Additive Influence on Bar-Coated CH3NH3PbI3–xClx Perovskite Thin Films
DOI:
https://doi.org/10.33736/jaspe.12629.2026Keywords:
Perovskite, characterization, bar coating, additivesAbstract
Understanding and controlling crystallization during scalable deposition of metal halide perovskites remains a central challenge for large-area device fabrication. In this work, we investigate the influence of small quantities of chemical additives - 1,8-diiodooctane (DIO), hydroiodic acid (HI), and deionized (DI) water - on the structural, morphological, and nanoscale properties of bar-coated CH₃NH₃PbI₃–xClx thin films deposited under ambient conditions. Optical absorption measurements reveal negligible variation in the optical bandgap (1.56–1.58 eV), indicating that the additives do not significantly alter the electronic structure of the perovskite. However, synchrotron-based grazing-incidence wide-angle and small-angle X-ray scattering (GIWAXS/GISAXS) demonstrate pronounced modifications in crystallization behaviour and nanoscale domain organization. Additive incorporation reduces the radius of gyration from ~1050 Å (pristine) to ~460–556 Å, indicating smaller and more compact scattering domains. Fractal analysis of GISAXS profiles suggests a transition in growth morphology, particularly for HI-treated films, which approach a mass-fractal regime. Thermogravimetric analysis further reveals accelerated solvent evaporation in additive-containing precursor inks, suggesting modified nucleation kinetics during film formation. Despite minimal changes in stoichiometry, the additives significantly influence film morphology, roughness, and crystallite distribution. These findings highlight the critical role of solvent–additive interactions in governing crystallization pathways during scalable bar-coating of perovskite thin films under ambient processing conditions.
References
Jena, A. K., Kulkarni, A., & Miyasaka, T. (2019). Halide perovskite photovoltaics: background, status, and future prospects. Chemical reviews, 119(5), 3036-3103. https://doi.org/10.1021/acs.chemrev.8b00539
Best Research-Cell Efficiency Chart | Photovoltaic Research | NLR, https://www.nlr.gov/pv/cell-efficiency
Arslan, M., Cai, M., Li, X., Chen, X., Li, Z., & Traore, A. (2025). Additive engineering in crystallization regulation of highly efficient perovskite solar cell. Materials and Sustainability, 1(4), 13. https://doi.org/10.53941/matsus.2025.100013
Tian, Y., Xu, Y., Yin, M. M., Wang, H., Zang, Z., & Mohammed, O. F. (2025). In situ interfacial engineering in perovskite solar cells: The importance of additives. ACS Energy Letters, 10(9), 4102-4130. https://doi.org/10.1021/ACSENERGYLETT.5C02002
Maschwitz, T., Merten, L., Ünlü, F., Majewski, M., Haddadi Barzoki, F., Wu, Z., Öz, S.D., Kreusel, C., Theisen, M., Wang, P., Schiffer, M., Boccarella, G., Marioth, G., Weidner, H., Schultheis, S., Schieferstein, T., Gidaszewski, D., Julliev, Z., Kneschaurek, E., Munteanu, V., Zaluzhnyy, I., Bertram, F., Jaffrès, A., He, J., Ashurov, N., Stolterfoht, M., Wolff, C.M., Unger, E., Olthof, S., Brocks, G., Tao, S., Grüninger, H., Ronsin, O.J.J., Harting, J., Kotthaus, A.F., Kirsch, S.F., Mathur, S., Hinderhofer, A., Schreiber, F., Riedl, T., Brinkmann, K.O. (2025). How crystallization additives govern halide perovskite grain growth. Nature Communications 2025 16:1, 16, 9894-. https://doi.org/10.1038/s41467-025-65484-7
