warkhade, S. K., Gaikwad, G. S., Zodape, S. P., Pratap, U., Maldhure, A. V., Wankhade, A. V. 2017. Low temperature synthesis of pure anatase carbon doped titanium dioxide: An efficient visible light active photocatalyst. Mater. Sci. Semicond Process., 63: 18–24. Doi:10.1016/j.mssp.2017.01.011 Xu, W., Zhou, K. S., Lin, S., Dai, M., Shi, Q., Wei, C. 2018. Structural properties of hydrogenated Al-doped diamond-like carbon films fabricated by a hybrid plasma system. Diam. Relat. Mater., 87(June): 177–185. Doi:10.1016/j.diamond.2018.06.012 Y. Huang, W. Ho, S. Lee, L. Zahng, Y. Li, J. Y. 2008. Effect of Carbon Doping on the Mesoporous Structure of Nanocrystalline Titanium Dioxide and Its Solar-Light-Driven Photocatalytic Degradation of NOx. Langmuir, 24(7): 3510-3516. Doi: 10.1021/la703333z Yan, X. B., Xu, T., Yang, S. R., Liu, H. W., Xue, Q. J. 2004. Characterization of hydrogenated diamond-like carbon films electrochemically deposited on a silicon substrate. J. Phys. D: Appl. Phys., 37(17): 2416–2424. Doi:10.1088/0022-3727/37/17/012 Yu, Y., & Zhang, J. 2009. Electrodeposition and characterization of Pd nanoparticles doped amorphous hydrogenated carbon films. Solid State Sci., 11(11), 1929–1932. Doi:10.1016/j.solidstatesciences.2009.07.012