Termal Buharlaştırma ile Üretilen Cu2-xSe İnce Filmlerin Yapısal, Morfolojik ve Optik Özellikleri Üzerine Araştırma

Abstract

Bu çalışmada, termal buharlaştırma yöntemi ile cam alttaşlar üzerine kaplanmış bakır selenür ince filmlerin yapısal, morfolojik ve optik özelliklerine, üretim sonrası ısıl işlemin etkisi detaylı olarak araştırıldı.Oda sıcaklığında üretilen ince filmlere, azot gazı altında farklı sıcaklıklarda üretim sonrasıısıl işlem uygulandı. X ışını kırınım (XRD) deseni analizi, üretilmiş filmlerin kübik yapıda Cu2-xSe fazında olduğunu ve ısıl işlem sıcaklığı arttıkça filmlerin kristalleşme seviyesinin arttığnı gösterdi. Ayrıca, artan sıcaklıkla ortalama kristal boyutunun arttığı sonucu elde edildi. Filmlerin yüzey morfolojisini araştırmak için taramalı elektron mikroskobu ve atomik kuvvet mikroskobu kullanıldı. Filmlerin kompakt ve sıkı paketlenmiş yüzey morfolojisine sahip olduğu ve artan ısıl işlem sıcaklığı ile yüzeydeki tanelerin boyutlarının arttığı görüldü.Isıl işlem sıcaklığı arttıkça, yüzey pürüzlülüğü 11 nm’den 53 nm’ye yükseldi. Diğer yandan, üretilen ve ısıl işlem uygulanan ince filmlerin optik özellikleri, ultraviyole- görünür ışık spektrofotometrekullanılarakincelendi. Filmlerin direkt bant aralıkları, iyi bilinen Tauc bağıntısı kullanılarak sırasıyla 2.34eV, 2.31eV ve 2.29 eV olarak bulundu. Ayrıca, ince filmlerin direkt bant aralıkları türev spektroskopi tekniği kullanılarak da hesaplandı.

Keywords

• İnce Film
• Karakterizasyon
• Üretim Sonrası Isıl İşlem
• Yarıiletken
• Termal Buharlaştırma

A Study on the Structural, Morphological and Optical Properties of Cu2-xse Thin Films Deposited by Thermal Evaporation

Abstract

In this work, the influence of post-annealing on the structural, morphological, and optical properties of copper selenide thin films deposited on glass substrate by thermal evaporation was investigated in detail. The post-annealing process at different ambient temperatures in a nitrogen atmosphere was applied to thin films deposited at room temperature. The X-ray diffraction (XRD) patterns showed the presence of cubic Cu2-xSe phase, and it was observed that the crystallinity improves with increasing annealing temperature. In addition, it was deduced that the average crystallite size increased with the annealing temperature. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were employed to investigate the surface morphology of thin films. It was seen that all samples have compact and densely packed surface morphology and grains on the surface become larger. Surface roughness increased from 11nm to 53 nm as the annealing temperature increased. On the other hand, the optical properties of as-deposited and annealed thin films were investigated by utilizing a UV-Visible spectrophotometer. The direct bandgap energies of as-deposited and annealed samples were estimated to be 2.34 eV, 2.31 eV, and 2.29 eV by using the well-known Tauc relation, respectively. The direct bandgap energy of thin films was also calculated using the derivative spectroscopy technique.

Keywords

• Thin Film
• Characterization
• Post-annealing
• Semiconductor
• Thermal Evaporation

References

1. Pathan, H., Desai, J., & Lokhande, C. (2002). Modified chemical deposition and physico-chemical properties of copper sulphide (Cu2S) thin films. Applied Surface Science, 202(1), 47–56.
2. Zhang, Y., Zhou, Q., Zhu, J., Yan, Q., Dou, S. X., & Sun, W. (2017). Nanostructured Metal Chalcogenides for Energy Storage and Electrocatalysis. Advanced Functional Materials, 27(35), 1702317.
3. Lee, K., & Lee, S. (2021). A nanoscale Cu2−xSe ultrathin film deposited via atomic layer deposition and its memristive effects. Nanotechnology, 32(24), 245202.
4. Ambade, S. B., Mane, R. S., Kale, S. S., Sonawane, S. H., Shaikh, A. V., & Han, S. H. (2006). Chemical synthesis of p-type nanocrystalline copper selenide thin films for heterojunction solar cells. Applied Surface Science, 253(4), 2123–2126.
5. Ni, S., Su, Y., Ai, Z., Hu, J., Yang, Z., Kong, E. S. W., & Zhang, Y. (2016). Bandgap tuning and photocatalytic activities of CuSe1–xSx nanoflakes. Ceramics International, 42(1), 211–219.
6. Vinod, T. P., Jin, X., & Kim, J. (2011). Hexagonal nanoplatelets of CuSe synthesized through facile solution phase reaction. Materials Research Bulletin, 46(3), 340–344.
7. Li, Y. Z., Gao, X. D., Yang, C., & Huang, F. Q. (2010). The effects of sputtering power on optical and electrical properties of copper selenide thin films deposited by magnetron sputtering. Journal of Alloys and Compounds, 505(2), 623–627.
8. Li, Y. D., Fan, P., Zheng, Z. H., Luo, J. T., Liang, G. X., & Guo, S. Z. (2016). The influence of heat treatments on the thermoelectric properties of copper selenide thin films prepared by ion beam sputtering deposition. Journal of Alloys and Compounds, 658, 880–884.

