H2O induced structural modification of pentacene crystal

Water is one of the obstacles for prolonged life-time of organic based field-effect-transistors (OFETs). Here, we show how H₂O molecules adsorb and affect pentacene crystal by using photoelectron spectroscopic methods. Diffusion into the crystal is accompanied with accumulation of H₂O onto the crystal. Valence band, core level, and X-ray absorption spectra show that H₂O molecules physisorb on the pentacene surface via oxygen, resulting in the increase of the hole-injection barrier. The diffused molecules results in the deteriorated crystallinity, and they reflect the weakening inter-molecular interactions of pentacene crystal.     

Interaction between surface migrating pentacene molecules and chemically modified surfaces of silicon oxides studied by pulsed molecular beam scattering

The interaction between pentacene molecules and organic self-assembling monolayers formed on silicon oxides (SiO₂) was studied by measuring the surface scattering time profile of the pulsed molecular beam of pentacene. It was found that the surface residence time (SRT) of pentacene was significantly reduced on a surface treated with hexamethyl silazarane (HMDS) compared with that on a bare SiO₂ surface. The activation energies derived from the temperature dependence of the SRT were 24 kJ/mol and 100 kJ/mol for HMDS-SiO₂ and the bare SiO₂, respectively. A surface treated with octadecyltrichlorosilane (OTS) showed SRT values almost the same as those on the bare SiO₂ surface, which was due to exposed SiO₂ regions on the thermally-degraded OTS-SiO₂. The growth mechanism with improved quality is due to the shallower adsorption potential and enhanced migration of pentacene by the surface alkylation.     

Organic thin-film transistors of pentacene films fabricated from a supersonic molecular beam source

Top-contact organic thin-film transistors (OTFTs) of pentacene have been fabricated on bare SiO₂ and SiO₂ modified with hexamethyldisilazane (HMDS) and octadecyltrichlorosilane (OTS). The pentacene films were deposited from a supersonic molecular beam source with kinetic energy of incident molecules ranging from 1.5 to 6.7 eV. The field-effect mobility of OTFTs was found to increase systematically with increasing kinetic energy of the molecular beam. The improvements are more important on HMDS- and OTS-treated surfaces than on bare SiO₂. Tapping mode atomic force microscopy images reveal that pentacene thin films deposited at high kinetic energy form with significantly larger grains—independent of surface treatment—than films deposited using low-energy beams.     

Influence of intramolecular vibrations in charge redistribution at the pentacene-graphite interface

We have investigated the relation between the intramolecular vibrational modes of pentacene and the charge redistribution at the pentacene-graphite interface by using high-resolution electron-energy-loss-spectroscopy. The three main vibrational peaks shift to lower energies as the pentacene film thickness decreases. In order to discuss this energy shift, we have calculated the vibrational energies of a free pentacene molecule by changing its charge state. We have also calculated the vibrational energies of a pentacene molecule adsorbed on a graphite sheet by changing the pentacene-graphite distance. Taking the experimental and calculation results into account, we conclude that the observed energy shifts result from an intramolecular charge redistribution. The present results indicate that the effect of an intramolecular charge redistribution is essential to discuss the origin of an energy shift observed in a vibrational study of an organic molecule/substrate interface.     

The chemisorption of pentacene on Si(0 0 1)-2 × 1

Adsorption structures of the pentacene (C₂₂H₁₄) molecule on the clean Si(0 0 1)-2 × 1 surface were investigated by scanning tunneling microscopy (STM) in conjunction with density functional theory calculations and STM image simulations. The pentacene molecules were found to adsorb on four major sites and four minor sites. The adsorption structures of the pentacene molecules at the four major sites were determined by comparison between the experimental and the simulated STM images. Three out of the four theoretically identified adsorption structures are different from the previously proposed adsorption structures. They involve six to eight Si-C covalent chemical bonds. The adsorption energies of the major four structures are calculated to be in the range 67-128 kcal/mol. It was also found that the pentacene molecule hardly hopped on the surface when applying pulse bias voltages on the molecule, but was mostly decomposed.     

Role of surface electronic structure in thin film molecular ordering

We show that the orientation of pentacene molecules is controlled by the electronic structure of the surface on which they are deposited. We suggest that the near-Fermi level density of states above the surface controls the interaction of the substrate with the pentacene pi orbitals. A reduction of this density as compared to noble metals, realized in semimetallic Bi(001) and Si(111)(5 x 2)Au surfaces, results in pentacene standing up. Interestingly, pentacene grown on Bi(001) is highly ordered, yielding the first vertically oriented epitaxial pentacene thin films observed to date.     

