Pentacene Islands Research Articles

Nanoscale electronic transport at graphene/pentacene van der Waals interfaces.

We report a study on the relationship between the structure and electron transport properties of nanoscale graphene/pentacene interfaces. We fabricated graphene/pentacene interfaces from 10 to 30 nm thick needle-like pentacene nanostructures down to two-three layer (2L-3L) dendritic pentacene islands, and we measured their electron transport properties by conductive atomic force microscopy (C-AFM). The energy barrier at the interfaces, i.e., the energy position of the pentacene highest occupied molecular orbital (HOMO) with respect to the Fermi energy of graphene and the C-AFM metal tip was determined and discussed with an appropriate electron transport model (a double Schottky diode model and a Landauer-Buttiker model, respectively) taking into account the voltage-dependent charge doping of graphene. In both types of samples, the energy barrier at the graphene/pentacene interface is slightly larger than that at the pentacene/metal tip interface, resulting in 0.47-0.55 eV and 0.21-0.34 eV, respectively, for the 10-30 nm thick needle-like pentacene islands, and 0.92-1.44 eV and 0.67-1.05 eV, respectively, for the 2L-3L thick dendritic pentacene nanostructures. We attribute this difference to the molecular organization details of the pentacene/graphene heterostructures, with pentacene molecules lying flat on graphene in the needle-like pentacene nanostructures, while standing upright in the 2L-3L dendritic islands, as observed from Raman spectroscopy.

Charge Carrier Inversion in a Doped Thin Film Organic Semiconductor Island.

Inducing an inversion layer in organic semiconductors is a highly nontrivial, but critical, achievement for producing organic field-effect transistor (OFET) devices, which rely on the generation of inversion, accumulation, and depletion regimes for successful operation. Here, we develop a pulsed bias technique to characterize the dopant type of any organic material system, without prior knowledge or characterization of the material in question. We use this technique on a pentacene/PTCDI heterostructure and thus deduce that pentacene is exhibiting n-doped like response. The source of the additional charges in the pentacene island can be identified by charging rings in the dissipation channel of the noncontact atomic force microscopy (AFM) signal, a typical signature for localized charge transfer from the AFM tip to the sample. Additionally, through tip-induced band-bending, we generate inversion, depletion, and accumulation regimes over a 20 nm radius, three monolayer thick n-doped pentacene island. Our findings demonstrate that nanometer-scale lateral extent and thickness are sufficient for an OFET device to operate in the inversion regime.

Effectively Enhanced Broadband Phototransistors Based on Multilayer WSe2/Pentacene

AbstractBroadband photodetectors sensitive to light from visible to near‐infrared are essential for various applications such as thermal evaluation, bio‐imaging mapping, and bio‐health monitoring. Multilayer WSe2 offers broad light spectral responses and roles in broadband phototransistors’ active matrix. However, it shows relatively lower photoresponsivity than monolayer WSe2 due to layer‐dependent energy band variations. Pentacene islands, a p‐type organic material, are formed on the multilayer WSe2 to enhance its photoresponsivity under broadband lights. Pentacene islands can prominently absorb ultra‐violet to visible lights and generate enormous excitons. Besides, they have relatively long exciton diffusion lengths in micrometer scales to effectively enable exciton migration and charge transfer at the pentacene and WSe2 interface. Consequently, the photocurrent (Iph) and the photoresponsivity (Rph) in WSe2/pentacene transistors are 1.41 µA and 19.313 A W−1 for 638‐nm light and 0.20 µA and 1.16 A W−1 for 852‐nm light. Therefore, WSe2/pentacene‐based phototransistors can be applied for broadband photodetectors under visible to near‐infrared.

