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열화학기상증착법을 이용한 CsPbBr3 박막 성장 및 특성 연구

A Growth and Characterization of CsPbBr3 Thin Film Grown by Thermal Chemical Vapor Deposition

  • 김가은 (전남대학교 화학공학부) ;
  • 김민진 (전남대학교 화학공학부) ;
  • 류혜수 (전남대학교 화학공학부) ;
  • 이상현 (전남대학교 화학공학부)
  • Ga Eun Kim (School of Chemical Engineering, Chonnam National University) ;
  • Min Jin Kim (School of Chemical Engineering, Chonnam National University) ;
  • Hyesu Ryu (School of Chemical Engineering, Chonnam National University) ;
  • Sang Hyun Lee (School of Chemical Engineering, Chonnam National University)
  • 투고 : 2023.06.21
  • 심사 : 2023.06.30
  • 발행 : 2023.06.30

초록

본 연구에서는 열화학기상증착법을 이용한 세슘계 무기 페로브스카이트의 성장기판에 따른 결정 구조의 변화 및 광학적 특성을 비교 분석하였다. 무기 페로브스카이트 결정은 CsBr과 PbBr2를 전구체로 사용하여 SiO2/Si와 c-Al2O3 기판 위에 동일한 조건으로 CsPbBr3를 성장하였다. 비정질 구조를 가진 SiO2 표면에서는 Cs4PbBr6-CsPbBr3 혼합상의 결정 입자가 성장하였으며, 단결정 구조인 c-Al2O3 기판에서는 CsPbBr3 (100) 결정 면방향이 우세한 단일상의 박막이 형성되었다. 광학적 분석 결과 CsPbBr3는 약 91 meV의 반치폭을 갖고 약 534 nm 중심의 발광특성을 보였으며, Cs4PbBr6-CsPbBr3 혼합구조에서는 청색 변이에 의해 523 nm의 발광 및 6.88 ns의 빠른 광 소결시간을 확인하였다. 열화학기상증착법을 이용한 페로브스카이트의 결정구조의 제어 및 광특성의 변화는 디스플레이, 태양 전지, 광센서 등 다양한 광전 소자에 적용할 수 있을 것으로 기대된다.

In this study, inorganic perovskite films with different compositions were grown by thermal chemical vapor deposition depending on the substrate and their optical properties were compared. Inorganic perovskite crystals were grown on SiO2/Si and c-Al2O3 substrates using CsBr and PbBr2, respectively, under the same growth conditions. Cs4PbBr6-CsPbBr3 crystallites were grown on the SiO2 with polycrystalline structure, while a CsPbBr3 (100) dominant thin film was formed on the c-Al2O3 substrate with single crystal structure. From the photoluminescence measurement, CsPbBr3 showed typical green emission centered at 534 nm with a full width at half maximum (FWHM) of about 91 meV. The Cs4PbBr6-CsPbBr3 mixed structure exhibits blue-shifted emission at 523 nm with a narrow FWHM of 63 meV and a fast decay time of 6.88 ns. These results are expected to be useful for application in photoelectric devices such as displays, solar cells, and light sensors based on inorganic metal perovskites.

키워드

과제정보

본 연구는 전남대학교 학술연구비 지원에 의하여 연구되었음.

