Standard deviation of microscopy images used as indicator for growth stages.

Photoelectron emission microscopy (PEEM) and low energy electron microscopy (LEEM) can easily distinguish between organic molecules adsorbed in crystallites or in the wetting layers as well as the bare metal substrate due to their different electronic properties. Already before (and during) the condensation of such solid phases (2D islands or 3D crystallites), there is a dilute 2D gas phase. Such a 2D gas phase consists of molecules, which are highly mobile and diffuse across the surface. The individual molecules are too small to be resolved in PEEM/LEEM images. Here, we discuss, how image features below and above the resolution limit of a PEEM/LEEM affect the mean electron yield and its (normalized) standard deviation. We support our findings with two experimental examples: the deposition of cobalt phthalocyanine (CoPc) on Ag(100) and of perfluoro-pentacene on Ag(110). Our results demonstrate, how a spatial and temporal analysis of image series can be used to obtain information about molecular phases, which cannot be directly resolved in microscopy images.

Molecular Reorientation during the Initial Growth of Perfluoropentacene on Ag(110).

Perfluoropentacene (PFP) is an organic material that has been widely studied over the last years and has already found applications in organic electronics. However, fundamental physical questions, such as the structural formation and the preferential orientation of the molecules during deposition on metal surfaces, are still not fully understood. In this work, we report on a unique in-plane molecular reorientation during the completion of the first monolayer of PFP on the Ag(110) surface. To characterize the molecular alignment, we have monitored the deposition process in real time using polarization-dependent differential reflectance spectroscopy and reflectance anisotropy spectroscopy. Abrupt changes in the optical signals reveal an intricate sequence of reorientation transitions of the PFP molecules upon monolayer completion and during the formation of the second monolayer, eventually leading to a full alignment of the long molecular axis along the [001] direction of the substrate and an enhanced structural ordering. Scanning tunneling microscopy and low-energy electron diffraction confirm the observed molecular reorientation upon monolayer compression and provide further details on the structural and orientational ordering of the PFP monolayer before and after compression.

Layer-Resolved Evolution of Organic Thin Films Monitored by Photoelectron Emission Microscopy and Optical Reflectance Spectroscopy.

Photoelectron emission microscopy (PEEM) and differential (optical) reflectance spectroscopy (DRS) have proven independently to be versatile analytical tools for monitoring the evolution of organic thin films during growth. In this paper, we present the first experiment in which both techniques have been applied simultaneously and synchronously. We illustrate how the combined PEEM and DRS results can be correlated to obtain an extended perspective on the electronic and optical properties of a molecular film dependent on the film thickness and morphology. As an example, we studied the deposition of the organic molecule α-sexithiophene on Ag(111) in the thickness range from submonolayers up to several monolayers.

The growth of α-sexithiophene films on Ag(111) studied by means of PEEM with linearly polarized light.

In this study, we used photo electron emission microscopy (PEEM) to investigate the growth of α-sexithiophene (α-6 T) on Ag(111) surfaces. The experiments were carried out with linearly polarized ultraviolet-light (Hg lamp with hν=4.9 eV) in order to probe the alignment of the molecules on the surface. In particular, we acquired images before, during, and after growth while changing the polarization in a stepwise manner. For the stationary states of the clean and the α-6 T covered surfaces, we monitored the local electron yield and the intensity of the ultraviolet C-light (100-280 nm) reflected from the whole sample using PEEM and a photodiode, respectively. Due to the high ionization potential (IP>5 eV), there is no direct photoelectron emission from the organic crystallites. However, the photoelectron emission of the metal/organic interface is influenced by anisotropic absorption of the incident light beam, since the adsorbed molecules act as dichroic filters with distinct orientations.