In Situ Wettability Characterization of Chemically Heterogeneous Surfaces Probed by Ionic Liquid Contact Angle in Vacuum: Pentacene on Single-Crystal SrTiO3(001)

Intrinsic surface wettability of pentacene thin films with different island coverages grown on single-crystal SrTiO3(001) was investigated by an in situ contact angle measurement in a high vacuum using ionic liquid as a probe fluid. The contact angle at the quasi-equilibrium state, which was measured at a certain time after its fast decay depending on the liquid viscosity, increased with the deposition amount of pentacene and saturated when the surface was fully covered with pentacene islands. The observed island coverage dependence of the in situ contact angle was well-fitted by a three-component Cassie equation composed of surface areas of not only the bare substrate and island pentacene but also adsorbed pentacene. The importance of the in situ contact angle measurement was confirmed by the result of an air exposure experiment, where the contact angle took almost irrelevant values to the integral coverage of pentacene, suggesting the significant effects of airborne contaminants on the surface wettability.

Surface morphology of vacuum-evaporated pentacene film on Si substrate studied by in situ grazing-incidence small-angle X-ray scattering: I. The initial stage of formation of pentacene film

The progress of the surface morphology of a growing sub-monolayered pentacene film on a Si substrate was studied by in situ grazing-incidence small angle X-ray scattering (GISAXS). The observed GISAXS profiles did not show sizes of pentacene islands but mainly protuberances on the boundaries around pentacene film. Scattering of X-ray by residual pits in the pentacene film was also detected in the GISAXS profiles of an almost fully covered film. The average radius of pentacene protuberances increased from 13 to 24 nm as the coverage increased to 0.83 monolayer, and the most frequent radius was almost constant at approximately 9 nm. This result suggests that the population of larger protuberances increase with increasing lengths of boundaries of the pentacene film. It can also be considered that the detected protuberances were crystallites of pentacene, since the average size of protuberances was nearly equal to crystallite sizes of pentacene films. The almost constant characteristic distance of 610 nm and amplitudes of pair correlation functions at low coverages suggest that the growth of pentacene films obeyed the diffusion-limited aggregation (DLA) model, as previously reported. It is also considered that the sites of islands show a triangular distribution for small variations of estimated correlation distances.

Epitaxial Growth of Pentacene on Alkali Halide Surfaces Studied by Kelvin Probe Force Microscopy

In the field of molecular electronics, thin films of molecules adsorbed on insulating surfaces are used as the functional building blocks of electronic devices. Control of the structural and electronic properties of the thin films is required for reliably operating devices. Here, noncontact atomic force and Kelvin probe force microscopies have been used to investigate the growth and electrostatic landscape of pentacene on KBr(001) and KCl(001) surfaces. We have found that, together with molecular islands of upright standing pentacene, a new phase of tilted molecules appears near step edges on KBr. Local contact potential differences (LCPD) have been studied with both Kelvin experiments and density functional theory calculations. Our images reveal that differently oriented molecules display different LCPD and that their value is independent of the number of molecular layers. These results point to the formation of an interface dipole, which may be explained by a partial charge transfer from the pentacene to the surface. Moreover, the monitoring of the evolution of the pentacene islands shows that they are strongly affected by dewetting: Multilayers build up at the expense of monolayers, and in the Kelvin images, previously unknown line defects appear, which reveal the epitaxial growth of pentacene crystals.

Electronic Polarization at Pentacene/Polymer Dielectric Interfaces: Imaging Surface Potentials and Contact Potential Differences as a Function of Substrate Type, Growth Temperature, and Pentacene Microstructure

Interfaces between organic semiconductors and dielectrics may exhibit interfacial electronic polarization, which is equivalently quantified as a contact potential difference (CPD), an interface dipole, or a vacuum level shift. Here we report quantitative measurements by scanning Kelvin probe microscopy (SKPM) of surface potentials and CPDs across ultrathin (1–2 monolayer) crystalline islands of the benchmark semiconductor pentacene thermally deposited on a variety of polymer dielectrics (e.g., poly(methyl methacrylate), polystyrene). The CPDs between the pentacene islands and the polymer substrates are in the range of −10 to +50 mV, they depend strongly on the polymer type and deposition temperature, and the CPD magnitude is correlated with the dipole moment of the characteristic monomers. Surface potential variations within 2 monolayer (3 nm) thick pentacene islands are ∼15 mV and may be ascribed to microstructure (epitaxial) differences. Overall, the microscopy results reveal both strong variations in i...