Abrusci, A., Stranks, S. D., Docampo, P., Yip, H. L., Jen, A. K. Y., & Snaith, H. J. (2013). High-performance perovskite-polymer hybrid solar cells via electronic coupling with fullerene monolayers. Nano letters, 13(7), 3124-3128. https://doi.org/10.1021/nl401044q
Xing, G., Mathews, N., Sun, S., Lim, S.S., Lam, Y.M., Gratzel, M., Mhaisalkar, S., Sum, T.C. (2013). Long-range balanced electron-and hole-transport lengths in organic-inorganic CH3NH3PbI3. Science, 342(6156), 344-347,. https://doi.org/10.1126/science.1243167
Lee, M.M., Teuscher, J., Miyasaka, T., Murakami, T.N., Snaith, H.J., O’Regan, B., Grätzel, M., Green, M.A., Emery, K., Hishikawa, Y., Warta, W., Dunlop, E.D., Han, L., Yella, A., Yu, G., Gao, J., Hummelen, J.C., Wudl, F., Heeger, A.J., Halls, J.J.M., Ip, A.H., Todorov, T.K., Reuter, K.B., Mitzi, D.B., Snaith, H.J., Dennler, G., Scharber, M.C., Brabec, C.J., Hardin, B.E., Snaith, H.J., McGehee, M.D., Bach, U., Burschka, J., Itzhaik, Y., Niitsoo, O., Page, M., Hodes, G., Chang, J.A., Nelson, J., Mitzi, D.B., Field, C.A., Harrison, W.T.A., Guloy, A.M., Chondroudis, K., Mitzi, D.B., Era, M., Tsutsui, T., Saito, S., Kagan, C.R., Mitzi, D.B., Dimitrakopoulos, C.D., Kojima, A., Teshima, K., Shirai, Y., Miyasaka, T., Im, J.H., Lee, C.R., Lee, J.W., Park, S.W., Park, N.G., Chung, I., Lee, B., He, J., Chang, R.P.H., Kanatzidis, M.G., Snaith, H.J., Poglitsch, A., Weber, D., Leijtens, T., Snaith, H.J., Melas-Kyriazi, J., Abrusci, A., Ding, I.-K., Docampo, P., Barkhouse, D.A.R., Gunawan, O., Gokmen, T., Todorov, T.K., Mitzi, D.B., Kojima, A., Ikegami, M., Teshima, K., Miyasaka, T., Rothenberger, G., Fitzmaurice, D., Graetzel, M., Boschloo, G., Hagfeldt, A., Docampo, P., Bisquert, J., Kavan, L., Grätzel, M., Ishihara, T., Takahashi, J. & Goto, T. (2012). Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites. Science, 338, 643–7. https://doi.org/10.1126/science.1228604
Docampo, P., Ball, J. M., Darwich, M., Eperon, G. E., & Snaith, H. J. (2013). Efficient organometal trihalide perovskite planar-heterojunction solar cells on flexible polymer substrates. Nature communications, 4(1), 2761. https://doi.org/10.1038/ncomms3761
Colella, S., Mosconi, E., Fedeli, P., Listorti, A., Gazza, F., Orlandi, F., Ferro, P., Besagni, T., Rizzo, A., Calestani, G., Gigli, G., De Angelis, F. & Mosca, R. (2013). MAPbI3-xClx mixed halide perovskite for hybrid solar cells: The role of chloride as dopant on the transport and structural properties. Chemistry of Materials, 25(22), 4613-4618. https://doi.org/10.1021/cm402919x
Liang, P.W., Liao, C.Y., Chueh, C.C., Zuo, F., Williams, S.T., Xin, X.K., Lin, J. & Jen, A.K.Y. (2014). Additive enhanced crystallization of solution-processed perovskite for highly efficient planar-heterojunction solar cells. Advanced Materials, 26(22), 3748–3754. https://doi.org/10.1002/adma.201400231
Heo, J.H., Han, H.J., Kim, D., Ahn, T.K. & Im, S.H. (2015). Hysteresis-less inverted CH3NH3PbI3 planar perovskite hybrid solar cells with 18.1% power conversion efficiency. Energy & Environmetal Science, 8(5), 1602–1608. https://doi.org/10.1039/c5ee00120j
