Tek Damla Yöntemi ile Oluşturulmuş Ca₂NaNb₄O₁₃⁻ Nanolevha Filmlerinin Yüzey Pürüzlülüğünün Atomik Kuvvet Mikroskobu ile Nicel Analizi

Abstract

Bu çalışmada, tek damla biriktirme yöntemi kullanılarak hazırlanan dielektrik Ca₂NaNb₄O₁₃⁻ iki boyutlu nanolevhalardan oluşan nanofilmlerin morfolojik değişimi, ısıl işlem sıcaklığının bir fonksiyonu olarak (oda sıcaklığından 450 °C’ye kadar) incelenmiştir. Yüzey parametreleri olan aritmetik ortalama pürüzlülük (Sa), kök ortalama kare yükseklik (Sq), Sq/Sa oranı ve eğim dağılımı, Atomik Kuvvet Mikroskobu görüntülerinden belirlenmiştir. Kruskal–Wallis ve Dunn testlerine göre, ısıl işlemin nanofilmlerin yüzey morfolojisi üzerinde istatistiksel olarak anlamlı bir etkisi olduğu anlaşılmıştır. 350 °C’de elde edilen Sq/Sa oranı (1.97 ± 0.33, p < 0.001), yüzeyde geçici bir morfolojik düzensizliğin oluştuğunu göstermiştir. Buna karşılık, 450 °C’de uygulanan ısıl işlem, en düşük pürüzlülük değerleri (Sa = 2.75 ± 0.89) ve azalmış eğim dağılımı (ortalama eğim 3.15°, p < 0.001) ile en düzgün yüzeyi sağlamıştır. Bu bulgular, 450 °C’de uygulanan ısıl işlemin, yeni nesil nanoelektronik uygulamalar için yüksek kaliteli dielektrik nanofilmlerin başarılı şekilde üretilmesinde önemli bir rol oynadığını açıkça göstermektedir.

Keywords

• Perovskit Nanolevhalar
• İki Boyutlu Malzemeler
• Tek Damla Biriktirme Yöntemi
• Atomik Kuvvet Mikroskobu
• Yüzey Morfolojisi

Quantitative Atomic Force Microscopy Assessment of Surface Roughness in Single-Droplet Assembled Ca2NaNb4O13- Nanosheet Films

Abstract

In this study, the morphological change of the nanofilms composed of dielectric Ca2NaNb4O13- two-dimensional nanosheets prepared via the single-droplet assembly method was investigated as a function of thermal treatment (room temperature to 450°C). The surface parameters, arithmetic mean roughness (Sa), root mean square height (Sq), Sq/Sa ratio, and slope distribution, were determined from Atomic Force Microscopy images. Based on the Kruskal-Wallis and Dunn’s tests, the heat treatment had a significant effect on the surface morphology of the nanofilms. The Sq/Sa ratio reached at 350°C (1.97 ± 0.33, p < 0.001) indicated that the temporary morphological irregularity. Conversely, the heat treatment at 450°C produced the most uniform surface with the lowest roughness (Sa = 2.75 ± 0.89) and a reduced slope distribution (mean slope of 3.15°, p < 0.001). These findings clearly indicate that the heat treatment at 450°C plays an important role in the successful fabrication of high-quality, dielectric nanofilms for next-generation nano-electronic applications.

Keywords

• Perovskite nanosheets
• Two-dimensional nanosheets
• Single-droplet assembly
• Atomic force microscopy
• Surface Morphology

References

1. [1] Bhimanapati GR, Lin Z, Meunier V, Jung Y, Cha J, Das S, Xiao D, Son Y, Strano MS, Cooper VR, Liang L. Recent advances in two-dimensional materials beyond graphene. ACS Nano 2015;9:11509-11539. https://doi.org/10.1021/acsnano.5b05556
2. [2] Dou L, Wong AB, Yu Y, Lai M, Kornienko N, Eaton SW, Fu A, Bischak CG, Ma J, Ding T, Ginsberg NS. Atomically thin two-dimensional organic-inorganic hybrid perovskites. Science 2015;349:1518-1521. https://doi.org/10.1126/science.aac7660
3. [3] Aziza MR, Chang CW, Mohapatra A, Chu CW, Kaun CC, Su YH. Dion–Jacobson Phase Perovskite Ca2Nan–3NbnO3n+1– (n = 4–6) Nanosheets as High-κ Photovoltaic Electrode Materials in a Solar Water Splitting Cell. ACS Applied Nano Materials 2020;3:6367-6375. https://doi.org/10.1021/acsanm.0c00747
4. [4] Osada M, Sasaki T. Nanoarchitectonics in dielectric/ferroelectric layered perovskites: from bulk 3D systems to 2D nanosheets. Dalton Transactions 2018; 47: 2841-2851. https://doi.org/10.1039/c7dt03719h
5. [5] Küçükcan B, Sağlam Ö. Flexible Transparent Nanocapacitors Based On High‐κ Perovskite Nanosheets. ChemNanoMat. 2025;202500331. https://doi.org/10.1002/cnma.202500331
6. [6] Küçükcan B, Günay B, Gordesli-Duatepe FP, Sağlam Ö. Langmuir-Blodgett deposition and physicochemical surface characterization of two-dimensional perovskite nanosheets on ITO-PET substrates. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2023;666:131338. https://doi.org/10.1016/j.colsurfa.2023.131338
7. [7] Jeong K, Lee D. Colloidal Wet Coating Techniques of Two‐Dimensional Materials. Advanced Materials Technologies 2025;e01805. https://doi.org/10.1002/admt.202501805
8. [8] Shi Y, Osada M, Ebina Y, Sasaki T. Single droplet assembly for two-dimensional nanosheet tiling. ACS Nano 2020;14: 15216-15226. https://doi.org//10.1021/acsnano.0c05434