High-performance pentacene thin-film transistor with ZrLaO gate dielectric passivated by fluorine incorporation

Pentacene thin-film transistor with high-κ ZrLaO gate dielectric has been fabricated for the first time. After treating the dielectric in a fluorine plasma, the carrier mobility of the transistor can be greatly improved to 0.717cm2/Vs, which is more than 40 times that of one without plasma treatment. The major reasons should be larger pentacene grains and fewer traps in the device with gate dielectric passivated by the fluorine plasma. AFM confirms that relatively large and high pentacene islands form on the plasma-treated dielectrics in the initial growth stage, and the growth pattern obviously follows the Vollmer–Weber growth model. Furthermore, the surfaces of the dielectrics with different plasma treatment times are investigated by AFM, XPS and contact-angle measurement to reveal the mechanism/effects of the fluorine incorporation. Lastly, after exposure to atmosphere without encapsulation for 6months, all the devices still display good transistor characteristics.

Growth of pentacene crystallinity control layers for high mobility organic field-effect transistors based on benzodithiophene-dimer films

We have investigated the growth process of benzodithiophene (BDT)-dimer films deposited on ∼1.1-monolayer-thick pentacene layers used as crystallinity control layers (CCLs). It has been found that the BDT-dimer film shows, on their initial stage, two-dimensional growth with the 2nd-layer pentacene islands of the CCLs working as the growth nuclei. Thus, we considerably reduced the density of the 2nd-layer pentacene islands of the CCLs by lowering their growth rate because the density is determined by the migration length of the pentacene molecules on the surfaces. As a result, we obtained BDT-dimer films consists of enlarged grains, and lowered the channel resistance of the pentacene-CCL/BDT-dimer FETs.

Behavior of pentacene molecules deposited onto roughness-controlled polymer dielectrics films and its effect on FET performance

We describe the effects of the polymer dielectric surface roughness on the nucleation and initial island growth of pentacene films in the submonolayer regime using poly(methylmethacrylate) and polystyrene films with highly controlled surface roughness value. The pentacene film structures were found to significantly affect the performances of pentacene field-effect transistors (FETs). As the dielectric surface roughness increased, the activation energies for pentacene island nucleation and molecule reevaporation from the surface were dramatically reduced. A high surface roughness greater than 0.9nm was found to limit the degree to which the FET performances could be improved. These results suggest a means for optimizing the nanostructural surfaces of polymer dielectrics by engineering OFET interfaces in an effort to improve device performance.

The interplay of topography and energy dissipation in pentacene thin films

Nonlinear photoemission electron microscopy was used to study the morphology-dependent lifetime of electronic excitations in pentacene islands on Si(001) and (√3×√3)R30°-Ag/Si(111). After an optical excitation of electrons by a λ=400nm femtosecond laser pulse the characteristic decay times were measured with spatial resolution in a pump-probe setup. For pentacene on Si(001), the observed lifetimes vary by a factor of two between the wetting layer and the fractal-shaped pentacene islands. The measured lifetime difference is explained by a difference in the electronic coupling of the pentacene islands and the wetting layer to the substrate. For pentacene on (√3×√3)R30°-Ag/Si(111), similar lifetimes are found, although the orientation of the pentacene molecules in the compact islands is rotated. Our findings suggest that electronic excitations in higher layers of the pentacene islands do not diffuse to the interface before they decay.

The effects of the surface morphology of poly(3,4-ethylenedioxythiophene) electrodes on the growth of pentacene, and the electrical performance of the bottom contact pentacene transistor

An investigation is presented of the effect of the surface roughness of poly(3,4-ethylenedioxythiophene) (PEDOT) electrodes on the growth of pentacene and the electrical performance of PEDOT electrode bottom contact pentacene transistor. Smooth PEDOT films contained well-oriented and small sized pentacene islands whilst rough PEDOT films exhibited randomly oriented islands with non-uniformly sized islands. In addition, PEDOT electrodes provided morphological continuity at the electrode–channel interface, making the accumulation channel of the pentacene formed on the electrodes a main contributor to the contact resistance. Accordingly, the smooth PEDOT surface yielded the low contact resistance (5.7 kΩ cm), approximately half of that obtained with the rough surface.