참고문헌

  1. J. A. Sichert, Y. Tong, N. Mutz, M. Vollmer, S. Fischer, K. Z. Milowska, R. G. Cortadella, B. Nickel, C. Cardenas-Daw, J. K. Stolarczyk, A. S. Urban, and J. Feldmann, "Quantum Size Effect in Organometal Halide Perovskite Nanoplatelets", Nano Lett., 15(10), 6521-6527 (2015).  https://doi.org/10.1021/acs.nanolett.5b02985
  2. J. Chen, D. J. Morrow, Y. Fu, W. Zheng, Y. Zhao, L. Dang, M. J. Stolt, D. D. Kohler, X. Wang, K. J. Czech, M. P. Hautzinger, S. Shen, L. Guo, A. Pan, J. C. Wright, and S. Jin, "Single-Crystal Thin Films of Cesium Lead Bromide Perovskite Epitaxially Grown on Metal Oxide Perovskite (SrTiO3)", J. Am. Chem. Soc., 139(38), 13525-13532 (2017).  https://doi.org/10.1021/jacs.7b07506
  3. Y. Zhou, K. Fernando, J. Wan, F. Liu, S. Shrestha, J. Tisdale, C. J. Sheehan, A. C. Jones, S. Tretiak, H. Tsai, H. Huang, and W. Nie, "Millimeter-Size All-inorganic Perovskite Crystalline Thin Film Grown by Chemical Vapor Deposition", Adv. Funct. Mater., 31(23), 2101058 (2021). 
  4. G. Xing, N. Mathews, S. Sun, S. S. Lim, Y. M. Lam, M. Gratzel, S. Mhaisalkar, and T. C. Sum, "Long-Range Balanced Electron- and Hole-Transport Lengths in Organic-Inorganic CH3NH3PbI3", Sci., 342(6156), 344-347 (2013).  https://doi.org/10.1126/science.1243167
  5. L. M. Herz, "Charge-Carrier Mobilities in Metal Halide Perovskites: Fundamental Mechanisms and Limits", ACS Energy Lett., 2(7), 1539-1548 (2017).  https://doi.org/10.1021/acsenergylett.7b00276
  6. M. A. Green, A. Ho-Baillie, and H. J. Snaith, "The emergence of perovskite solar cells", Nat. Photon., 8, 506-514 (2014).  https://doi.org/10.1038/nphoton.2014.134
  7. Z. Xiao, R. A. Kerner, L. Zhao, N. L. Tran, K. M. Lee, T.-W. Koh, G. D. Scholes, and B. P. Rand, "Efficient perovskite light-emitting diodes featuring nanometer-sized crystallites", Nat. Photon., 11, 108-115 (2017).  https://doi.org/10.1038/nphoton.2016.269
  8. X. Zhang, B. Xu, J. Zhang, Y. Gao, Y. Zheng, K. Wang, and X. W. Sun, "All-inorganic Perovskite Nanocrystals for High-Efficiency Light Emitting Diodes: Dual-Phase CsPbBr3-CsPb2Br5 Composites", Adv. Funct. Mater., 26(25), 4595-4600 (2016).  https://doi.org/10.1002/adfm.201600958
  9. J. Liang, C. Wang, Y. Wang, Z. Xu, Z. Lu, Y. Ma, H. Zhu, Y. Hu, C. Xiao, X. Yi, G. Zhu, H. Lv, L. Ma, T. Chen, Z. Tie, Z. Jin, and J. Liu, "All-Inorganic Perovskite Solar Cells", J. Am. Chem. Soc., 138(49), 15829-15832 (2016).  https://doi.org/10.1021/jacs.6b10227
  10. H. Wang, X. Zhang, Q. Wu, F. Cao, D. Yang, Y. Shang, Z. Ning, W. Zhang, W. Zheng, Y. Yan, S. V. Kershaw, L. Zhang, A. L. Rogach, and X. Yang, "Trifluoroacetate induced smallgrained CsPbBr3 perovskite films result in efficient and stable light-emitting devices", Nat. Commun., 10, 665 (2019). 
  11. J. Chen, Y. Fu, L. Samad, L. Dang, Y. Zhao, S. Shen, L. Guo, and S. Jin, "Vapor-Phase Epitaxial Growth of Aligned Nanowire Networks of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, I)", Nano Lett., 17(1), 460-466 (2017).  https://doi.org/10.1021/acs.nanolett.6b04450