Lee, H., Kim, A., Kwon, H.C., Yang, W., Oh, Y., Lee, D. & Moon, J. (2016). Retarding crystallization during facile single coating of NaCl-incorporated precursor solution for efficient large-area uniform perovskite solar cells. ACS applied materials & interfaces, 8(43), 29419-29426. https://doi.org/10.1021/ACSAMI.6B08783/SUPPL_FILE/AM6B08783_SI_003.AVI
Mohamad, D.K., Freestone, B.G., Masters, R., Reinhardt, M., Canning, S., Rodenburg, C. & Lidzey, D.G. (2017). Optimized organometal halide perovskite solar cell fabrication through control of nanoparticle crystal patterning. J. Mater. Chem. C, 5(9), 2352–2359. https://doi.org/10.1039/C6TC05189H
Gong, X., Li, M., Shi, X. B., Ma, H., Wang, Z. K., & Liao, L. S. (2015). Controllable perovskite crystallization by water additive for high‐performance solar cells. Advanced Functional Materials, 25(42), 6671-6678. https://doi.org/10.1002/adfm.201503559
Tan, W.L., Kirby, N.M., Cheng, Y.B., & McNeill, C.R. (2021). Origin of vertical slab orientation in blade-coated layered hybrid perovskite films revealed with in-situ synchrotron X-ray scattering. Nano Energy, 83, 105818. https://doi.org/10.1016/J.NANOEN.2021.105818
Tang, M.C., Fan, Y., Barrit, D., Chang, X., Dang, H.X., Li, R., Wang, K., Smilgies, D.M., Liu, S.F., De Wolf, S., Anthopoulos, T.D., Zhao, K., & Amassian, A. (2020). Ambient blade coating of mixed cation, mixed halide perovskites without dripping: In situ investigation and highly efficient solar cells. Journal of Materials Chemistry A, 8(3), 1095-1104. https://doi.org/10.1039/c9ta12890e
Zhong, J. X., Wu, W. Q., Ding, L., & Kuang, D. B. (2021). Blade‐coating perovskite films with diverse compositions for efficient photovoltaics. Energy & Environmental Materials, 4(3), 277-283. https://doi.org/10.1002/EEM2.12118;ISSUE:ISSUE:DOI
Yang, W. S., Noh, J. H., Jeon, N. J., Kim, Y. C., Ryu, S., Seo, J., & Seok, S. I. (2015). High-performance photovoltaic perovskite layers fabricated through intramolecular exchange. Science, 348(6240), 1234-1237. https://doi.org/10.1126/science.aaa9272
Xu, Y., Wang, M., Lei, Y., Ci, Z., & Jin, Z. (2020). Crystallization kinetics in 2D perovskite solar cells. Advanced Energy Materials, 10(43), 2002558. https://doi.org/10.1002/AENM.202002558
Yang, Z., Chueh, C. C., Zuo, F., Kim, J. H., Liang, P. W., & Jen, A. K. Y. (2015). High‐performance fully printable perovskite solar cells via blade‐coating technique under the ambient condition. Advanced Energy Materials, 5(13), 1500328. https://doi.org/10.1002/aenm.201500328
Jacobsson, T.J., Correa-Baen, J.P., Pazoki, M., Saliba, M., Schenk, K., Gratzel, M., Hagfeldt, A. (2016). Exploration of the compositional space for mixed lead halogen perovskites for high efficiency solar cells. Energy & Environmental Science, 9(5), 1706-1724. https://doi.org/10.1039/c6ee00030d
Huang, Y., Zhang, W., Xiong, Y., Yi, Z., Huang, C., Jiang, Q., Basit, A., Shen, G., Luo, Y., Li, X., & Yang, J. (2025). Recent advancements in ambient‐air fabrication of perovskite solar cells. In Exploration (Vol. 5, No. 3, p. 20240121). https://doi.org/10.1002/EXP.20240121