The effect of oxygen exposure on pentacene electronic structure

We use ultraviolet photoelectron spectroscopy to investigate the effect of oxygen and air exposure on the electronic structure of pentacene single crystals and thin films. It is found that O₂ and water do not react noticeably with pentacene, whereas singlet oxygen/ozone readily oxidize the organic compound. Also, we obtain no evidence for considerable p-type doping of pentacene by O₂ at low pressure. However, oxygen exposure lowers the hole injection barrier at the interface between Au and pentacene by 0.25 eV, presumably due to a modification of the Au surface properties.     

Exploring the magnetic and organic microstructures with photoemission electron microscope

We present photoemission electron microscopy (PEEM) studies on geometrically constrained ferromagnetic, organic, and organics–ferromagnet hybrid structures. Powered by an elliptically polarized undulator, the PEEM at Taiwan Light Source (TLS) is capable of recording polarization enhanced X-ray images and has been employed to examine the domain configurations in a lithographically patterned permalloy film as well as the orientations of pentacene molecules adsorbed on self-assembled monolayers (SAMs) modified gold surfaces. In addition, magnetic images acquired on cobalt/pentacene and pentacene/cobalt bilayers reveal that in hybrid structures the order of thin film deposition can lead to distinct domain configurations. Spectroscopic evidence further suggests that there is significant orbital hybridization at the interface where metallic cobalt was deposited directly on organic pentacene.     

Solid state solvation in amorphous organic thin films

The photoluminescence (PL) of the red laser dye DCM2, doped into blended thin films of polystyrene (PS) and the polar small molecule camphoric anhydride (CA), redshifts as the CA concentration increases. The DCM2 PL peaks at 2.20 eV (lambda=563 nm) for pure PS films and shifts to 2.05 eV (lambda=605 nm) for films with 24.5% CA (by mass). The capacitively measured electronic permittivity also increases from epsilon=2.4 to epsilon=5.6 with CA concentration. These results are consistent with the theory of solvatochromism developed for organic molecules in liquid solvents. To our knowledge, this work is the first application of a quantitative theory of solvation to organic molecules in amorphous thin films with continuously controllable permittivity, and demonstrates that "solid state solvation" can be used to predictably tune exciton energies in organic thin film structures.     

Enhanced electrical properties of pentacene-based organic thin-film transistors by modifying the gate insulator surface

A reliable surface treatment for the pentacene/gate dielectric interface was developed to enhance the electrical transport properties of organic thin-film transistors (OTFTs). Plasma-polymerized fluorocarbon (CFx) film was deposited onto the SiO₂ gate dielectric prior to pentacene deposition, resulting in a dramatic increase of the field-effect mobility from 0.015 cm²/(V s) to 0.22 cm²/(V s), and a threshold voltage reduction from −14.0 V to −9.9 V. The observed carrier mobility increase by a factor of 10 in the resulting OTFTs is associated with various growth behaviors of polycrystalline pentacene thin films on different substrates, where a pronounced morphological change occurs in the first few molecular layers but the similar morphologies in the upper layers. The accompanying threshold voltage variation suggests that hole accumulation in the conduction channel-induced weak charge transfer between pentacene and CFx.     

Group 14 Metallafluorenes as Sensitive Luminescent Probes of Surfactants in Aqueous Solution

Journal of Fluorescence - Sila- and germafluorenes containing alkynyl(aryl) substituents at the 2,7- position are strongly emissive with high quantum yields in organic solvents. Provided they are...     

Surface morphology characterization of pentacene thin film and its substrate with under-layers by power spectral density using fast Fourier transform algorithms

Surface morphology of pentacene thin films and their substrates with under-layers is characterized by using atomic force microscopy (AFM). The power values of power spectral density (PSD) for the AFM digital data were determined by the fast Fourier transform (FFT) algorithms instead of the root-mean-square (rms) and peak-to-valley value. The PSD plots of pentacene films on glass substrate are successfully approximated by the k-correlation model. The pentacene film growth is interpreted the intermediation of the bulk and surface diffusion by parameter C of k-correlation model. The PSD plots of pentacene film on Au under-layer is approximated by using the linear continuum model (LCM) instead of the combination model of the k-correlation model and Gaussian function. The PSD plots of SiO₂ layer on Au under-layer as a gate insulator on a gate electrode of organic thin film transistors (OTFTs) have three power values of PSD. It is interpreted that the specific three PSD power values are caused by the planarization of the smooth SiO₂ layer to rough Au under-layer.     

