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Controlling the growth of multiple ordered heteromolecular phases by utilizing intermolecular repulsion


Metal/organic interfaces and their structural, electronic, spintronic and thermodynamic properties have been investigated intensively, aiming to improve and develop future electronic devices. In this context, heteromolecular phases add new design opportunities simply by combining different molecules. However, controlling the desired phases in such complex systems is a challenging task. Here, we report an effective way of steering the growth of a bimolecular system composed of adsorbate species with opposite intermolecular interactions—repulsive and attractive, respectively. The repulsive species forms a two-dimensional lattice gas, the density of which controls which crystalline phases are stable. Critical gas phase densities determine the constant-area phase diagram that describes our experimental observations, including eutectic regions with three coexisting phases. We anticipate the general validity of this type of phase diagram for binary systems containing two-dimensional gas phases, and also show that the density of the gas phase allows engineering of the interface structure.

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Figure 1: Schematic models and LEED patterns for all five homomolecular and heteromolecular phases of CuPc and PTCDA that occur following adsorption on Ag(111) at 380 K, as a function of the initial CuPc coverage.
Figure 2: Deposition of CuPc on a 0.17 ML film of PTCDA on Ag(111) at 380 K.
Figure 3: Deposition of PTCDA on a 0.73 ML film of CuPc on Ag(111).
Figure 4: Phase diagram for PTCDA and CuPc homo- and heteromolecular structures in the submonolayer regime, as obtained from experiment and the thermodynamic model.
Figure 5: The role of the critical CuPc gas phase density in the eutectic regions.


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Author information




C.H. and C.K. conceived and designed this research project. C.H., J.F. and D.S. performed the experiments and C.H. analysed the data. C.H., C.K. and F.S.T. developed the thermodynamic model on which the interpretation of the phase diagram is based, and wrote the paper.

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Correspondence to Christian Kumpf.

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The authors declare no competing financial interests.

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Henneke, C., Felter, J., Schwarz, D. et al. Controlling the growth of multiple ordered heteromolecular phases by utilizing intermolecular repulsion. Nature Mater 16, 628–633 (2017).

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