9. Quiao, L.N., Wang, H. C., Shen, Y., Lin., Y.H., & Nan, C. W. (2017). Enhanced Photocatalytic Performance under Visible and Near-Infrared Irradiation of Cu1.8Se/Cu₃Se₂ Composite via a Phase Junction. Nanomaterials (Basel, Switzerland), 7(1).
10. Gu, Y., Su, Y., Chen, D., Geng, H., Li, Z., Zhang, L., & Zhang, Y. (2014). Hydrothermal synthesis of hexagonal CuSe nanoflakes with excellent sunlight-driven photocatalytic activity. Cryst Eng Comm, 16(39), 9185–9190.
11. Bayraklı, Ö., Terlemezoglu, M., Güllü, H. H., & Parlak, M. (2017). Investigation of precursor sequence and post-annealing effects on the properties of Cu2SnZnSe4 thin films deposited by the elemental thermal evaporation. Materials Research Express, 4(8), 086411.
12. Tanaka, T., Sueishi, T., Saito, K., Guo, Q., Nishio, M., Yu, K. M., & Walukiewicz, W. (2012). Existence and removal of Cu2Se second phase in coevaporated Cu2ZnSnSe4 thin films. Journal of Applied Physics, 111(5), 053522.
13. Zhang, G., Zhu, L., & Ba, N. (2016). Hydrothermal synthesis of hexagonal Cu2−xSe microplates and optical properties. Materials Engineering and Environmental Science, 158–164.
14. Lippkow, D., & Strehblow, H. H. (1998). Structural investigations of thin films of copper–selenide electrodeposited at elevated temperatures. Electrochimica Acta, 43(14–15), 2131–2140.
15. Okimura, H., Matsumae, T., & Makabe, R. (1980). Electrical properties of Cu2−xSethin films and their application for solar cells. Thin Solid Films, 71(1), 53–59.
16. Peranantham, P., Jeyachandran, Y. L., Viswanathan, C., Praveena, N. N., Chitra, P. C., Mangalaraj, D., & Narayandass, S. K. (2007). The effect of annealing on vacuum-evaporated copper selenide and indium telluride thin films. Materials Characterization, 58(8–9), 756–764.
17. Xue, M.Z., Zhou, Y.N., Zhang, B., Yu, L., Zhang, H., & Fu, Z.-W. (2006). Fabrication and Electrochemical Characterization of Copper Selenide Thin Films by Pulsed Laser Deposition. Journal of The Electrochemical Society, 153(12), A2262.
18. Astam, A., Akaltun, Y., & Yildirim, M. (2016). Conversion of SILAR deposited Cu3Se2 thin films to Cu2−xSe by annealing. MaterialsLetters, 166, 9–11.
19. Surucu, O., Isik, M., Terlemezoglu, M., Gasanly, N. M., & Parlak, M. (2021). Structural and temperature-tuned bandgap characteristics of thermally evaporated β-In2S3 thin films. Journal of Materials Science: Materials in Electronics 2021 32:12, 32(12), 15851–15856.
20. Terlemezoglu, M., Bayrakli Sürücü, O., Colakoǧlu, T., Abak, M. K., Güllü, H. H., Ercelebi, C., & Parlak, M. (2019). Construction of self-assembled vertical nanoflakes on CZTSSe thin films. Materials Research Express. 6(2),026421.
21. Erturk, K., Isik, M., Terlemezoglu, M., & Gasanly, N. M. (2021). Optical and structural characteristics of electrodeposited Cd 1-xZnxS nanostructured thin films. Optical Materials, 114, 110966.
22. Terlemezoglu, M., Bayraklı Sürücü, Ö., Dogru, C., Güllü, H. H., Ciftpinar, E. H., Erçelebi, Ç., & Parlak, M. (2019). CZTSSe thin films fabricated by single step deposition for superstrate solar cell applications. Journal of Materials Science: Materials in Electronics, 30, 11301–11306.
23. Surucu, O., Isik, M., Gasanly, N. M., Terlemezoglu, M., & Parlak, M. (2020). Temperature-tuned band gap properties of MoS2 thin films. Materials Letters, 275, 128080.
24. Caglar, Y., Caglar, M., Ilican, S., & Ates, A. (2009). Morphological, optical and electrical properties of CdZnO films prepared by sol–gel method. Journal of Physics D: Applied Physics, 42(6), 065421.
25. Akin, N., Kinaci, B., Ozen, Y., & Ozcelik, S. (2017). Influence of RF power on the opto-electrical and structural properties of gallium-doped zinc oxide thin films. Journal of Materials Science: Materials in Electronics, 28(10), 7376–7384.
26. López-Suárez, A., Acosta, D., Magaña, C., & Hernández, F. (2020). Optical, structural and electrical properties of ZnO thin films doped with Mn. Journal of Materials Science: Materials in Electronics, 31(10), 7389–7397.