Perfluoropentacene Research Articles

Perfluoropentacene thin films on Au(1 1 1) surfaces: Effect of kinetic energy and vibrational properties

We studied vibrational properties and the effect of beam kinetic energy on perfluoropentacene (PFP) thin films grown by supersonic molecular beam deposition (SMBD) technique on gold surfaces. Though similar growth mechanism was observed for different beam kinetic energies, in the case of low coverage (less than 1 monolayer) films and for low deposition rates significant differences were observed in the properties of films grown by using helium and argon carrier gasses with the former case resulting in higher average grain size. For multilayer films however there were no significant differences between helium and argon grown films. Vibrational properties were investigated by using Infrared Scattering-type Scanning Nearfield Optical Microscopy (s-SNOM) on clean and m-carborane-1-thiol (M1) coated template-stripped gold (TSAu) substrates. For both substrates thick PFP films (15 nm) had similar spectra whereas there were significant differences in the spectra of thin films (1 nm) due to PFP-substrate interactions. Davydov splitting of the IR modes were observed for both 1 nm and 15 nm films indicating similar molecular arrangements in both type of films.

Thickness‐Dependent Energy‐Level Alignment at the Organic–Organic Interface Induced by Templated Gap States

AbstractPlanar organic heterostructures are widely explored and employed in photovoltaic cells, light‐emitting diodes, and bilayer field‐effect transistors. An important role for device performance plays the energy level alignment at the inorganic–organic and organic–organic interfaces. In this work, incremental ultraviolet photoelectron spectroscopy measurements and real‐time X‐ray scattering experiments are used to thoroughly investigate the thickness‐dependent electronic and structural properties of a perfluoropentacene (PFP)‐on‐[6]phenacene heterostructure. For both materials an incremental increase of the material work function (positive interface dipole) is found. For [6]phenacene, this can be assigned to a thickness‐dependent change of molecular arrangement evident from a change of the unit cell volume and a consequential alteration of the ionization energy. In the case of PFP the interface dipole stems from charge transfer from the substrate into unoccupied molecular orbitals resulting in an electrostatic potential on the surface. The magnitude of this potential can be correlated with an increased gap state density resulting from templated structural defects mediated by the bottom layer.

Engineering of TMDC-OSC hybrid interfaces: the thermodynamics of unitary and mixed acene monolayers on MoS2.

Hybrid systems of two-dimensional (2D) materials such as transition metal dichalcogenides (TMDCs) and organic semiconductors (OSCs) have become subject of great interest for future device architectures. Although OSC–TMDC hybrid systems have been used in first device demonstrations, the precise preparation of ultra-thin OSC films on TMDCs has not been addressed. Due to the weak van der Waals interaction between TMDCs and OSCs, this requires precise knowledge of the thermodynamics at hand. Here, we use temperature-programmed desorption (TPD) and Monte Carlo (MC) simulations of TPD traces to characterize the desorption kinetics of pentacene (PEN) and perfluoropentacene (PFP) on MoS2 as a model system for OSCs on TMDCs. We show that the monolayers of PEN and PFP are thermally stabilized compared to their multilayers, which allows preparation of nominal monolayers by selective desorption of multilayers. This stabilization is, however, caused by entropy due to a high molecular mobility rather than an enhanced molecule–substrate bond. Consequently, the nominal monolayers are not densely packed films. Molecular mobility can be suppressed in mixed monolayers of PEN and PFP that, due to intermolecular attraction, form highly ordered films as shown by scanning tunneling microscopy. Although this reduces the entropic stabilization, the intermolecular attraction further stabilizes mixed films.

Pentacene/perfluoropentacene bilayers on Au(111) and Cu(111): impact of organic-metal coupling strength on molecular structure formation.

As crucial element in organic opto-electronic devices, heterostructures are of pivotal importance. In this context, a comprehensive study of the properties on a simplified model system of a donor–acceptor (D–A) bilayer structure is presented, using ultraviolet photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction (LEED) and normal-incidence X-ray standing wave (NIXSW) measurements. Pentacene (PEN) as donor and perfluoropentacene (PFP) as acceptor material are chosen to produce bilayer structures on Au(111) and Cu(111) by sequential monolayer deposition of the two materials. By comparing the adsorption behavior of PEN/PFP bilayers on such weakly and strongly interacting substrates, it is found that: (i) the adsorption distance of the first layer (PEN or PFP) indicates physisorption on Au(111), (ii) the characteristics of the bilayer structure on Au(111) are (almost) independent of the deposition sequence, and hence, (iii) in both cases a mixed bilayer is formed on the Au substrate. This is in striking contrast to PFP/PEN bilayers on Cu(111), where strong chemisorption pins PEN molecules to the metal surface and no intermixing is induced by subsequent PFP deposition. The results illustrate the strong tendency of PEN and PFP molecules to mix, which has important implications for the fabrication of PEN/PFP heterojunctions.

