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@PHDTHESIS{Henneke:667469,
      author       = {Henneke, Caroline},
      othercontributors = {Kumpf, Christian and Mayer zu Heringdorf, Frank and Mayer,
                          Joachim},
      title        = {{K}inetic and thermodynamic considerations on the formation
                      of heteromolecular layers on metal surfaces},
      school       = {RWTH Aachen University},
      type         = {Dissertation},
      address      = {Aachen},
      reportid     = {RWTH-2016-06249},
      pages        = {1 Online-Ressource (vii, 157, XIV Seiten) : Illustrationen,
                      Diagramme},
      year         = {2015},
      note         = {Veröffentlicht auf dem Publikationsserver der RWTH Aachen
                      University 2016; Dissertation, RWTH Aachen University, 2015},
      abstract     = {A systematic study of the growth of a heteromolecular
                      adsorbate system consisting of
                      3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and
                      copper phthalocyanine (CuPc) on the substrates Ag(111) and
                      Cu(001) in the submonolayer regime is presented.The key
                      finding is the phase diagram of the PTCDA-CuPc system on
                      Ag(111) in the complete coverage regime up to 1 ML at 300 K.
                      It contains eight different regions with one or two
                      different crystalline phases which coexist with areas of a
                      disordered phase of both molecules. Only the disordered
                      phase is present on the surface in a ninth region. The
                      reason for this complicated phase diagram is the complex
                      interplay between energetic aspectsof the island formation
                      (adhesion energy) and the involved entropic effects which
                      are both investigated in detail.The phase formation is
                      strongly influenced by the deposition parameters for the
                      PTCDA-CuPc system on Cu(001). Heteromolecular phases only
                      grow when PTCDA is deposited on a submonolayer film of
                      CuPc, while the PTCDA islands remain unchanged for the
                      reversed deposition sequence when CuPc is deposited on a
                      submonolayer film of PTCDA. This is different on Ag(111).
                      PTCDA islands are transformed into three different
                      heteromolecular phases with increasing CuPc:PTCDA
                      stoichiometry during the deposition of CuPc on a
                      submonolayer film of PTCDA. It is found that the phases are
                      in thermodynamic equilibrium since they only depend on
                      coverage (of CuPc and PTCDA) and temperature, but (in
                      contrast to Cu(001)) not on other deposition parameters.
                      This allows the determination of the above mentioned phase
                      diagram. Its form can be explained by an ab-initio model
                      without any fit parameters. It is based on the model for an
                      intermetallic compound at 1 ML coverages and includes the
                      additional assumption that critical densities of CuPc in the
                      disordered phase must be exceeded for the growth of each
                      heteromolecular phase. The existence of such critical
                      densities of CuPc can be explained by the interplay between
                      the intermolecular PTCDA-CuPc interactions and the entropy
                      of the entire system. Both homomolecular systems were
                      characterized in a prefixed part of the work since their
                      understanding is essential for a successful analysis of the
                      heteromolecular system. Here, it is found that the strong
                      attractive intermolecular interaction dominates the growth
                      of PTCDA, while entropic effects can influence the growth
                      of CuPc molecules due to their weakly repulsive
                      interaction.The characterization of both homo- and
                      heteromolecular systems shows that an improved understanding
                      of the self-assembly of molecules on surfaces enables the
                      selective fabrication of heteromolecular thin films with
                      desired properties which potentially influences the
                      production of commercially used organic layers.},
      cin          = {139320 / 130000},
      ddc          = {530},
      cid          = {$I:(DE-82)139320_20140620$ / $I:(DE-82)130000_20140620$},
      typ          = {PUB:(DE-HGF)11},
      urn          = {urn:nbn:de:hbz:82-rwth-2016-062498},
      url          = {https://publications.rwth-aachen.de/record/667469},
}