Fundamental processes in the context of ultra-thin organic film growth, adsorption, desorption, diffusion, nucleation and wetting/dewetting phenomena are reviewed. The focus is put on the film growth of rod-like molecules (quaterphenyl, sexiphenyl, pentacene), plate-like molecules (HATCN, rubicene), and molecules which form intermolecular hydrogen bonds (indigo, quinacridone). As substrates Au(111), Ag(111), mica, and silicon dioxide were used. Thermal desorption spectroscopy and atomic force microscopy were applied to study the growth kinetics. Additionally, low-energy electron diffraction, X-ray photoelectron spectroscopy, and X-ray diffraction were used. The objective of this work is to extract general rules and trends in ultra-thin organic film growth, based on the large number of investigated adsorbate/substrate systems.

This article examines the properties of some self-organized nanostructured surfaces with respect to specific model reactions, from a surface-science point of view. It begins with an overview of the most important types of nanostructured surfaces, their preparation and characterization. It then considers the fundamentals of reaction processes, focusing on the kinetics and dynamics of adsorption and desorption. It also describes the experimental techniques used in the context of reaction studies under ultrahigh-vacuum conditions. Finally, it presents some experimental results of model reactions, including hydrogen adsorption and desorption on stepped nickel surfaces, methanol adsorption on self-assembled copper-copper oxide surfaces, and hydrogen desorption and water formation on vanadium-oxide nanostructures on palladium surfaces.

Epindolidione, a hydrogen-bonded derivative of the organic semiconductor tetracene, is an organic pigment which has previously been used to produce stable OFETs with relatively high hole mobilities. Despite its use as an inkjet pigment and organic semiconductor, the crystal structure of epindolidione has proved elusive and is currently unknown. In this work, we report a crystal structure solution of epindolidione determined from vapor deposited thin films using a combined experimental and theoretical approach. The structure is found to be similar to one of the previously reported epindolidione derivatives and is most likely a surface-mediated polymorph, with a slightly different crystal packing compared to the bulk powder. The effect of substrate temperature on film morphology and structure is also investigated, where it is found that the crystallite orientation can be tuned by deposition at different substrate temperatures. The results also illustrate the possibilities for crystal structures to be solved from thin films.

We report on in situ performance evaluations as a function of layer thickness and substrate temperature for bottom-gate, bottom-gold contact epindolidione organic thin-film transistors on various gate dielectrics. Experiments were carried out under ultra-high vacuum conditions, enabling quasi simultaneous electrical and surface analysis. Auger electron spectroscopy and thermal desorption spectroscopy (TDS) were applied to characterize the quality of the substrate surface and the thermal stability of the organic films. Ex situ atomic force microscopy (AFM) was used to gain additional information on the layer formation and surface morphology of the hydrogen-bonded organic pigment. The examined gate dielectrics included SiO2, in its untreated and sputtered forms, as well as the spin coated organic capping layers poly(vinyl-cinnamate) (PVCi) and poly((+/-)endo,exo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid, diphenylester) (PNDPE, from the class of polynorbornenes). TDS and AFM revealed Volmer-Weber island growth dominated film formation with no evidence of a subjacent wetting layer. This growth mode is responsible for the comparably high coverage required for transistor behavior at 90-95% of a monolayer composed of standing molecules. Surface sputtering and an increased sample temperature during epindolidione deposition augmented the surface diffusion of adsorbing molecules and therefore led to a lower number of better-ordered islands. Consequently, while the onset of charge transport was delayed, higher saturation mobility was obtained. The highest, bottom-contact configuration, mobilities of approximately 2.5 x 10(-3)cm(2)/Vs were found for high coverages (50 nm) on sputtered samples. The coverage dependence of the mobility showed very different characteristics for the different gate dielectrics, while the change of the threshold voltage with coverage was approximately the same for all systems. An apparent decrease of the mobility with increasing coverage on the less polar PNDPE was attributed to a change in molecular orientation from upright standing in the thin-film phase to tilted in the bulk phase. From temperature-dependent mobility measurements we calculated activation barriers for the charge transport between 110 meV and 160 meV, depending on the dielectric configuration. (C) 2016 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license.

In this article, some fundamental topics related to the initial steps of organic film growth are reviewed. General conclusions will be drawn based on experimental results obtained for the film formation of oligophenylene and pentacene molecules on gold and mica substrates. Thin films were prepared via physical vapor deposition under ultrahigh-vacuum conditions and characterized in-situ mainly by thermal desorption spectroscopy, and ex-situ by X-ray diffraction and atomic force microscopy. In this short review article the following topics will be discussed: What are the necessary conditions to form island-like films which are either composed of flat-lying or of standing molecules? Does a wetting layer exist below and in between the islands? What is the reason behind the occasionally observed bimodal island size distribution? Can one describe the nucleation process with the diffusion-limited aggregation model? Do the impinging molecules directly adsorb on the surface or rather via a hot-precursor state? Finally, it will be described how the critical island size can be determined by an independent measurement of the deposition rate dependence of the island density and the capture-zone distribution via a universal relationship.