Spatial Anisotropy of Charge Transfer at Perfluoropentacene-Pentacene (001) Single-Crystal Interfaces and its Relevance for Thin Film Devices.

Archetypal donor-acceptor (D-A) interfaces composed of perfluoropentacene (PFP) and pentacene (PEN) are examined for charge transfer (CT) state formation and energetics as a function of their respective molecular configuration. To exclude morphological interference, our structural as well as highly sensitive differential reflectance spectroscopy studies were carried out on PFP thin films epitaxially grown on PEN(001) single-crystal facets. Whereas the experimental data supported by complementary theoretical calculations confirm the formation of a strong CT state in the case of a cofacial PFP-PEN stacking, CT formation is energetically less favorable and thus absent for the corresponding head-to-tail configuration as disclosed for the first time. In view of technological implementations, the knowledge gained on the single-crystal references is transferred to thin-film diodes composed of either stacked PFP/PEN bilayers or mixed PFP:PEN heterojunction interfaces. As demonstrated, their electronic and electroluminescent behavior can be consistently described by the absence or presence of interfacial CT states. Thus, our results hint at the thorough design of D-A interfaces to achieve the highest device performances.

Van der Waals Bound Organic/2D Insulator Hybrid Structures: Epitaxial Growth of Acene Films on hBN(001) and the Influence of Surface Defects.

Combining 2D materials with functional molecular films enables the fabrication of van der Waals bound organic/inorganic hybrids that are of interest for future device architectures. Recently, the 2D dielectric hexagonal boron nitride (hBN) has received particular attention since exfoliation allows the preparation of crystalline layers which have been utilized as ultrathin dielectrics in electronic devices. Here, we have studied the formation and structure of molecular films of the prototypical organic semiconductors pentacene (PEN) and perfluoropentacene (PFP) on hBN. Special attention was paid to the influence of substrate surface defects on the film formation by comparing molecular films that were grown on hBN substrates of various quality, including single crystals (representing the most ideal surface), briefly ion bombarded substrates, and exfoliated flakes. While X-ray diffraction (XRD) yields precise information about the crystalline structure of films grown on (large) single crystals, it is hardly applicable to analyze the films formed on exfoliated flakes because of their small size. Here, we demonstrate that in the case of flakes detailed structural analyses of the molecular films are possible by combining atomic force microscopy (AFM) with microspot UV/vis spectroscopy and optical polarization microscopy. On well-ordered hBN single crystal surfaces both acenes form very smooth and epitaxial crystalline films where molecules adopt a recumbent orientation (even in 100 nm thick films). By contrast, both materials adopt an upright molecular orientation and different polymorphs on defective hBN surfaces and reveal distinctly different film morphologies. On exfoliated flakes, PFP shows a film structure similar to that on the hBN single crystals, while PEN films exhibit a structure as on defective hBN substrates. In addition, a pronounced decoration of defect steps, which are probably created by the exfoliation process, was observed for PEN leading to the formation of tall and extended fibers where molecules adopt a recumbent orientation. The present study reveals different robustness in film growth on exfoliated hBN flakes for various molecules, which has to be considered in their device integration, especially with regard to their optoelectronic properties such as light absorption or charge transport, which depend critically on the molecular orientation and crystalline order.

Unilaterally Fluorinated Acenes: Synthesis and Solid-State Properties.

The rapid development of organic electronics is closely related to the availability of molecular materials with specific electronic properties. Here, we introduce a novel synthetic route enabling a unilateral functionalization of acenes along their long side, which is demonstrated by the synthesis of 1,2,10,11,12,14‐hexafluoropentacene (1) and the related 1,2,9,10,11‐pentafluorotetracene (2). Quantum chemical DFT calculations in combination with optical and X‐ray absorption spectroscopy data indicate that the single‐molecule properties of 1 are a connecting link between the organic semiconductor model systems pentacene (PEN) and perfluoropentacene (PFP). In contrast, the crystal structure analysis reveals a different packing motif than for the parent molecules. This can be related to distinct F⋅⋅⋅H interactions identified in the corresponding Hirshfeld surface analysis and also affects solid‐state properties such as the exciton binding energy and the sublimation enthalpy.