Zhang, W., Du, J., Qiu, C., Yang, K., Huang, Q., Wang, Q., Zhang, W., Han, H., Gao, X., & Hu, Y. (2021). Enhanced efficiency of printable mesoscopic perovskite solar cells using ionic liquid additives. Chemical Communications, 57(33), 4027–4030. https://doi.org/10.1039/D1CC00169H
Chen, P., Yin, X., Chen, W.H., Song, L., Du, P., Huang, Y., Li, N., Xiong, J. (2021). Perovskite solar cells with PCE over 19% fabricated under air environment by using a dye molecule additive. Sustain. Energy Fuels, 5, 2266–2272. https://doi.org/10.1039/D1SE00013F
Song, Z., Sun, K., Meng, Y., Zhu, Z., Wang, Y., Zhang, W., Tian, R., Bai, Y., Lu, X., Yang, M., Liu, C., & Ge, Z. (2025). High efficiency and stable inverted perovskite solar cells enabled by a multifunctional organic salt additive. Science China Chemistry, 68(11), 5765–5775. https://doi.org/10.1007/S11426-025-2647-6
Barrows, A. T., Lilliu, S., Pearson, A. J., Babonneau, D., Dunbar, A. D., & Lidzey, D. G. (2016). Monitoring the formation of a CH3NH3PbI3–xClx perovskite during thermal annealing using X‐Ray scattering. Advanced Functional Materials, 26(27), 4934-4942. https://doi.org/10.1002/ADFM.201601309
Wu, K., Bera, A., Ma, C., Du, Y., Yang, Y., Li, L., & Wu, T. (2014). Temperature-dependent excitonic photoluminescence of hybrid organometal halide perovskite films. Physical Chemistry Chemical Physics, 16(41), 22476-22481. https://doi.org/10.1039/C4CP03573A
Baikie, T., Fang, Y., Kadro, J. M., Schreyer, M., Wei, F., Mhaisalkar, S. G., ... & White, T. J. (2013). Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3) PbI3 for solid-state sensitised solar cell applications. Journal of Materials Chemistry A, 1(18), 5628-5641.https://doi.org/10.1039/c3ta10518k
Chang, C. Y., Huang, Y. C., Tsao, C. S., & Su, W. F. (2016). Formation mechanism and control of perovskite films from solution to crystalline phase studied by in situ synchrotron scattering. ACS Applied Materials & Interfaces, 8(40), 26712-26721. https://doi.org/10.1021/acsami.6b07468
Qin, M., Chan, P. F., & Lu, X. (2021). A systematic review of metal halide perovskite crystallization and film formation mechanism unveiled by in situ GIWAXS. Advanced Materials, 33(51), 2105290. https://doi.org/10.1002/ADMA.202105290
Steele, J.A., Solano, E., Hardy, D., Dayton, D., Ladd, D., White, K., Chen, P., Hou, J., Huang, H., Saha, R.A., Wang, L., Gao, F., Hofkens, J., Roeffaers, M.B.J., Chernyshov, D., & Toney, M.F. (2023 How to GIWAXS: grazing incidence wide angle X‐ray scattering applied to metal halide perovskite thin films. Advanced Energy Materials, 13(27), 2300760. https://doi.org/10.1002/AENM.202300760
Wang, C., Zuo, C., Chen, Q., & Ding, L. (2021). GIWAXS: A powerful tool for perovskite photovoltaics. Journal of Semiconductors, 42(6), 060201.https://doi.org/10.1088/1674-4926/42/6/060201
Magubane, S. S., Arendse, C. J., Ngqoloda, S., Cummings, F., Mtshali, C., & Bolokang, A. S. (2021). Chemical Vapor Deposited Mixed Metal Halide Perovskite Thin Films. Materials, 14(13), 3526. https://doi.org/10.3390/MA14133526/S1
Lee, K. M., Chan, S. H., Hou, M. Y., Chu, W. C., Chen, S. H., Yu, S. M., & Wu, M. C. (2021). Enhanced efficiency and stability of quasi-2D/3D perovskite solar cells by thermal assisted blade coating method. Chemical Engineering Journal, 405, 126992. https://doi.org/https://doi.org/10.1016/j.cej.2020.126992