Electron-phonon coupling spectrum in photodoped pentacene crystals

The coupling between conduction charges and the vibrational modes of the molecular lattice plays a defining role in the transport characteristics of organic semiconductors. Using electron tunneling spectroscopy, we obtain the electron--optical-phonon coupling spectrum in photodoped pentacene crystals at energies <30 meV. Comparison of the tunneling spectrum to infrared absorption data on the optical phonon density of states yields the energy dependence of the electron-phonon scattering matrix element. The integrated spectral weight of the electron-phonon coupling shows that superconductivity in pentacene is likely of electron-phonon origin.     

N-doping of pentacene by decamethylcobaltocene

We demonstrate n-type doping of pentacene with the powerful reducing molecule decamethylcobaltocene (CoCp₂^*). Characterization of pentacene films deposited in a background pressure of CoCp₂^* by X-ray photoemission spectroscopy and Rutherford backscattering confirm that the concentration of incorporated donor molecules can be controlled to a level as high as 1%. Ultraviolet photoemission spectroscopy show Fermi level (E _F) shifts toward unoccupied pentacene states, indicative of an increase in the electron concentration. A 1% donor incorporation level brings E _F to 0.6 eV below the pentacene lowest unoccupied molecular orbital. The corresponding electron density of ∼10¹⁸ cm⁻³ is confirmed by capacitance–voltage measurements on a metal–pentacene–oxide–silicon structure. The demonstration of n-doping suggests applications of CoCp₂^* to pentacene contacts or channel regions of pentacene OTFTs.     

Estimation of Ground-State and Singlet Excited-State Dipole Moments of Substituted Schiff Bases Containing Oxazolidin-2-one Moiety through Solvatochromic Methods

Absorption and fluorescence studies on novel Schiff bases (E)-4-(4-(4-nitro benzylideneamino)benzyl)oxazolidin-2-one (NBOA) and (E)-4-(4-(4-chlorobenzylidene amino)benzyl)oxazolidin-2-one (CBOA) were recorded in a series of twelve solvents upon increasing polarity at room temperature. Large Stokes shift indicates bathochromic fluorescence band for both the molecules. The photoluminescence properties of Schiff bases containing electron withdrawing and donating substituents were analyzed. Intramolecular charge transfer behavior can be studied based on the influence of different substituents in Schiff bases. Changes in position and intensity of absorption and fluorescence spectra are responsible for the stabilization of singlet excited-states of Schiff base molecules with different substituents, in polar solvents. This is attributed to the Intramolecular charge transfer (ICT) mechanism. In case of electron donating (?Cl) substituent, ICT contributes largely to positive solvatochromism when compared to electron withdrawing (?NO₂) substituent. Ground-state and singlet excited-state dipole moments of NBOA and CBOA were calculated experimentally using solvent polarity function approaches given by Lippert–Mataga, Bakhshiev, Kawskii-Chamma-Viallet and Reichardt. Due to considerable π- electron density redistribution, singlet excited-state dipole moment was found to be greater than ground-state dipole moment. Ground-state dipole moment value which was determined by quantum chemical method was used to estimate excited-state dipole moment using solvatochromic correlations. Kamlet-Abboud-Taft and Catalan multiple linear regression approaches were used to study non-specific solute-solvent interaction and hydrogen bonding interactions in detail. Optimized geometry and HOMO-LUMO energies of NBOA and CBOA have been determined by DFT and TD-DFT/PCM (B3LYP/6-311G (d, p)). Mulliken charges and molecular electrostatic potential have also been evaluated from DFT calculations.     

The interaction of oxygen and ozone with pentacene

We use ultraviolet photoemission spectroscopy (UPS) to investigate the effect of oxygen and air exposure on pentacene thin film electronic structure. It is found that O₂ and water do not react noticeably with pentacene on the timescale of several hours, whereas a mixture of oxygen atoms, singlet oxygen and ozone readily oxidizes the organic compound. We obtain no evidence for irreversible intercalation of oxygen into pentacene or considerable p-type doping after re-evacuation. Infrared spectroscopy and atomic force microscopy are used to study the oxidation of pentacene thin films. Our data suggest the oxidation of pentacene with reactive oxygen species to yield highly volatile reaction products as evidenced by significant mass-losses of the films.     