Monolayer and Bilayer Perfluoropentacene on Cu(111)

Perfluoropentacene (PFP), an $n$-type organic semiconductor, is deposited at monolayer and bilayer coverage on Cu(111). Scanning tunneling microscopy at various bias voltages is used to investigate the geometric and electronic structure of the layer. The appearances of the first layer and second layer differ, probably because of perturbation to the first layer electronic structure by the substrate. This has been previously observed for pentacene (Pn), the isostructural $p$-type organic semiconductor. The PFP film has a unit cell of (4 -3,3 4) relative to the substrate, which is larger than that of Pn/Cu(111), representing a half-integer increment in each direction.

Study on the Effect of Chemically Different Substrates on Nucleation and Growth Mechanism of Perfluoropentacene Thin Films

We studied the effect of chemical properties of substrates on the structural properties of perfluoropentacene (PFP) thin films grown by the supersonic molecular beam deposition technique. To this e...

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.

Perfluoropentacene adsorption on Cu(110)

The adsorption of perfluoropentacene (PFP) on the Cu(110) surface has been investigated using reflectance difference spectroscopy (RDS), low-energy electron diffraction, and low-temperature scanning tunneling microscopy. The PFP molecules within the first monolayer align their long molecular axis exclusively oriented along the [001] azimuthal direction of the Cu substrate. In comparison with the adsorption behavior of pentacene on the same surface, a strong effect of the fluorination regarding the molecular orientation and the intermolecular and molecule-substrate interactions was identified. Furthermore, a two-dimensional gas-solid phase transition accompanied by a reversible azimuthal rotation of the PFP molecules was observed at the beginning of the second monolayer growth. The change of the optical anisotropy associated with this reorientation was used to explore the two-dimensional (2D) condensation as a function of coverage and temperature by RDS, and the 2D heat of condensation in the PFP bilayer on Cu(110) was determined to be 105 meV.

A new instrumentation for in situ characterization of the charge transport and crystallographic properties in co-evaporated organic thin film transistor

ABSTRACTA new instrumentation was developed to study the in situ electrical and crystallographic properties of organic thin film transistor during vacuum deposition. We characterized pentacene (PEN) and perfluoro-pentacene (PFP) co-deposited organic thin film transistor with various mixing ratio using this equipment. Lattice parameters and crystal orientations of PEN and PFP alloyed phases (named σ-phase and λ-phase) were determined using an in situ two-dimensional grazing incidence X-ray diffraction (2D-GIXD) measurement. The observed 2D-GIXD patterns clarified that the σ-phase is in triclinic unit cell with the following lattice parameters: a = 0.67 nm, b = 0.75 nm, c = 1.58 nm, α = 95.7° β = 94.2° and γ = 84.0°. The c plane of σ-phase crystal is parallel to the substrate surface. The λ-phase is also in triclinic with the following lattice parameters: a = 0.66 nm, b = 0.69 nm, c = 1.56 nm, α = 109.5° β = 113.0° and γ = 81.5°. The a plane of λ-phase crystal was parallel to the substrate surface. It was also found the best symmetric hole and electron mobility (μh = 5.5 × 10−4 cm2V−1s−1 and μe = 5.1 × 10−4 cm2V−1s−1) were obtained at PEN: PFP = 1:1.

