Meniscus-guided coating methods, such as zone casting, dip coating and solution shearing, are scalable laboratory models for large-area solution coating of functional materials for thin-film electronics. Unfortunately, the general lack of understanding of how the coating parameters affect the dry-film morphology upholds trial-and-error experimentation and delays lab-to-fab translation. We present herein a model that predicts dry-film morphologies produced by meniscus-guided coating of a crystallizing solute. Our model reveals how the interplay between coating velocity and evaporation rate determines the crystalline domain size, shape anisotropy and regularity. If coating is fast, evaporation drives the system quickly past supersaturation, giving isotropic domain structures. If coating is slow, depletion due to crystallization stretches domains in the coating direction. The predicted morphologies have been experimentally confirmed by zone-casting experiments of the organic semiconductor 4-tolyl-bithiophenyl-diketopyrrolopyrrole. Although here we considered a small molecular solute, our model can be applied broadly to polymers and organic–inorganic hybrids such as perovskites.
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The data represented in Figs. 2c,d, 3, 5a–c and 6a,b are available online at https://edmond.mpdl.mpg.de/imeji/collection/uF7qtH6vi9ocht7q?q=. Other data from the current study are available from the corresponding author upon reasonable request.
The code that support the findings of this study are available from the corresponding author upon reasonable request.
Diao, Y., Shaw, L., Bao, Z. & Mannsfeld, S. C. B. Morphology control strategies for solution-processed organic semiconductor thin films. Energy Environ. Sci. 7, 2145–2159 (2014).
Gu, X., Shaw, L., Gu, K., Toney, M. F. & Bao, Z. The meniscus-guided deposition of semiconducting polymers. Nat. Commun. 9, 534–549 (2018).
Patel, B. B. & Diao, Y. Multiscale assembly of solution-processed organic electronics: the critical roles of confinement, fluid flow, and interfaces. Nanotechnology 29, 044004 (2018).
Sele, C. W. et al. Controlled deposition of highly ordered soluble acene thin films: effect of morphology and crystal orientation on transistor performance. Adv. Mater. 21, 4926–4931 (2009).
Rogowski, R. Z. & Darhuber, A. A. Crystal growth near moving contact lines on homogeneous and chemically patterned surfaces. Langmuir 26, 11485–11493 (2010).
Zhang, K. et al. Crystallization control of organic semiconductors during meniscus-guided coating by blending with polymer binder. Adv. Funct. Mater. 28, 1805594 (2018).
Gans, A. et al. Dip-coating of suspensions. Soft Matter 15, 252–261 (2019).
Grosso, D. How to exploit the full potential of the dip-coating process to better control film formation. J. Mater. Chem. 21, 17033–17038 (2011).
Giri, G. et al. Tuning charge transport in solution-sheared organic semiconductors using lattice strain. Nature 480, 504–508 (2011).
Gsänger, M. et al. High-performance organic thin-film transistors of J-stacked squaraine dyes. J. Am. Chem. Soc. 136, 2351–2362 (2014).
Galindo, S., Tamayo, A., Leonardi, F. & Mas-Torrent, M. Control of polymorphism and morphology in solution sheared organic field-effect transistors. Adv. Funct. Mater. 27, 1700526 (2017).
Haase, K. et al. Solution shearing of a high‐capacitance polymer dielectric for low‐voltage organic transistors. Adv. Electron. Mater. 5, 1900067 (2019).
Tamayo, A., Riera-Galindo, S., Jones, A. O. F., Resel, R. & Mas-Torrent, M. Impact of the ink formulation and coating speed on the polymorphism and morphology of a solution‐sheared thin film of a blended organic semiconductor. Adv. Mater. Interfaces 6, 1900950 (2019).
Pisula, W. et al. A zone‐casting technique for device fabrication of field‐effect transistors based on discotic hexa‐peri‐hexabenzocoronene. Adv. Mater. 17, 684–689 (2005).
Tang, C., Wu, W., Smilgies, D.-M., Matyjaszewski, K. & Kowalewski, T. Robust control of microdomain orientation in thin films of block copolymers by zone casting. J. Am. Chem. Soc. 133, 11802–11809 (2011).
Su, Y. et al. Uniaxial alignment of triisopropylsilylethynyl pentacene via zone-casting technique. Phys. Chem. Chem. Phys. 15, 14396–14404 (2013).
Janneck, R., Vercesi, F., Heremans, P., Genoe, J. & Rolin, C. Predictive model for the meniscus-guided coating of high-quality organic single-crystalline thin films. Adv. Mater. 28, 8007–8013 (2016).
Xie, Y.-M. et al. Solution processable small molecule based organic light-emitting devices prepared by dip-coating method. Org. Electron. 55, 1–5 (2018).