  12. L. Wu, H. Hu, Y. Xu, S. Jiang, M. Chen, Q. Zhong, D. Yang, Q. Liu, Y. Zhao, B. Sun, Q. Zhang, and Y. Yin, "From Non-luminescent Cs4PbX6 (X = Cl, Br, I) Nanocrystals to Highly Luminescent CsPbX3 Nanocrystals: Water-Triggered Transformation through a CsX-Stripping Mechanism", Nano Lett., 17(9), 5799-5804 (2017).  https://doi.org/10.1021/acs.nanolett.7b02896
  13. Q. A. Akkerman, G. Raino, M. V. Kovalenko, and L. Manna, "Genesis, challenges and opportunities for colloidal lead halide perovskite nanocrystals", Nat. Mater., 17, 394-405 (2018).  https://doi.org/10.1038/s41563-018-0018-4
  14. F. Liu, Y. Zhang, C. Ding, S. Kobayashi, T. Izuishi, N. Nakazawa, T. Toyoda, T. Ohta, S. Hayase, T. Minemoto, K. Yoshino, S. Dai, and Q. Shen, "Highly Luminescent PhaseStable CsPbI3 Perovskite Quantum Dots Achieving Near 100% Absolute Photoluminescence Quantum Yield", ACS Nano, 11(10), 10373-10383 (2017).  https://doi.org/10.1021/acsnano.7b05442
  15. B. A. Koscher, J. K. Swabeck, N. D. Bronstein, and A. P. Alivisatos, "Essentially Trap-Free CsPbBr3 Colloidal Nanocrystals by Postsynthetic Thiocyanate Surface Treatment", J. Am. Chem. Soc., 139(19), 6566-6569 (2017).  https://doi.org/10.1021/jacs.7b02817
  16. J.-H. Cha, J. H. Han, W. Yin, C. Park, Y. Park, T. K. Ahn, J. H. Cho, and D.-Y. Jung, "Photoresponse of CsPbBr3 and Cs4PbBr6 Perovskite Single Crystals", J. Phys. Chem. Lett., 8(3), 565-570 (2017).  https://doi.org/10.1021/acs.jpclett.6b02763
  17. M. He, C. Wang, J. Li, J. Wu, S. Zhang, H. Kuo, L. Shao, S. Zhao, J. Zhang, F. Kang, and G. Wei, "The CsPbBr3-Cs4PbBr6 composite nanocrystals for highly efficient pure green light emission", Nanoscale, 11, 22899-22906 (2019).  https://doi.org/10.1039/C9NR07096F
  18. Q. A. Akkerman, A. L. Abdelhady, and L. Manna, "Zero-dimensional cesium lead halides: history, properties, and challenges", J. Phys. Chem. Lett., 9, 2326-2337 (2018).  https://doi.org/10.1021/acs.jpclett.8b00572
  19. J. Zhang, A. Wang, L. Kong, L. Zhang, and Z. Deng, "Controlled synthesis of zero-dimensional phase-pure Cs4PbBr6 perovskites crystals with high photoluminescence quantum yield", J. Alloys Compd., 797, 1151-1156 (2019).  https://doi.org/10.1016/j.jallcom.2019.05.194
  20. Y.-M. Chen, Y. Zhou, Q. Zhao, J.-Y. Zhang, J. Ma, T.-T. Xuan, S.-Q. Guo, Z.-J. Yong, J. Wang, Y. Kuroiwa, C. Moriyoshi, and H.-T. Sun, "Cs4PbBr6/CsPbBr3 Perovskite Composites with Near-Unity Luminescence Quantum Yield: Large-Scale Synthesis, Luminescence and Formation Mechanism, and White Light-Emitting Diode Application", ACS Appl. Mater. Interfaces, 10, 15905-15912 (2018).  https://doi.org/10.1021/acsami.8b04556
  21. S. B. Jathar, S. R. Rondiya, B. R. Bade, M. P. Nasane, S. V. Barma, Y. A. Jadhav, A. V. Rokade, K. B. Kore, D. S. Nilegave, P. U. Tandale, S. R. Jadkar, and A. M. Funde, "Facile method for synthesis of CsPbBr3 perovskite at room temperature for solar cell applications", 12, 72-77 (2021). 
  22. X. Peng, J. Chen, F. Wang, C. Zhang, and B. Yang, "One-pot synthesis of CsPbBr3/Cs4PbBr6 perovskite composite", Optik, 208, 164579 (2020). 
