LPCVD yöntemiyle dielektrik yüzeyler üzerinde ultra ince hekzagonal bor nitrürün büyüme koşullarının optimizasyonu

Öz

Bu çalışmada, katalitik olmayan kuvars altlıklar üzerinde ultra ince altıgen Bor Nitrür (h-BN) filmlerinin doğrudan ve transfer gerektirmeyen sentezi, Düşük Basınçlı Kimyasal Buhar Biriktirme (LPCVD) yöntemi kullanılarak incelenmiştir. Yüksek kaliteli film büyümesini elde etmek amacıyla büyüme süresi (15–90 dk), prekürsör miktarı (50–200 mg) ve prekürsör ayrışma sıcaklığı (80–100°C) gibi temel büyüme parametrelerinin etkileri sistematik olarak araştırılmıştır. Spektroskopik karakterizasyon, Raman spektrumlarında karakteristik E₂g titreşim modunun gözlenmesi ve FT-IR analizinde sırasıyla 1370 ve 800 cm⁻¹’de belirgin B–N gerilme ve B–N–B bükülme bağlarının tespit edilmesiyle h-BN fazının oluşumunu doğrulamıştır. UV-Vis spektroskopisi, görünür bölgede yüksek optik geçirgenlik (> %95) olduğunu ortaya koymuş ve Tauc grafiği analizi optik bant aralığını 5,68 eV olarak belirlemiştir. Yığın h-BN’e (~5,2 eV) kıyasla bant aralığındaki bu artış, kuantum sınırlama etkisi nedeniyle filmlerin birkaç katmanlı doğasına dair nicel kanıt sunmaktadır. Elde edilen sonuçlar, optimize edilmiş LPCVD sürecinin dielektrik yüzeyler üzerinde h-BN sentezinin hassas şekilde kontrol edilmesine olanak tanıdığını ve optoelektronik uygulamalar için metal katalizörler ile karmaşık transfer süreçlerine olan ihtiyacı ortadan kaldırdığını göstermektedir.

Anahtar Kelimeler

• LPCVD
• h-BN ince film
• katalitik olmayan etki
• dielektrik alttaş
• derin ultraviyole fotodedektörler.

Optimization for growth condition of ultrathin hexagonal boron nitride on dielectric substrates via LPCVD method

Öz

In this study, the direct and transfer-free synthesis of ultrathin hexagonal Boron Nitride (h BN) films on non-catalytic quartz substrates was investigated using the Low-Pressure Chemical Vapor Deposition (LPCVD) method. The effects of key growth parameters, including growth duration (15-90 min), precursor amount (50-200 mg), and precursor decomposition temperature (80-100°C), were systematically investigated to achieve high quality film growth. Spectroscopic characterization confirmed the formation of the h-BN phase, with Raman spectra exhibiting the characteristic E2g vibrational mode and FT-IR analysis showing the distinct B-N stretching and B-N-B bending bonds at 1370 and 800 cm-1, respectively. UV-Vis spectroscopy revealed high optical transparency (>95%) in the visible region, and Tauc plot analysis yielded an optical bandgap of 5.68 eV. This widening of the bandgap relative to bulk h-BN (~5.2 eV) provides quantitative evidence of the few-layer nature of the films due to the quantum confinement effect. The results demonstrate that the optimized LPCVD process allows for the precise control of h-BN synthesis on dielectric surfaces, eliminating the need for metal catalysts and complex transfer processes for optoelectronic applications.

Anahtar Kelimeler

• LPCVD
• h-BN thin film
• non-catalytic effect
• dielectric substrates
• deep ultraviolet photodetectors.

