TY - JOUR

T1 - Experimental and theoretical analysis of H-bonded supramolecular assemblies of PTCDA molecules

AU - Mura, M.

AU - Sun, X.

AU - Silly, F.

AU - Jonkman, H. T.

AU - Briggs, G. A. D.

AU - Castell, M. R.

AU - Kantorovich, L. N.

PY - 2010/5/15

Y1 - 2010/5/15

N2 - Using a systematic method based on considering all possible hydrogen bond connections between molecules and subsequent density-functional theory (DFT) calculations, we investigated planar superstructures that the perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride (PTCDA) molecules can form in one and two dimensions. Structures studied are mostly based on two molecule unit cells and all assemble in flat periodic arrays. We show that 42 different monolayer structures are possible, which can be split into eight families of distinct structures. A single representative of every family was selected and relaxed using DFT. We find square, herringbone and brick wall phases (among others) which were already observed on various substrates. Using scanning tunneling microscopy in ultrahigh vacuum, we also observed herringbone and square phases after sublimation of PTCDA molecules on the Au(111) surface at room temperature, the square phase being observed for the first time on this substrate. The square phase appears as a thin stripe separating two herringbone domains and provides a perfect structural matching for them. A similar structural formation serving as a domain wall between two other phases has been recently reported on the same surface formed by melamine molecules [F. Silly et al., J. Phys. Chem. C 112, 11476 (2008)]. Our theoretical analysis helps to account for these and other observed complex structures.

AB - Using a systematic method based on considering all possible hydrogen bond connections between molecules and subsequent density-functional theory (DFT) calculations, we investigated planar superstructures that the perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride (PTCDA) molecules can form in one and two dimensions. Structures studied are mostly based on two molecule unit cells and all assemble in flat periodic arrays. We show that 42 different monolayer structures are possible, which can be split into eight families of distinct structures. A single representative of every family was selected and relaxed using DFT. We find square, herringbone and brick wall phases (among others) which were already observed on various substrates. Using scanning tunneling microscopy in ultrahigh vacuum, we also observed herringbone and square phases after sublimation of PTCDA molecules on the Au(111) surface at room temperature, the square phase being observed for the first time on this substrate. The square phase appears as a thin stripe separating two herringbone domains and provides a perfect structural matching for them. A similar structural formation serving as a domain wall between two other phases has been recently reported on the same surface formed by melamine molecules [F. Silly et al., J. Phys. Chem. C 112, 11476 (2008)]. Our theoretical analysis helps to account for these and other observed complex structures.

KW - SCANNING-TUNNELING-MICROSCOPY

KW - ORGANIC THIN-FILM

KW - HOMOPAIRING POSSIBILITIES

KW - CYANURIC ACID

KW - 3,4,9,10-PERYLENETETRACARBOXYLIC-DIANHYDRIDE PTCDA

KW - AU(111) SURFACE

KW - METAL-SURFACES

KW - NETWORKS

KW - MELAMINE

KW - GROWTH

U2 - 10.1103/PhysRevB.81.195412

DO - 10.1103/PhysRevB.81.195412

M3 - Article

VL - 81

SP - 195412-1-195412-11

JO - Physical Review. B: Condensed Matter and Materials Physics

JF - Physical Review. B: Condensed Matter and Materials Physics

SN - 0163-1829

IS - 19

M1 - 195412

ER -