Understanding the F 1s NEXAFS Dichroism in Fluorinated Organic Semiconductors

The analysis of NEXAFS spectra acquired at the absorption edge of heteroatoms like fluorine, nitrogen, or oxygen enables the determination of the molecular orientation of individual compounds even in multinary structures. Such an analysis requires detailed knowledge about the nature of the corresponding electronic excitations, especially because 1s-π* and 1s-σ* excitations frequently feature disparate transition dipole moments in planar molecules. Unlike intuitively assumed, the resulting dichroisms of both excitation types in planar systems are, however, not necessarily inverted. Instead, both the structure of the molecules and their alignment on the substrate determine the actual dichroisms. In this study, the NEXAFS signature and dichroisms of thin films of the organic n-type semiconductor perfluoropentacene (PFP) in different crystalline orientations at the carbon and fluorine absorption K-edge are thoroughly analyzed. For lying molecular orientations, an inverted dichroism at the fluorine K-edge compared to the carbon K-edge is found. In contrast, for upright molecular configurations the dichroisms at both absorption edges are similar. With the help of density functional theory methods, this behavior is explained by the different nature of the excitations. While at the carbon K-edge 1s-π* excitations are most prominent, 1s-σ*-related signals are dominant at the fluorine K-edge. Computations of the NEXAFS signatures and corresponding excitations at different levels of theory are compared with particular focus on electronic relaxation. Energetic positions and oscillator strengths, especially for resonances of σ*-type, depend strongly on the theoretical approach whereas the π*-related signals are barely affected by the methods applied in the present work. Similar effects were also found for the analysis of the smaller perfluoronaphthalene and are explained by the different relaxation effects for 1s-σ*- and 1s-π*-type excitations. As the investigated acenes are representative model systems for π-conjugated molecular semiconductors, the present findings are important for the understanding of the electronic properties and the application of NEXAFS for structural analysis in such materials.

Molecular-Level Realignment in Donor–Acceptor Bilayer Blends on Metals

Molecular bilayers made up of a donor–acceptor blend in contact with the metal and capped with a single-component layer show a tunable energy level alignment at both metal–organic and organic–organic interfaces. To ensure sharp heteromolecular interfaces, a contact layer is formed by a stable blend of pentacene (PEN) and perfluorinated copper phthalocyanine (F16CuPc) on Au(111) and Ag(111) and of perfluoropentacene (PFP) and copper phthalocyanine (CuPc) on Ag(111). Core-level and valence band photoemission reveal that, upon capping with pure F16CuPc, CuPc, and PEN, the electronic states of both contact and capping layers “realign” with respect to the monolayer and the multilayer references. The sign of the shift depends clearly on whether the capping layer is donor-like (PEN, CuPc) or acceptor-like (F16CuPc). As revealed by NEXAFS, the shift in electronic levels of the contact layer upon capping leads to a spectral density variation across the Fermi edge (EF); i.e., it induces molecule/metal charge transfer.

Identification of an organic semiconductor superlattice structure of pentacene and perfluoro-pentacene through resonant and non-resonant X-ray scattering

Highly crystalline and stable molecular superlattices are grown with the smallest possible stacking period using monolayers (MLs) of the organic semiconductors pentacene (PEN) and perfluoro-pentacene (PFP). Superlattice reflections in X-ray reflectivity and their energy dependence in resonant soft X-ray reflectivity measurements show that PFP and PEN MLs indeed alternate even though the coherent ordering is lost after ∼ 4 ML. The observed lattice spacing of 15.9 Å in the superlattice is larger than in pure PEN and PFP films, presumably because of more upright standing molecules and lack of interdigitation between the incommensurate crystalline PEN and PFP layers. The findings are important for the development of novel organic quantum optoelectronic devices.

Microstructural Characterization of Organic Heterostructures by (Transmission) Electron Microscopy

Transmission electron microscopy can be a powerful tool to characterize organic heterostructures, if suitable methods are applied. Here, we present with the example of codeposited films of pentacene (PEN) and perfluoropentacene (PFP) different techniques, which can also be applied to the radiation-sensitive organic materials. The structure and morphology of codeposited films of PEN and PFP on a KCl(100) substrate have been investigated by different (transmission) electron microscopy techniques. When prepared by stoichiometrically equivalent coevaporation of both compounds, the films exhibit an intermixed phase that consists of a 1:1 mixture of the two molecules. Unavoidable excess of one of the two molecules was shown to lead to a spread-out film consisting of the respective molecule, which was verified for the case of PEN excess and whose growth was shown in detail. Interestingly, the film of segregated PEN exhibits a distinctly distinguishable growth from the pure PEN on the same substrate material, forming a 4-fold symmetry aligned with the KCl⟨001⟩ directions. The adaption of an automated nanocrystal orientation and phase mapping technique for the transmission electron microscope, commercially available as the so-called ASTAR system, to these beam-sensitive materials will be discussed as this method not only offers additional functionality for the nanoscale characterization of the films but is inherently advantageous for materials that are prone to beam-induced structural changes.