Kaynakça

1. Liu, X., Lv, Z., Liao, Z., Sun, Y., Zhang, Z., Sun, K., ... & Zhou, S. (2024). Highly efficient AlGaNbased deep-ultraviolet light-emitting diodes: from bandgap engineering to device craft. Microsystems & Nanoengineering, 10(1), 110. https://doi.org/10.1038/s41378-024-00737-x
2. Long, J. P., Varadaraajan, S., Matthews, J., & Schetzina, J. F. (2002). UV detectors and focal plane array imagers based on AlGaN pin photodiodes. Optoelectronics Review, (4), 251-260.
3. Cao, T., Wang, P., Wu, T., Wang, M., Zhang, H., Wang, K., & Song, J. (2025). Performance analysis of non-lineof- sight ultraviolet communications under periodic pulse jamming attack through turbulent channels. Optics Express, 33(17), 35146-35163. https://doi.org/10.1364/OE.566788
4. Sharma, V. K., & Demir, H. V. (2022). Bright future of deep-ultraviolet photonics: Emerging UVC chip-scale light-source technology platforms, benchmarking, challenges, and outlook for UV disinfection. ACS Photonics, 9(5), 1513-1521. https://doi.org/10.1021/acsphotonics.2c00041
5. Hao, J., Li, L., Gao, P., Jiang, X., Ban, C., & Shi, N. (2023). Deep ultraviolet detectors based on wide bandgap semiconductors: a review. Journal of Nanoparticle Research, 25(4), 81. https://doi.org/10.1007/s11051-023-05694-6
6. Chen, R., Li, Q., Zhang, Q., Li, J., Zhang, Z., Fang, W., ... & Hao, Y. (2023). High-crystallinity and high-temperature S-stability of the hexagonal boron nitride film grown on sapphire. Crystal Growth & Design, 23(12), 8783-8792. https://doi.org/10.1021/acs.cgd.3c00902
7. Veeralingam, S., Durai, L., Yadav, P., and Badhulika, S. (2021). Record-high responsivity and detectivity of a flexible deep-ultraviolet photodetector based on solid state-assisted synthesized hBN nanosheets. ACS Applied Electronic Materials, 3(3), 1162-1169. https://doi.org/10.1021/acsaelm.0c01021
8. Kaushik, S., & Singh, R. (2021). 2D layered materials for ultraviolet photodetection: A review. Advanced Optical Materials, 9(11), 2002214. https://doi.org/10.1002/adom.202002214