9. [9] Shi Y, Yamamoto E, Kobayashi M, Osada M. Automated one-drop assembly for facile 2D film deposition. ACS Applied Materials and Interfaces 2023;15:22737-22743. https://doi.org/10.1021/acsami.3c02250
10. [10] Gordesli‐Duatepe FP, Küçükcan B, Sağlam Ö. Effect of UV Light Exposure Duration on the Removal of Exfoliation Agent Residues in Two‐Dimensional Perovskite Nanosheets: An AFM Study. ChemPlusChem 2025;90:e202400678. https://doi.org/10.1002/cplu.202400678
11. [11] Carneiro K, Jensen CP, Jørgensen JF, Garnæs J, McKeown PA. Roughness parameters of surfaces by atomic force microscopy. CIRP Annals 1995; 44: 517-522. https://doi.org/10.1016/S0007-8506(07)62376-2.
12. [12] Im M, Kweon SH, Kim DH, Lee WH, Nahm S, Choi JW, Hwang SJ. Structural and electrical properties of Sr2NaNb4O13 thin film grown by electrophoretic method using nanosheets synthesized from K (Sr2Na) Nb4O13 compound. Journal of the European Ceramic Society. 2017;37(6):2407-13. https://doi.org/10.1016/j.jeurceramsoc.2017.02.012
13. [13] Kweon SH, Im M, Lee WH, Nahm S, Choi JW, Hwang SJ. Electrophoretic deposition of Ca2Nb3O10− nanosheets synthesized by soft-chemical exfoliation. Journal of Materials Chemistry C. 2016;4(1):178-84. https://doi.org/10.1039/c5tc03815d
14. [14] Li BW, Osada M, Ebina Y, Akatsuka K, Fukuda K, Sasaki T. High thermal robustness of molecularly thin perovskite nanosheets and implications for superior dielectric properties. ACS Nano. 2014;8(6):5449-61. https://doi.org/10.1021/nn502014c
15. [15] Ma R, Sasaki T. Nanosheets of oxides and hydroxides: ultimate 2D charge‐bearing functional crystallites. Advanced Materials 2010;22: 5082-5104. https://doi.org/10.1002/adma.201001722
16. [16] Chang CW, Nurpratiwi AA, Su YH. A comparison study of molten-salt and solid-state method for the photoelectrochemical water splitting performance of Dion-Jacobson layers perovskite Ca2Nan-3NbnO3n+1- (n= 4, 5, and 6) nanosheets. International Journal of Hydrogen Energy 2022;47:40573-40581. https://doi.org/10.1016/j.ijhydene.2021.07.227
17. [17] Nečas D, Klapetek P. Gwyddion: An open-source software for SPM data analysis. Central European Journal of Physics 2012; 10, 181-188. https://doi.org/10.2478/s11534-011-0096-2 [18] McKight PE, Najab J. Kruskal‐wallis test. The Corsini Encyclopedia of Psychology. 2010; 1-1. https://doi.org/10.1002/9780470479216
18. [19] Dunn OJ. Multiple comparisons using rank sums. Technometrics. 1964; 6 (3): 241-52. https://doi.org/10.1080/00401706.1964.10490181
19. [20] Sağlam Ö, Küçükcan B, Orhon A, Cantas A, Gordesli-Duatepe FP, Unal U. Dimensionality and surface-state effect on upconversion and optical thermometry in Yb3+/Ho3+-doped KCa2Nb3O10 and its exfoliated two-dimensional nanosheets. ChemNanoMat. 2026;12:e70278. https://doi.org/10.1002/cnma.70278
20. [21] Kim YH, Kim HJ, Osada M, Li B, Ebina Y, Sasaki T. 2D perovskite nanosheets with thermally-stable high-κ response: A new platform for high-temperature capacitors. ACS Applied Materials and Interfaces 2014; 6(22): 19510-19514. https://doi.org/10.1021/am506629g
21. [22] Sasaki T, Ebina Y, Fukuda K, Tanaka T, Harada M, Watanabe M. Titania nanostructured films derived from a titania nanosheet/polycation multilayer assembly via heat treatment and UV irradiation. Chemistry of Materials. 2002; 14(8):3524-3530. http://dx.doi.org/10.1021/cm02024