  23. Y. Li, W. Shao, L. Chen, J. Wang, J. Nie, H. Zhang, S. Zhang, R. Gao, X. Ouyang, X. Ouyang, and Q. Xu, "Lead-halide Cs4PbBr6 single crystals for high-sensitivity radiation detection", NPG Asia Mater., 13, 40 (2021). 
  24. Y. Rakita, N. Kedem, S. Gupta, A. Sadhanala, V. Kalchenko, M. L. Bohm, M. Kulbak, R. H. Friend, D. Cahen, and G. Hodes, "Low-Temperature Solution-Grown CsPbBr3 Single Crystals and Their Characterization", Cryst. Growth Des., 16, 5717-5725 (2016).  https://doi.org/10.1021/acs.cgd.6b00764
  25. Y. Zhong, K. Liao, W. Du, J. Zhu, Q. Shang, F. Zhou, X. Wu, X. Sui, J. Shi, S. Yue, Q. Wang, Y. Zhang, Q. Zhang, X. Hu, and X. Liu, "Large-Scale Thin CsPbBr3 Single-Crystal Film Grown on Sapphire via Chemical Vapor Deposition: Toward Laser Array Application", ACS Nano, 14, 15605-15615 (2020).  https://doi.org/10.1021/acsnano.0c06380
  26. E. Oksenberg, A. Merdasa, L. Houben, I. Kaplan-Ashiri, A. Rothman, I. G. Scheblykin, E. V. Unger, and E. Joselevich, "Large lattice distortions and size-dependent bandgap modulation in epitaxial halide perovskite nanowires", Nat. Commun., 11, 489 (2020). 
  27. H. Zhou, S. Yuan, X. Wang, T. Xu, X. Wang, H. Li, W. Zheng, P. Fan, Y. Li, L. Sun, and A. Pan, "Vapor growth and tunable lasing of band gap engineered cesium lead halide perovskite micro/nanorods with triangular cross section", ACS Nano, 11, 1189-1195 (2017).  https://doi.org/10.1021/acsnano.6b07374
  28. K. Decka, A. Sucha, J. Kral, I. Jakubec, M. Nikl, V. Jary, V. Babin, E. Mihokova, and V. Cuba, "On the Role of Cs4PbBr6 Phase in the Luminescence Performance of Bright CsPbBr3 Nanocrystals", Nanomater., 11, 1935 (2021). 
  29. G. Tong, H. Li, Z. Zhu, Y. Zhang, L. Yu, J. Xu, and Y. Jiang, "Enhancing Hybrid Perovskite Detectability in the Deep Ultraviolet Region with Down-Conversion Dual-Phase (CsPbBr3-Cs4PbBr6) Films", J. Phys. Chem. Lett., 9, 1592-1599 (2018).  https://doi.org/10.1021/acs.jpclett.8b00429
  30. Y. Rakita, N. Kedem, S. Gupta, A. Sadhanala, V. Kalchenko, M. L. Bohm, M. Kulbak, R. H. Friend, D. Cahen, and G. Hodes, "Low-Temperature Solution-Grown CsPbBr3 Single Crystals and Their Characterization", Cryst. Growth Des., 16, 5717-5725 (2016).  https://doi.org/10.1021/acs.cgd.6b00764
  31. D. Bi, C. Yi, J. Luo, J.-D. Decoppe, F. Zhang, S. M. Zakeeruddin, X. Li, A. Hagfeldt, and M. Gratzel, "Polymer-templated nucleation and crystal growth of perovskite films for solar cells with efficiency greater than 21%", Nat. Energy, 1, 16142 (2016). 
  32. X. Wan, Z. Yu, W. Tian, F. Huang, S. Jin, X. Yang, Y. Cheng, A. Hagfeldt, and L. Sun, "Efficient and stable planar all-inorganic perovskite solar cells based on high-quality CsPbBr3 films with controllable morphology", J. Energy Chem., 46, 8-15 (2020).  https://doi.org/10.1016/j.jechem.2019.10.017
  33. J. Chen, C. Zhang, X. Liu, L. Peng, J. Lin, and X. Chen, "Carrier dynamic process in all-inorganic halide perovskites explored by photoluminescence spectra", Photonics Res., 9, 151-170 (2021). https://doi.org/10.1364/PRJ.410290