Effect of modifying a methyl siloxane-based dielectric by a polymer thin film for pentacene thin-film transistors

We report on the fabrication of pentacene thin-film transistors (TFTs) utilizing a spun methyl siloxane-based spin-on-glass (SOG) dielectric and show that these devices can give a similar electrical performance as achieved by using pentacene TFTs with a silicon dioxide (SiO₂) dielectric. To improve the electrical performance of pentacene TFTs with the SOG dielectric, we employed a hybrid dielectric of an SOG/cross-linked poly-4-vinylphenol (PVP) polymer. The PVP film was deposited onto the spun SOG dielectric prior to pentacene evaporation, resulting in an improvement of the saturation field effect mobility (μ_sat) from 0.01 cm²/(V s) to 0.76 cm²/(V s). The good surface morphology and the matching surface energy of the SOG dielectric that was modified with the polymer thin film allow the optimized growth of crystalline pentacene domains whose nuclei are embedded in an amorphous phase.     

Tuning the work function of graphene with the adsorbed organic molecules: first-principles calculations

We have investigated the energetics and work function (WF) of graphene (GR) with depositing pentacene (C₂₂H₁₄, PEN) and perfluorinated pentacene (C₂₂F₁₄, PFP) using the electronic structure calculations based on the density functional theory with van der Waals (vdW) corrections. Both molecules are adsorbed on GR in flat-laying form with the height of 3.2 Å through vdW interaction, and no explicit exchange of electrons was found between GR and adsorbed molecules. However, we found charge redistribution in the surface to interface region and this brings about the vacuum level shifts, Δ = ?0.06 eV for PEN and Δ = +0.10 eV for PFP, demonstrating that the work function of GR can be tuned by the physisorption of organic molecules.     

First-principles study of the pentacene/Cu(1 1 1) interface: Adsorption states and vacuum level shifts

We have studied the interaction of pentacene with a Cu(1 1 1) surface using density functional theory (DFT) within a generalized gradient approximation (GGA) and the van der Waals density functional [vdW-DF, M. Dion, H. Rydberg, E. Schröder, D.C. Langreth, B.I. Lundqvist, Phys. Rev. Lett. 92 (2004) 246401]. The adsorption energy is accurately predicted by vdW-DF, while the equilibrium distances between pentacene and the metal substrate (Z_C) are overestimated by both GGA and vdW-DF. The work function changes depend significantly on Z_C. The experimental work function change can be successfully reproduced by GGA if the experimentally reported adsorption geometry is used, whereas the magnitude of the work function change is underestimated if calculated adsorption geometries are applied. We examined the IDIS model [H. Vázquez, R. Qszwaldowski, P. Pou, J. Ortega, R. Pérez, F. Flores, A. Kahn, Europhys. Lett. 65 (2004) 802] to compare it with the GGA results. The interface dipoles estimated by the IDIS model fairly agree with the GGA results, provided that the adsorption distance is large. On the other hand, they tend to deviate from the GGA results as the adsorption distance becomes smaller, where back donation from the metal surface to the adsorbate occurs. Our analysis reveals that at experimentally reported metal–organic distance, back donation is significant enough to induce polarization of pentacene molecules perpendicular to the surface, which leads to a reduction of the work function. Thus, at the experimentally reported metal–organic distance, the work function change estimated by a simple IDIS model deviates from that calculated by self-consistent GGA calculations. We also found that at the experimentally reported metal–organic distance, the transferred electrons create weak chemical bonds between pentacene and the Cu(1 1 1) surface, illustrating the reactive nature of pentacene.     

Synthesis, characterization of the pentacene and fabrication of pentacene field-effect transistors

A comprehensive understanding of the organic semiconductor material pentacene is meaningful for organic field-effect transistors (OFETs). Thin films of pentacene are the most mobile molecular films known to date. This paper reported that the pentacene sample was successfully synthesized. The purity of pentacene is up to 95\%. The results of a joint experimental investigation based on a combination of infrared absorption spectra, mass spectra (MS), element analysis, x-ray diffraction (XRD) and atom force microscopy (AFM). The authors fabricated OFET with the synthesized pentacene. Its field effect mobility is about 1.23\,cm$^2$/(V$\cdot$s) and on--off ratio is above 10$^{6}$.