Direct Observation and Measurement of Mobile Charge Carriers in a Monolayer Organic Semiconductor on a Dielectric Substrate

We report the electrical characterization of a single layer of an organic semiconductor grown on a dielectric surface. The dynamic response of the charge carriers in the monolayer film of pentacene was characterized through the electrostatic interactions between an electric force microscope (EFM) probe and pentacene islands of various sizes. These islands were formed in situ by segmenting a coalesced pentacene monolayer into separated regions. The size-dependent dielectric responses of the pentacene islands suggest that mobile charges exist in the organic monolayer. Local capacitance spectroscopy revealed that the charge carriers in the p-type pentacene monolayer could be depleted at high bias voltages, enabling a further determination of the charge-carrier concentration in the organic semiconductor ultrathin film.

Behavior of Pentacene Initial Nucleation on Various Dielectrics and Its Effect on Carrier Transport in Organic Field-Effect Transistor

The influence of dielectric surface energy on the initial nucleation and the growth of pentacene films as well as the electrical properties of the pentacene-based field-effect transistors are investigated. We have examined a range of organic and inorganic dielectrics with different surface energies, such as polycarbonate/SiO2, polystyrene/SiO2, and PMMA/SiO2 bi-layered dielectrics and also the bare SiO2 dielectric. Atomic force microscopy measurements of sub-monolayer and thick pentacene films indicated that the growth of pentacene film was in Stranski-Kranstanow growth mode on all the dielectrics. However, the initial nucleation density and the size of the first-layered pentacene islands deposited on different dielectrics are drastically influenced by the dielectric surface energy. With the increasing of the surface energy, the nucleation density increased and thus the average size of pentacene islands for the first mono-layer deposition decreased. The performance of fabricated pentacene-based thin film transistors was found to be highly related to nucleation density and the island size of deposited Pentacene film, and it had no relationship to the final particle size of the thick pentacene film. The field effect mobility of the thin film transistor could be achieved as high as 1.38 cm2Ns with on/off ratio over 3 x 10(7) on the PS/SiO2 where the lowest surface energy existed among all the dielectrics. For comparison, the values of mobility and on/off ratio were 0.42 cm2Ns and 1 x 10(6) for thin film transistor deposited directly on bare SiO2 having the highest surface energy.

Multiscale Morphology of Organic Semiconductor Thin Films Controls the Adhesion and Viability of Human Neural Cells

We investigate how multiscale morphology of functional thin films affects the in vitro behavior of human neural astrocytoma 1321N1 cells. Pentacene thin film morphology is precisely controlled by means of the film thickness, Θ (here expressed in monolayers (ML)). Fluorescence and atomic force microscopy allow us to correlate the shape, adhesion, and proliferation of cells to the morphological properties of pentacene films controlled by saturated roughness, σ, correlation length, ξ, and fractal dimension, df. At early incubation times, cell adhesion exhibits a transition from higher to lower values at Θ ≈ 10 ML. This is explained using a model of conformal adhesion of the cell membrane onto the growing pentacene islands. From the model fitting of the data, we show that the cell explores the surface with a deformation of the membrane whose minimum curvature radius is 90 (± 45) nm. The transition in the adhesion at ∼10 ML arises from the saturation of ξ accompanied by the monotonic increase of σ, which leads to a progressive decrease of the pentacene local radius of curvature and hence to the surface area accessible to the cell. Cell proliferation is also enhanced for Θ < 10 ML, and the optimum morphology parameter ranges for cell deployment and growth are σ ≤ 6 nm, ξ > 500 nm, and df > 2.45. The characteristic time of cell proliferation is τ ≈ 10 ± 2 h.

Molecular structure of extended defects in monolayer-scale pentacene thin films

The growth of pentacene thin films for applications in thin-film transistors and other organic electronic devices results in a variety of extended structural defects including dislocations, grain boundaries, and stacking faults. We have used scanning tunneling microscopy (STM) to probe the molecular-scale structure of grain boundaries and stacking faults in a pentacene thin film on a Si (001) surface modified with styrene. Styrene/Si (001) substrates produce pentacene films that are structurally similar to those grown on insulating substrates, but which are sufficiently smooth and conductive for STM studies. STM images show two types of grain boundaries: in-plane high-angle tilt grain boundaries at the junctions between pentacene islands, and twist boundaries between molecular layers. Segments of the tilt grain boundaries are faceted along low-energy crystallographic directions. Stacking faults are found in the plane of individual pentacene grains. Two rows of molecules near the stacking fault are shifted along the surface normal by 60 pm. Electronically relevant trap states may thus be associated with stacking faults in pentacene thin films.