9. Fang, W., Li, Q., Li, J., Li, Y., Zhang, Q., Chen, R., & Wang, T. (2023). Deep ultraviolet photodetector: Materials and devices. Crystals, 13(6), 915. https://doi.org/10.3390/cryst13060915
10. Lv, J., Lu, X., Li, X., Xu, M., Zhong, J., Zheng, X., … & Zhang, Q. (2022). Epitaxial growth of lead-free 2D Cs3Cu2I5 perovskites for high-performance UV photodetectors. Small, 18(27), 2201715. https://doi.org/10.1002/smll.202201715
11. Zhang, K., Feng, Y., Wang, F., Yang, Z., & Wang, J. (2017). Two-dimensional hexagonal boron nitride (2D-hBN): Synthesis, properties and applications. Journal of Materials Chemistry C, 5(46), 11992-12022. https://doi.org/10.1039/C7TC04300G
12. Zhang, J., Tan, B., Zhang, X., Gao, F., Hu, Y., Wang, L., … & Hu, P. (2021). Atomically thin hexagonal boron nitride and its heterostructures. Advanced Materials, 33(6), 2000769. https://doi.org/10.1002/adma.202000769
13. Lin, C. H., Fu, H. C., Cheng, B., Tsai, M. L., Luo, W., Zhou, L., ... & He, J. H. (2018). A flexible solar-blind 2D boron nitride nanopaper-based photodetector with high thermal resistance. 2D Materials and Applications, 2(1), 23. https://doi.org/10.1038/s41699-018-0070-6
14. Li, J., Majety, S., Dahal, R., Zhao, W. P., Lin, J. Y., & Jiang, H. X. (2012). Dielectric strength, optical absorption, and deep ultraviolet detectors of hexagonal boron nitride epilayers. Applied Physics Letters, 101(17). https://doi.org/10.1063/1.4764533
15. Zhang, X., Yang, H., Su, Z., Tian, Y., Feng, Y., Ding, Y., … & Hu, P. (2025). Ultraflat single-crystal hexagonal boron nitride film grown on Cu/Ni (1 1 1) for highperformance deep ultraviolet photodetectors. Chemical Engineering Journal, 163316. https://doi.org/10.1016/j.cej.2025.163316
16. Chen, X., Tan, C., Liu, X., Luan, K., Guan, Y., Liu, X., … & Chen, Z. (2021). Growth of hexagonal boron nitride films on silicon substrates by low-pressure chemical vapor deposition. Journal of Materials Science: Materials in Electronics, 32, 3713-3719. https://doi.org/10.1007/s10854-020-05116-6
17. Li, L., Chen, H., Fang, Z., Meng, X., Zuo, C., Lv, M., … & Ding, L. (2020). An electrically modulated singlecolor/ dual-color imaging photodetector. Advanced Materials, 32(24), 1907257. https://doi.org/10.1002/adma.201907257
18. Sutter, P., Lahiri, J., Zahl, P., Wang, B., & Sutter, E. (2013). Scalable synthesis of uniform few-layer hexagonal boron nitride dielectric films. Nano Letters, 13(1), 276-281. https://doi.org/10.1021/nl304080y
19. Li, D., Gao, W., Sun, X., Yu, H., Liu, C., & Yin, H. (2021). Direct growth of hexagonal boron nitride thick films on dielectric substrates by ion beam assisted deposition for deep-UV photodetectors. Advanced Optical Materials, 9(12), 2100342. https://doi.org/10.1002/adom.202100342
20. Li, Q., Wu, Q., Gao, J., Wei, T., Sun, J., Hong, H., … & Liu, Z. (2018). Direct growth of 5 in. uniform hexagonal boron nitride on glass for high-performance deepultraviolet light-emitting diodes. Advanced Materials Interfaces, 5(18), 1800662. https://doi.org/10.1002/admi.201800662
21. Behura, S., Nguyen, P., Debbarma, R., Che, S., Seacrist, M. R., & Berry, V. (2017). Chemical interaction-guided, metal-free growth of large-area hexagonal boron nitride on silicon-based substrates. ACS Nano, 11(5), 4985-4994. https://doi.org/10.1021/acsnano.7b01666
22. Gao, M., Meng, J., Chen, Y., Ye, S., Wang, Y., Ding, C., & Zhang, X. (2019). Catalyst-free growth of twodimensional hexagonal boron nitride few-layers on sapphire for deep ultraviolet photodetectors. Journal of Materials Chemistry C, 7(47), 14999-15006. https://doi.org/10.1039/C9TC05206B
23. Singhal, R., Echeverria, E., McIlroy, D. N., & Singh, R. N. (2021). Synthesis of hexagonal boron nitride films on silicon and sapphire substrates by low-pressure chemical vapor deposition. Thin Solid Films, 733, 138812. https://doi.org/10.1016/j.tsf.2021.138812
24. Li, D., Gao, W., Sun, X., Yu, H., Liu, C., & Yin, H. (2021). Direct growth of hexagonal boron nitride thick films on dielectric substrates by ion beam assisted deposition for deep-UV photodetectors. Advanced Optical Materials, 9(12), 2100342. https://doi.org/10.1002/adom.202100342