Dörling, B. et al. Uniaxial macroscopic alignment of conjugated polymer systems by directional crystallization during blade coating. J. Mater. Chem. C. 2, 3303–3310 (2014).
He, M. et al. Meniscus-assisted solution printing of large-grained perovskite films for high-efficiency solar cells. Nat. Commun. 8, 16045 (2017).
Lee, J.-C., Kim, J.-O., Lee, H.-J., Shin, B. & Park, S. Meniscus-guided control of supersaturation for the crystallization of high quality metal organic framework thin films. Chem. Mater. 31, 7377–7385 (2019).
Dimitrov, A. S. & Nagayama, K. Continuous convective assembling of fine particles into two-dimensional arrays on solid surfaces. Langmuir 13, 1303–1311 (1996).
Jing, G., Bodiguel, H., Doumenc, F., Sultan, E. & Guerrier, B. Drying of colloidal suspensions and polymer solutions near the contact line: deposit thickness at low capillary number. Langmuir 26, 2288–2293 (2010).
Berteloot, G., Pham, C.-T., Daerr, A., Lequeux, F. & Limat, L. Evaporation-induced flow near a contact line: consequences on coating and contact angle. Europhys. Lett. 83, 14003 (2008).
Doumenc, F. & Guerrier, B. Drying of a solution in a meniscus: a model coupling the liquid and the gas phases. Langmuir 26, 13959–13967 (2010).
Doumenc, F. & Guerrier, B. Self-patterning induced by a solutal Marangoni effect in a receding drying meniscus. EPL 103, 14001 (2013).
Dey, M., Doumenc, F. & Guerrier, B. Numerical simulation of dip-coating in the evaporative regime. Eur. Phys. J. E 39, 19 (2016).
Le Berre, M., Chen, Y. & Baigl, D. From convective assembly to Landau–Levich deposition of multilayered phospholipid films of controlled thickness. Langmuir 25, 2554–2557 (2009).
Doumenc, F., Salmon, J.-B. & Guerrier, B. Modeling flow coating of colloidal dispersions in the evaporative regime: prediction of deposit thickness. Langmuir 32, 13657–13668 (2016).
Landau, L. & Levich, B. G. Dragging of a liquid by a moving plate. Acta Physicochim. U.R.S.S 17, 42–54 (1942).
Deryaguin, B. C. R. Thickness of liquid layer adhering to walls of vessels on their emptying and the theory of photo- and motion-picture film coating. Acad. Sci. USSR 39, 13–16 (1943).
Peng, B., Wang, Z. & Chan, P. K. L. A simulation-assisted solution-processing method for a large-area, high-performance C10-DNTT organic semiconductor crystal. J. Mater. Chem. C. 4, 8628–8633 (2016).
Zhang, Z., Peng, B., Ji, X., Pei, K. & Chan, P. K. L. Marangoni‐effect‐assisted bar‐coating method for high‐quality organic crystals with compressive and tensile strains. Adv. Funct. Mater. 27, 1703443 (2017).
Janneck, R., Karagiannis, D., Heremans, P., Genoe, J. & Rolin, C. Influence of solute concentration on meniscus-guided coating of highly crystalline organic thin films. Adv. Mater. Interfaces 6, 1900614 (2019).
Provatas, N. & Elder, K. Phase-Field Methods in Materials Science and Engineering (Wiley, 2010).
Eres, M. H., Weidner, D. E. & Schwartz, L. W. Three-dimensional direct numerical simulation of surface-tension-gradient effects on the leveling of an evaporating multicomponent fluid. Langmuir 15, 1859–1871 (1999).
Vieyra Salas, J. A., van der Veen, J. M., Michels, J. J. & Darhuber, A. A. Active control of evaporative solution deposition by modulated infrared illumination. J. Phys. Chem. C. 116, 12038–12047 (2012).
van Franeker, J. J. et al. Controlling the dominant length scale of liquid–liquid phase separation in spin‐coated organic semiconductor films. Adv. Funct. Mater. 25, 855–863 (2015).
Sharifi Dehsari, H., Michels, J. J. & Asadi, K. Processing of ferroelectric polymers for microelectronics: from morphological analysis to functional devices. J. Mater. Chem. C. 5, 10490–10497 (2017).
Abolhasani, M. M. et al. Thermodynamic approach to tailor porosity in piezoelectric polymer fibers for application in nanogenerators. Nano Energy 62, 594–600 (2019).
Allen, S. M. & Cahn, J. W. A microscopic theory for antiphase boundary motion and its application to antiphase domain coarsening. Acta Metall. 27, 1085–1095 (1979).
