title: Substrate selected polymorphism of epitaxially aligned tetraphenyl-porphyrin thin films.
abstract: Porphyrin molecules, of interest as versatile materials for organic electronics, are highly prone to formation of significantly different polymorphic phases. To elucidate the determinants for the specific polymorphic phase formed in thin films as well as for the arrangement of the molecules on a given substrate two different anisotropic substrate surfaces have been selected: KCl(100) and the oxygen reconstructed Cu(110) surface. We observe that the crystal structure of the thin films depends on the substrate, whereas the relative molecular orientations in both cases are similar. X-Ray and transmission electron diffraction of 30 nm thick tetraphenyl-porphyrin (H(2)TPP) and platinum tetraphenyl-porphyrin (PtTPP) thin films deposited on KCl(100) surfaces reveals that both kinds of molecules crystallize in a tetragonal polymorph with the (001) lattice planes, i.e. with their macrocycles, parallel to the substrate. Films deposited on the oxygen reconstructed Cu(110)-(2 × 1)O surface exhibit in contrast the triclinic polymorph even though molecules again align nearly parallel to the substrate surface as observed by LEED and X-ray diffraction. On both substrates we identify two driving forces for the epitaxial alignment of porphyrins: (i) molecules aligning with their macrocycles (nearly) parallel to the substrate surface and (ii) the porphyrin molecules forming a commensurate unit cell with the respective substrate. The polymorphic phase meeting both requirements is the most favorable to be formed on a given substrate and due to this structural flexibility in both cases well-ordered, epitaxially aligned porphyrin thin films are achieved.
authors.affiliation: Institute of Solid State Physics, Graz University of Technology, Austria. tatjana.djuric@tugraz.at
authors.forename: Tatjana
authors.initials: T
authors.lastname: Djuric
authors.forename: Thomas
authors.initials: T
authors.lastname: Ules
authors.forename: Sina
authors.initials: S
authors.lastname: Gusenleitner
authors.forename: Navaphun
authors.initials: N
authors.lastname: Kayunkid
authors.forename: Harald
authors.initials: H
authors.lastname: Plank
authors.forename: Gregor
authors.initials: G
authors.lastname: Hlawacek
authors.forename: Christian
authors.initials: C
authors.lastname: Teichert
authors.forename: Martin
authors.initials: M
authors.lastname: Brinkmann
authors.forename: Mike
authors.initials: M
authors.lastname: Ramsey
authors.forename: Roland
authors.initials: R
authors.lastname: Resel