The evaporation of quinacridone from a stainless steel Knudsen cell leads to the partial decomposition of this molecule in the cell, due to its comparably high sublimation temperature. At least one additional type of molecules, namely indigo, could be detected in the effusion flux. Thermal desorption spectroscopy and atomic force microscopy have been used to study the co-deposition of these molecules on sputter-cleaned and carbon-covered silicon dioxide surfaces. Desorption of indigo appears at temperatures of about 400 K, while quinacridone desorbs at around 510 K. For quinacridone, a desorption energy of 2.1 eV and a frequency factor for desorption of 1 × 10(19) s(-1) were calculated, which in this magnitude is typical for large organic molecules. A fraction of the adsorbed quinacridone molecules (∼5%) decomposes during heating, nearly independent of the adsorbed amount, resulting in a surface composed of small carbon islands. The sticking coefficients of indigo and quinacridone were found to be close to unity on a carbon covered SiO2 surface but significantly smaller on a sputter-cleaned substrate. The reason for the latter can be attributed to insufficient energy dissipation for unfavorably oriented impinging molecules. However, due to adsorption via a hot-precursor state, the sticking probability is increased on the surface covered with carbon islands, which act as accommodation centers.

In the wake of the increasing importance of organic electronics, a more in-depth understanding of the early stages of organic film growth is indispensable. In this review a survey of several rod-like and plate-like organic molecules (p-quaterphenyl, p-sexiphenyl, hexaazatriphenylene–hexacarbonitrile (HATCN), rubicene, indigo) deposited on various application relevant substrates (gold, silver, mica, silicon dioxide) is given. The focus is particularly put on the application of thermal desorption spectroscopy to shed light on the kinetics and energetics of the molecule–substrate interaction. While each adsorption system reveals a manifold of features that are specific for the individual system, one can draw some general statements on the early stages of organic film formation from the available datasets. Among the important issues in this context is the formation of wetting layers and the dewetting as a function of the substrate surface conditions, organic film thickness and temperature.

We report on the electrical in-situ characterisation of organic thin film transistors under high vacuum conditions. Model devices in a bottom-gate/bottom-contact (coplanar) configuration are electrically characterised in-situ, monolayer by monolayer (ML), while the organic semiconductor (OSC) is evaporated by organic molecular beam epitaxy (OMBE). Thermal SiO2 with an optional polymer interface stabilisation layer serves as the gate dielectric and pentacene is chosen as the organic semiconductor. The evolution of transistor parameters is studied on a bi-layer dielectric of a 150 nm of SiO2 and 20 nm of poly((±)endo,exo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid, diphenylester) (PNDPE) and compared to the behaviour on a pure SiO2 dielectric. The thin layer of PNDPE, which is an intrinsically photo-patternable organic dielectric, shows an excellent stabilisation performance, significantly reducing the calculated interface trap density at the OSC/dielectric interface up to two orders of magnitude, and thus remarkably improving the transistor performance.

In this work we present in situ electrical and surface analytical, as well as ex situ atomic force microscopy (AFM) studies on temperature and surface condition induced pentacene layer growth modifications, leading to the selection of optimized deposition conditions and entailing performance improvements. We prepared p++-silicon/silicon dioxide bottom-gate, gold bottom-contact transistor samples and evaluated the pentacene layer growth for three different surface conditions (sputtered, sputtered+carbon and unsputtered+carbon) at sample temperatures during deposition of 200K, 300K and 350K. The AFM investigations focused on the gold contacts, the silicon dioxide channel region and the highly critical transition area. Evaluations of coverage dependent saturation mobilities, threshold voltages and corresponding AFM analysis were able to confirm that the first 3–4 full monolayers contribute to the majority of charge transport within the channel region. At high temperatures and on sputtered surfaces uniform layer formation in the contact–channel transition area is limited by dewetting, leading to the formation of trenches and the partial development of double layer islands within the channel region instead of full wetting layers. By combining the advantages of an initial high temperature deposition (well-ordered islands in the channel) and a subsequent low temperature deposition (continuous film formation for low contact resistance) we were able to prepare very thin (8ML) pentacene transistors of comparably high mobility.

Thin films of quinacridone deposited by physical vapor deposition on silicon dioxide were investigated by thermal desorption spectroscopy (TDS), mass spectrometry (MS), atomic force microscopy (AFM), specular and grazing incidence X-ray diffraction (XRD, GIXD), and Raman spectroscopy. Using a stainless steel Knudsen cell did not allow the preparation of a pure quinacridone film. TDS and MS unambiguously showed that in addition to quinacridone, desorbing at about 500 K (γ-peak), significant amounts of indigo desorbed at about 420 K (β-peak). The existence of these two species on the surface was verified by XRD, GIXD, and Raman spectroscopy. The latter spectroscopies revealed that additional species are contained in the films, not detected by TDS. In the film mainly composed of indigo a species was identified which we tentatively attribute to carbazole. The film consisting of mainly quinacridone contained in addition p-sexiphenyl. The reason for the various decomposition species effusing from the metal Knudsen cell is the comparably high sublimation temperature of the hydrogen bonded quinacridone. With special experimental methods and by using glass Knudsen-type cells we were able to prepare films which exclusively consist of molecules either corresponding to the β-peak or the γ-peak. These findings are of relevance for choosing the proper deposition techniques in the preparation of quinacridone films in the context of organic electronic devices.

Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation of dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer desorption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption.

The fabrication of organic thin film transistors with highly reproducible characteristics presents a very challenging task. We have prepared and analyzed model pentacene thin film transistors under ultra-high vacuum conditions, employing surface analytical tools and methods. Intentionally contaminating the gold contacts and SiO2 channel area with carbon through repeated adsorption, dissociation, and desorption of pentacene proved to be very advantageous in the creation of devices with stable and reproducible parameters. We mainly focused on the device properties, such as mobility and threshold voltage, as a function of film morphology and preparation temperature. At 300 K, pentacene displays Stranski-Krastanov growth, whereas at 200 K fine-grained, layer-like film growth takes place, which predominantly influences the threshold voltage. Temperature dependent mobility measurements demonstrate good agreement with the established multiple trapping and release model, which in turn indicates a predominant concentration of shallow traps in the crystal grains and at the oxide-semiconductor interface. Mobility and threshold voltage measurements as a function of coverage reveal that up to four full monolayers contribute to the overall charge transport. A significant influence on the effective mobility also stems from the access resistance at the gold contact-semiconductor interface, which is again strongly influenced by the temperature dependent, characteristic film growth mode.

It is known in thin-film deposition that the density of nucleated clusters N varies with the deposition rate F as a power law, N ∼ Fα. The exponent α is a function of the critical nucleus size i in a way that changes with the aggregation limiting process. We extend here the derivation of the analytical capture-zone distribution function Pβ(s) = aß·sβ·exp(-bβs2) of Pimpinelli and Einstein to generic aggregation-limiting processes. We show that the parameter β is generally related to the critical nucleus size i and to the exponent α by the equality α·β = i, in the case of compact islands. This remarkable result allows one to measure i with no a priori knowledge of the actual aggregation mechanism. We apply this equality to measuring the critical nucleus size for pentacene deposition on mica. This system shows a crossover from diffusion-limited to attachment-limited aggregation with increasing deposition rates.

Full text: The morphology of organic thin films is crucial for the functionality of organic electronic devices. Understanding the initial growth and formation of organic thin films requires a detailed description of island nucleation. The island density as a function of the deposition rate and the distribution of the areas of the capture zones of islands measurements are used for determination of critical island size. Here we consider the aggregation of pentacene islands on sputter amorphized mica as a model system for weakly interacting substrates. We show that nucleation and growth is diffusion limited at low deposition rates, and becomes limited by hindered attachment at high deposition rates. (author)

The film growth of the conjugated organic molecule rubicene on silicon dioxide was studied in detail. Since no structural data of the condensed material were available, we first produced high quality single crystals from solution and determined the crystal structure. This high purity material was used to prepare ultrathin films under ultrahigh vacuum conditions, by physical vapor deposition. Thermal desorption spectroscopy (TDS) was applied to delineate the adsorption and desorption kinetics. It could be shown that the initial sticking coefficient is only 0.2 ± 0.05, but the sticking coefficient increases with increasing coverage. TDS further revealed that first a closed, weakly bound bilayer develops (wetting layer), which dewets after further deposition of rubicene, leading to an island-like layer. These islands are crystalline and exhibit the same structure as the solution grown crystals. The orientation of the crystallites is with the (001) plane parallel to the substrate. A dewetting of the closed bilayer was also observed when the film was exposed to air. Furthermore, Ostwald ripening of the island-like film takes place under ambient conditions, leading to films composed of few, large crystallites. From TDS, we determined the heat of evaporation from the multilayer islands to be 1.47 eV, whereas the desorption energy from the first layer is only 1.25 eV.

It is known in thin-film deposition that the density of nucleated clusters $N$ varies with the deposition rate $R$ as a power law, $N \sim R^\alpha$. The exponent $\alpha$ is a function of the critical nucleus size $i$ in a way that changes with the aggregation-limiting process active in a given system. We extend here to generic aggregation-limiting processes the derivation of the analytical capture-zone distribution function $P_\beta(s) = a_\beta s^\beta \exp(-b_\beta s^2)$ of Pimpinelli and Einstein [Phys. Rev. Lett. 99, 226102 (2007)]. We show that the exponent $\beta$ is generally related to the critical nucleus size $i$ and to the exponent $\alpha$ by the equality $\alpha (2\beta + d_f - 2) = 2i$ where $d_f$ is the fractal dimensionality of the clusters. This remarkable results allows one to measure $i$ with no a priori knowledge of the actual aggregation mechanism. We apply this equality to measuring the critical nucleus size in pentacene deposition on mica.