Deng, Y., Peng, E., Shao, Y., Xiao, Z., Dong, Q., & Huang, J. (2015). Scalable fabrication of efficient organolead trihalide perovskite solar cells with doctor-bladed active layers. Energy & Environmental Science, 8(5), 1544-1550. https://doi.org/10.1039/C4EE03907F
Colella, S., Mosconi, E., Pellegrino, G., Alberti, A., Guerra, V.L.P., Masi, S., Listorti, A., Rizzo, A., Condorelli, G.G., De Angelis, F., & Gigli, G. (2014). Elusive presence of chloride in mixed halide perovskite solar cells. The Journal of Physical Chemistry Letters, 5(20), 3532-3538. https://doi.org/10.1021/JZ501869F
Fan, L., Ding, Y., Luo, J., Shi, B., Yao, X., Wei, C., Zhang, D., Wang, G., Sheng, Y., Chen, Y., Hagfeldt, A., Zhao, Y., & Zhang, X. (2017). Elucidating the role of chlorine in perovskite solar cells. Journal of Materials Chemistry A, 5(16), 7423-7432. https://doi.org/10.1039/C7TA00973A
Vidyasagar, D., Yun, Y.H., Shin, S., Jung, J., Park, W., Lee, J.W., Han, G.S., Ko, C., & Lee, S. (2021). In-situ nano-auger probe of chloride-ions during CH3NH3PbI3−xClx perovskite formation. Materials, 14(5), 1102. https://doi.org/10.3390/MA14051102
Pineda De La O, E., Alhazmi, N., Ebbens, S. J., & Dunbar, A. D. (2021). Influence of additives on the in situ crystallization dynamics of methyl ammonium lead halide perovskites. ACS Applied Energy Materials, 4(2), 1398-1409.. https://doi.org/10.1021/ACSAEM.0C02625/SUPPL_FILE/AE0C02625_SI_003.MP4
Schlipf, J., & Müller‐Buschbaum, P. (2017). Structure of organometal halide perovskite films as determined with grazing‐incidence x‐ray scattering methods. Advanced Energy Materials, 7(16), 1700131. https://doi.org/10.1002/AENM.201700131
Liao, H.-C., Tsao, C.-S., Jao, M.-H., Hsu, C.-P., Huang, Y.-C., Tian, K.-Y., Shyue, J.-J., Chen, C.-Y., Su, C.-J., & Su, W.-F. (2015). Hierarchical i–p and i–n porous heterojunction in planar perovskite solar cells. Journal of Materials Chemistry A, 3(19), 10526-10535. https://doi.org/10.1039/c5ta02184g
Huang, Y.C., Tsao, C.S., Cho, Y.J., Chen, K.C., Chiang, K.M., Hsiao, S.Y., Chen, C.W., Su, C.J., Jeng, U.S., & Lin, H.W. (2015). Insight into evolution, processing and performance of multi-length-scale structures in planar heterojunction perovskite solar cells. Scientific reports, 5(1), 13657. https://doi.org/10.1038/srep13657
Xu, C., Zhang, Z., Zhang, S., Si, H., Ma, S., Fan, W., Xiong, Z., Liao, Q., Sattar, A., Kang, Z., & Zhang, Y. (2021). Manipulation of perovskite crystallization kinetics via Lewis base additives. Advanced Functional Materials, 31(13), 2009425. https://doi.org/10.1002/ADFM.202009425
Shargaieva, O., Näsström, H., Smith, J. A., Többens, D., Munir, R., & Unger, E. (2020). Hybrid perovskite crystallization from binary solvent mixtures: interplay of evaporation rate and binding strength of solvents. Materials Advances, 1(9), 3314-3321. https://doi.org/10.1039/d0ma00815j
Alhazmi, N., Pineda, E., Rawle, J., Howse, J. R., & Dunbar, A. D. (2020). Perovskite crystallization dynamics during spin-casting: an in situ wide-angle X-ray scattering study. ACS applied energy materials, 3(7), 6155. https://doi.org/10.1021/acsaem.9b02470
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