Adsorption of perfluoropentacene on aluminum (1 0 0) surface: Structural and electronic properties from first principle study

The adsorption of organic molecules on the metal surfaces has received considerable attention due to their potential applications in molecular electronic devices. We have performed first principle density functional theory calculations based on the projected augmented wave (PAW) method to investigate the structural and electronic properties of perfluoropentacene/Al(100) interface. Perfluoropentacene (PFP) prefers to stay planar on Al(100) surface at bridge site, with 45° of rotation and vertical distance of 3.6Å within LDA, 4.2Å within GGA and 3.8Å within DFT-D2 methods. Calculated results show that the adsorption of PFP molecule on Al(100) surface is physisorption. The change in work-function of the Al(100) surface upon the adsorption of PFP is calculated. Further, the electronic properties such as density of states (DOS), partial density of states (PDOS), Mulliken population analysis and Schottky barrier height (SBH) are studied for the stable adsorption geometry. This study shows that the charge is transferred from aluminum surface to PFP molecule and PFP/Al(100) interface is favorable for electron transport.

Structural Defects Control the Energy Level Alignment at Organic/Organic Interfaces

The dependence of the energy level alignment (ELA) on structural defects at an organic/organic heterojunction (OOH) of perfluoropentacene (PFP)‐on‐diindenoperylene (DIP) was investigated using X‐ray scattering and ultraviolet photoelectron spectroscopy. The density of structural defects near the interface between the PFP and DIP layers was varied by changing the growth temperature of the DIP film. A direct relationship was found between the defect density and the ELA at the OOH; the ELA together with the change in the electrostatic potential (quasi‐interface dipole layer) at the OOH varies systematically with the defect density near the interface. This indicates that a key factor affecting the ELA is the electrostatic potential change across the OOH interface, which is produced by electron transfer from DIP occupied gap states to PFP unoccupied gap states. These gap states originate from the defects and are effectively controlled by adjusting the growth conditions of the organic films. As a result, the ELA at OOH interfaces can be controlled by the density of structural defect, which is important for organic devices employing OOHs, such as organic photovoltaic cells.

Structure formation in perfluoropentacene:diindenoperylene blends and its impact on transient effects in the optical properties studied in real-time during growth

We discuss the result of the competing effects of favourable intermolecular interactions and steric incompatibilities due to the size mismatch of perfluoropentacene (PFP) and diindenoperylene (DIP) on the structure formation and associated optical properties in mixed films. Using real-time grazing incidence X-ray diffraction we investigate the size of coherently scattering islands l(s) as a function of film thickness and mixing ratio. We find that for PFP:DIP 1:2 blends l(s) is by a factor of ~4 smaller than in pure DIP films, while l(s) of the PFP:DIP 2:1 blends is not significantly reduced compared with pure PFP. Yet, we observe an increase in l(s) with film thickness for all of the samples, independent on the mixing ratio. In parallel with the structural characterization we investigate the evolution of the absorption spectra in the visible spectral range and its dependence on l(s) in situ during film growth using differential reflectance spectroscopy. We observe a surprisingly strong effect of changes in the structural order on the shape of ε(2, xy)(E), evident by a pronounced evolution of characteristic peaks in the thickness range from 1.6 nm to 9.6 nm. The combined results of the real-time experiments allow to identify the thickness dependent crystal grain size as the origin of the observed transient effects in the absorption spectra.

A Comparative Study on the Adsorption Behavior of Pentacene and Perfluoropentacene Molecules on Au(111) Surfaces

In this study, we use low-temperature scanning tunneling microscopy and X-ray photoemission spectroscopy to study two closely related molecules, pentacene (PEN) and perfluoropentacene (PFP), adsorbed on a herringbone reconstructed Au(111) surface. PEN molecules are mobile under the probe tip at an elevated positive sample bias voltage with the direction of diffusion being correlated to the surface structure and the initial molecular orientation. Moreover, an induced rearrangement of the herringbone reconstruction is observable after manipulation. PFP molecules rearrange into flat, densely packed islands and the herringbone structure is undisturbed by the adsorbed PFP molecules. In addition, the X-ray photoelectron spectroscopy (XPS) C 1s and F 1s core level spectra of PFP show a shift toward high binding energy at high coverage. In comparison only a subtle shift for the C 1s core level of PEN at high coverage is seen. This indicates a different molecular arrangement for PFP in the bulk and in close proximity to the gold substrate.