Schaefer, C., Michels, J. J. & van der Schoot, P. Structuring of thin-film polymer mixtures upon solvent evaporation. Macromolecules 49, 6858–6870 (2016).
Schaefer, C., Michels, J. J. & van der Schoot, P. Dynamic surface enrichment in drying thin-film binary polymer solutions. Macromolecules 50, 5914–5919 (2017).
Fan, D., Chen, S. P., Chen, L.-Q. & Voorhees, P. W. Phase-field simulation of 2-D Ostwald ripening in the high volume fraction regime. Acta Mater. 50, 1895–1907 (2002).
Cogswell, D. A. & Carter, W. C. Thermodynamic phase-field model for microstructure with multiple components and phases: the possibility of metastable phases. Phys. Rev. E 83, 061602 (2011).
Li, M. et al. Ferroelectric phase diagram of PVDF: PMMA. Macromolecules 45, 7477–7485 (2012).
Gránásy, L., Börzsönyi, T. & Pusztai, T. Nucleation and bulk crystallization in binary phase field theory. Phys. Rev. Lett. 88, 206105 (2002).
Gránásy, L., Pusztai, T. & Warren, J. A. Modelling polycrystalline solidification using phase field theory. J. Phys.: Condens. Matter 16, R1205 (2004).
Gránásy, L., Pusztai, T., Tegze, G., Warren, J. A. & Douglas, J. F. Growth and form of spherulites. Phys. Rev. E 72, 011605 (2005).
Dai, X., Deng, Y., Van Brackle, C. H. & Huang, J. Meniscus fabrication of halide perovskite thin films at high throughput for large area and low-cost solar panels. Int. J. Extrem. Manuf. 1, 022004 (2019).
Yang, M. et al. Facile fabrication of large-grain CH3NH3PbI3–xBrx films for high-efficiency solar cells via CH3NH3Br-selective Ostwald ripening. Nat. Commun. 7, 12305 (2016).
Wheeler, A. A., Boettinger, W. J. & McFadden, G. B. Phase-field model for isothermal phase transitions in binary alloys. Phys. Rev. A 45, 7424–7439 (1992).
Wang, S.-L. et al. Thermodynamically-consistent phase-field models for solidification. Physica D 69, 189–200 (1993).
Egry, I., Ricci, E., Novakovic, R. & Ozawa, S. Surface tension of liquid metals and alloys—recent developments. Adv. Colloid Interface Sci. 159, 198–212 (2010).
de Gennes, P. G. Dynamics of fluctuations and spinodal decomposition in polymer blends. J. Chem. Phys. 72, 4756–4763 (1980).
Nagele, G., Dhont, J. K. G. & Meier, G. in Diffusion in Condensed Matter: Methods, Materials, Models (eds Heitjans, P. & Kärger, J.) 706 (Springer, 2005).
Kramer, E. J., Green, P. & Palmstrøm, C. J. Interdiffusion and marker movements in concentrated polymer-polymer diffusion couples. Polymer 25, 473–480 (1984).
Ronsin, O. J. J. & Harting, J. Strict equivalence between Maxwell–Stefan and fast-mode theory for multicomponent polymer mixtures. Macromolecules 52, 6035–6044 (2019).
Michels, J. J. & Moons, E. Simulation of surface-directed phase separation in a solution-processed polymer/PCBM blend. Macromolecules 46, 8693–8701 (2013).
Wedershoven, H. M. J. M., Zeegers, J. C. H. & Darhuber, A. A. Polymer film deposition from a receding solution meniscus: the effect of laminar forced air convection. Chem. Eng. Sci. 181, 92–100 (2018).
Saylor, D. M., Kim, C.-S., Patwardhan, D. V. & Warren, J. A. Diffuse-interface theory for structure formation and release behavior in controlled drug release systems. Acta Biomater. 3, 851–864 (2007).
The authors acknowledge P. W. M. Blom for stimulating discussions. K.Z. acknowledges the China Scholarship Council (CSC) for financial support. T.M. acknowledges the Foundation for Polish Science financed by the European Union under the European Regional Development Fund (POIR.04.04.00-00-3ED8/17-01).
The authors declare no competing interests.
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Synthesis details and spectra, supplementary discussion, Figs. S1–S13 and Tables S1–S5.
Video of coating of aligned domains.
Video of coating of stretched domains.
Video of coating of isotropic domains.
Video of coating of isotropic domains for a large field-of-view.
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Michels, J.J., Zhang, K., Wucher, P. et al. Predictive modelling of structure formation in semiconductor films produced by meniscus-guided coating. Nat. Mater. (2020). https://doi.org/10.1038/s41563-020-0760-2