Key role of molecular kinetic energy in early stages of pentacene island growth

Organic molecular beam deposition is studied systematically at thermal and hyperthermal regimes aiming at investigating the role of molecular kinetic energy on the growth mechanism of pentacene submonolayers on SiOx/Si. We show that the kinetic energy of the impinging molecule (Ek) plays a crucial role in determining island structure and shape, distribution of island sizes, the crystalline quality of the first monolayer, and even the growth mode of subsequent layers. With increasing Ek, the island structure changes from fractal to nonfractal, the shape becomes more anisotropic and the island size more uniform, pointing to correlated island growth. Moreover, while 3D island growth is observed for thermal organic molecular beam deposition, supersonic molecular beam deposition gives rise to layer-by-layer growth, at least for the first two layers. When Ek≥5.0 eV, the first monolayer is composed of large single crystalline domains which can extend over up to 10 μm, inferred from comparing atomic force micrographs of height and net transverse shear force. In these growth conditions both the high surface diffusivity and energy redistribution play a major role. We propose a mechanism where the energy dissipation occurring during the molecule–surface collision leads to the reorientation of whole islands during island coalescence, resulting in the elimination of grain boundaries.

Enhancement of Electrical Conductance for Pentacene Thin Film Transistor by Controlling an Initial Layer-by-Layer Growth Mode Directly on SiO2 Insulator

Initial nucleation and growth of pentacene films on various pre-cleaning treated SiO2 gate insulators were systematically examined by atomic force microscope. The performance of fabricated pentacene thin film transistor devices was found to be highly related to the initial film growth modes. In contrast to the film in the three-dimensional island-like growth mode on SiO2 under an organic cleaning process, a layer-by-layer initial growth mode occurred on the SiO2 insulator cleaned with ammonia solution which has shown much improved electrical properties of the thin film transistors. Field effect mobility of the thin film transistor devices could be achieved as high as 1.0 cm2 V-1 s-1 on the bared SiO2/Si substrate and the on/off ratio was over 106. The enhanced electrical conductance was further confirmed by an electrostatic force microscopic observation of quantized electrical potentials via charge-injection to the submonolayer pentacene islands with layer-by-layer growth mode.

Evaluation of organic sub-monolayers by X-ray based measurements under gracing incident conditions

The structural investigations of model organic systems like pentacene on silicon oxide in the monolayer regime is very important for the basic understanding of initial nucleation process together with the electronic performance of transistor devices. A method for the evaluation of the island formation and layer closing of the first monolayer is introduced. The method is based on specular X-ray reflectivity and diffuse scattering and reveal integral information on the coverage together with the size and separation of pentacene islands. The results are in good agreement with AFM investigation that encourages the use of this type of investigation in in-situ experiments.

Carbon attachment on the aluminum nitride gate dielectric in the pentacene-based organic thin-film transistors

This study presents carbon attachment on an aluminum nitride (AlN) gate dielectric to improve the device performance of pentacene-based organic thin-film transistors (OTFTs). This approach produces high OTFT performance on an aged AlN surface. A high mobility of 0.67 cm2/V s was achieved on an AlN surface aged for 14 days, compared to a mobility of 0.05 cm2/V s on an as-deposited AlN surface. This improvement in device performance is correlated with carbon attachment on the AlN surface, which lowers surface energy. The lowered surface energy made the surface less polar, as measured by a contact angle instrument. The chemical composition of the aged AlN surface was analyzed using x-ray photoelectron spectroscopy before pentacene deposition. Enhanced C=C bonding at 284.5 eV was observed on the aged AlN surface. These enhanced C=C bonds favored the growth of large pentacene islands in the initial growth stage, which may improve OTFT device performance.