25. Chen, R., Li, Q., Zhang, Q., Li, J., Zhang, Z., Fang, W., … & Hao, Y. (2023). High-crystallinity and hightemperature stability of the hexagonal boron nitride film grown on sapphire. Crystal Growth & Design, 23(12), 8783-8792. https://doi.org/10.1021/acs.cgd.3c00902
26. Aldalbahi, A., & Feng, P. (2015). Development of 2-D boron nitride nanosheets UV photoconductive detectors. IEEE Transactions on Electron Devices, 62(6), 1885-1890. https://doi.org/10.1109/TED.2015.2423253
27. Roy, S., Zhang, X., Puthirath, A. B., Meiyazhagan, A., Bhattacharyya, S., Rahman, M. M., … & Ajayan, P. M. (2021). Structure, properties and applications of two dimensional hexagonal boron nitride. Advanced Materials, 33(44), Article 2101589. https://doi.org/10.1002/adma.202101589
28. Cao, F., Liu, Y., Liu, M., Han, Z., Xu, X., Fan, Q., & Sun, B. (2024). Wide bandgap semiconductors for ultraviolet photodetectors: Approaches, applications, and prospects. Research, 7, 0385. https://doi.org/10.34133/research.0385
29. Chalmpes, N., Bourlinos, A. B., Alsmaeil, A. W., Aljarrah, A. S., Salmas, C. E., Karakassides, M. A., & Giannelis, E. P. (2024). First synthesis of 2D materials by hypergolic reactions and evaluation of their dispersions for ink formulation: Hexagonal boron nitride and fluorinated carbon nanosheets. Materials Research Express, 11(3), 035002. https://doi.org/10.1088/2053-1591/ad2d42
30. Zemlyanov, D. Y., Jespersen, M., Zakharov, D. N., Hu, J., Paul, R., Kumar, A., ... & Voevodin, A. A. (2018). Versatile technique for assessing thickness of 2D layered materials by XPS. Nanotechnology, 29(11), 115705. https://doi.org/10.1088/1361-6528/aaa6ef
31. Weston, L., Wickramaratne, D., Mackoit, M., Alkauskas, A., & Van de Walle, C. G. (2018). Native point defects and impurities in hexagonal boron nitride. Physical Review B, 97(21), 214104. https://doi.org/10.1103/PhysRevB.97.214104
32. Rousseau, A., Valvin, P., Elias, C., Xue, L., Li, J., Edgar, J. H., ... & Cassabois, G. (2022). Stacking-dependent deep level emission in boron nitride. Physical Review Materials, 6(9), 094009. https://doi.org/10.1103/PhysRevMaterials.6.094009
33. Chen, X., Yue, X., Zhang, L., Xu, X., Liu, F., Feng, M., ... & Fu, X. (2024). Activated single photon emitters and enhanced deep-level emissions in hexagonal boron nitride strain crystal. Advanced Functional Materials, 34(1), 2306128. https://doi.org/10.1002/adfm.202306128
34. Du, X. Z., Li, J., Lin, J. Y., & Jiang, H. X. (2015). The origin of deep-level impurity transitions in hexagonal boron nitride. Applied Physics Letters, 106(2). https://doi.org/10.1063/1.4905908
35. Tsushima, E., Tsujimura, T., & Uchino, T. (2018). Enhancement of the deep-level emission and its chemical origin in hexagonal boron nitride. Applied Physics Letters, 113(3). https://doi.org/10.1063/1.5038168
36. Choutipalli, V. S. K., Esackraj, K., Varathan, E., & Subramanian, V. (2022). Vacancy defect assisted enhanced nitrogen fixation in boron nitride nanomaterials. Applied Surface Science, 602, 154406. https://doi.org/10.1016/j.apsusc.2022.154406
37. Singh, B., Kaur, G., Singh, P., Singh, K., Kumar, B., Vij, A., ... & Kumar, A. (2016). Nanostructured boron nitride with high water dispersibility for boron neutron capture therapy. Scientific Reports, 6(1), 35535. https://doi.org/10.1038/srep35535
38. Shen, T., Liu, S., Yan, W., & Wang, J. (2019). Highly efficient preparation of hexagonal boron nitride by direct microwave heating for dye removal. Journal of Materials Science, 54(12), 8852-8859. https://doi.org/10.1007/s10853-019-03514-8
39. Huang, C., Chen, C., Ye, X., Ye, W., Hu, J., Xu, C., & Qiu, X. (2013). Stable colloidal boron nitride nanosheet dispersion and its potential application in catalysis. Journal of Materials Chemistry A, 1(39), 12192-12197. https://doi.org/10.1039/C3TA12231J
40. Stefanovsky, S. V., Fox, K. M., & Marra, J. C. (2013). Infrared and Raman spectroscopic study of glasses in the Al2O3-B2O3-Fe2O3-Na2O-SiO2 System. MRS Online Proceedings Library (OPL), 1518, 53-58. https://doi.org/10.1557/opl.2013.143
41. Xu, H., Li, K., Tan, Z., Jia, J., Wang, L., & Chen, S. (2025). Recent advances in chemical vapor deposition of hexagonal boron nitride on insulating substrates. Nanomaterials, 15(14), 1059. https://doi.org/10.3390/nano15141059