title: Langmuir and Langmuir-Blodgett films of amphiphilic hexa-peri-hexabenzocoronene: new phase transitions and electronic properties controlled by pressure.
abstract: We present the synthesis as well as the structural and electronic properties of an amphiphilic derivative of hexaalkylhexa-peri-hexabenzocoronene (HBC), which contains one alkyl substituent that is terminated with a carboxylic acid group. The molecules form well-defined Langmuir films when spread from a solution at the air-water interface. Grazing-incidence X-ray diffraction (GIXD) and X-ray reflectivity studies of the Langmuir monolayer reveal two crystallographic phases at room temperature which depend on the surface pressure applied to the film. Scattering from very well-ordered (zeta = 200-400 A) pi-stacked lamellae of HBC molecules tilted approximately 45 degrees relative to the surface normal is observed in the low-pressure phase. In this phase, the HBC molecules pack in a rectangular two-dimensional unit cell with a = 22.95 A and b = 4.94 A. In the high-pressure phase, coherence from the pi stack is lost. This is a consequence of stress induced by the crystallization of the substituent alkyl chains into a hexagonal lattice, which has a trimerized superstructure in one direction: a = 3 x b = 15.78 A, b = 5.26 A, gamma = 120 degrees, A = 71.9 A2 = 3 x 23.9 A2. Thin monolayer films can be transferred to solid supports by the Langmuir-Blodgett (LB) technique. Atomic force microscopy (AFM) with atomic resolution reveals the crystalline packing of alkyl chains in the high-pressure phase. Kelvin force microscopy (KFM) shows a clear potential difference between the high- and low-pressure phases. This is discussed in terms of orbital delocalization (band formation) in the highly coherent low-pressure phase, which is in contrast to the localized molecular orbitals present in the high-pressure phase. The highly coherent pi stack is expected to sustain a very high charge-carrier mobility.
authors.affiliation: Nano-Science Center, Department of Chemistry, University of Copenhagen, Denmark.
authors.forename: N
authors.initials: N
authors.lastname: Reitzel
authors.forename: T
authors.initials: T
authors.lastname: Hassenkam
authors.forename: K
authors.initials: K
authors.lastname: Balashev
authors.forename: T R
authors.initials: TR
authors.lastname: Jensen
authors.forename: P B
authors.initials: PB
authors.lastname: Howes
authors.forename: L K
authors.initials: LK
authors.lastname: Kjaer
authors.forename: A
authors.initials: A
authors.lastname: Fechtenkötter
authors.forename: N
authors.initials: N
authors.lastname: Tchebotareva
authors.forename: S
authors.initials: S
authors.lastname: Ito
authors.forename: L K
authors.initials: LK
authors.lastname: Müllen
authors.forename: T
authors.initials: T
authors.lastname: Bjørnholm