Microdot pattern of multiple organic molecules prepared by laser photopolymerization process with a nanosecond pulsed laser

A microdot pattern of multiple organic molecules was prepared. Fluorescent molecules, which absorb visible light, were added to a commercial ultraviolet photopolymerization polymer solution and the polymer solution was polymerized by irradiating with nanosecond pulsed visible laser light. The size and the shape of the polymerized dots differed with the irradiation condition and the kind of the added molecules. Based on these results, a microdot pattern of multiple organic molecules was prepared by repeating a micropatterning process with the molecules. PACS 82.50.Hp; 81.65.Cf; 81.05.Lg     

Laser-induced implantation of organic molecules into sub-micrometer regions of polymer surfaces

Organic molecules adhered to the point of a micropipette were transferred onto the surface of a polymer film by pulsed laser light guided through a quartz optical fiber which was inserted into the micropipette. Controlled by a high-resolution piezoelectric driver designed for scanning probe microscopy, the distance between the micropipette point and the polymer surface was kept to a few tens of nm. After laser irradiation, the deposited molecules on the polymer surface were examined with optical transmission, fluorescence, atomic force, and scanning near-field optical microscopy. It was demonstrated that various kinds of organic molecules can be implanted into sub-micrometer regions at the surfaces of polymer films without their decomposition. The hypothetical mechanism of the molecular transfer is discussed in relation to the morphology of crystalline molecules adhered at the micropipette apertures.     

Nonlinear ionization of organic molecules in high intensity laser fields

We use a series of 23 organic molecules to study ionization of complex media caused by their interaction with intense 40 fs, 0.8 &mgr;m pulses. All molecules reach saturated ionization at higher intensities than would be expected for atoms of the same ionization potential, reminiscent to what has been reported for dielectric breakdown with femtosecond pulses. Dependence of the ionization rate on the alignment of the molecule with the laser field is ruled out as the cause of the high saturation intensities. All molecules allow a significant range of intensities between the region of approximately 100% ionization and before the second and subsequent electrons are removed.     

Polarization characteristics of stimulated emission of organic molecules when excited by intense XeCl laser radiation

We study the influence of the molecular structure, medium, and exciting-radiation parameters on the polarization, energy, and spectral characteristics of the emission of laser-active media based on the dicarboxylic derivative of p-terphenyl, rhodamine 101, and phenalemine 512. We found that the polarization of the stimulated emission of molecules when strongly excited under the conditions studied significantly depends on their structure, the pumping mode, the intensity and polarization of the exciting radiation, the shape and dimensions of the excited volume, and the phase state of the medium.     

Stepwise photoionization of complex organic molecules in the gas phase induced by UV laser radiation

We measured the photoionization cross-sections of anthracene, 1,2-benzanthracene,p-terphenyl, and 2,5-diphenylfuran molecules excited to the singlet and triplet electronic states intermediate in the stepwise two-photon ionization process at 266 nm (all compounds) and at 355, 391 and 417 nm (anthracene).     

Two-color laser manipulation of single organic molecules based on nonlinear optical response

We theoretically propose two-color laser manipulation with greatly improved efficiency to mechanically manipulate single organic molecules. The present method is based on the nonlinear resonant laser manipulation proposed in a recent study. In the first part, we describe a method to trap single organic molecules that can be more effective than ever before utilizing two-color beams. In the second part, we demonstrate the possibility to selectively “pull” single organic molecules with a particular type of electronic-level scheme by using single-side illumination of traveling light.     

Alignment of molecules by strong laser pulses

We review how moderately intense laser fields offer an approach to alignment of molecules [1]. In particular, molecules can be aligned along a given space fixed axis, forced to a plane, or their rotations about all three possible axes can be eliminated by choosing a linearly polarized, a circularly polarized, or an elliptically polarized alignment field, respectively. We show how molecules in the gas phase can be aligned by turning on the laser field either slowly (a few nanoseconds) or fast (a few picoseconds) with respect to the rotational period of the molecules. The role of the intensity of the laser field and the rotational temperature of the molecules is discussed. Before concluding we describe how aligned molecules enables control and selectivity in the interaction between polarized light and molecules.Received: 15 November 2002, Published online: 18 March 2003PACS: 33.15.Bh General molecular conformation and symmetry; stereochemistry - 32.80.Lg Mechanical effects of light on atoms, molecules, and ions - 33.80.Gj Diffuse spectra; predissociation, photodissociation - 33.80.Rv Multiphoton ionization and excitation to highly excited states (e.g. Rydberg states) - 34.50.Lf Chemical reactions, energy disposal, and angular distribution, as studied by atomic and molecular beams     

Polymer films filled with organic molecules by CO2 laser evaporation in vacuum

A new p-type of material for organic field-effect transistors (OFETs) is 5,5′-di(9,9′-di-(butyl)-fluorene′)-2,2′-bithiophene (DBFBT). DBFBT films have been prepared by casting, by thermal evaporation in vacuum, and by means of CO₂ laser evaporation. The photon energy from a CO₂ laser is too small to break chemical bonds of the DBFBT molecule, but the heating rate is extremely high. Pressed pellets of powders composed of DBFBT and polychlorotrifluoroethylene (PCTFE) were used as targets for the fabrication of films. These targets were irradiated by a laser beam of 40 W cw-power and 0.5 cm diameter. The deposition rate was 30-50 nm/s. The films have been characterised by optical spectroscopy and by AFM. The structure of DBFBT films produced by casting from solution and thermal deposition is composed of elongated crystals, while the laser deposited layers show cluster structure. By FTIR the films show the absorption band of pure DBFBT, with intensity proportional to the DBFBT concentration in the PCTFE matrix. The absorption bands for a pure DBFBT film, for a film with 22 vol.% and with 34 vol.% of DBFBT in the PCTFE matrix are situated at 274, 298 and 402 nm, where the latter is the most intense one. No significant difference in the band positions of all samples has been found. We concluded that no interaction between chromophore and matrix occurs. The DBFBT molecules in the PCTFE matrix did not oxidize during storage under ambient condition over a period of a year.     

Resonance capture of electrons by electroactive organic molecules

Bound states of electrons with electroactive aromatic molecules, promising for use in molecular electronics, are studied employing electron attachment spectroscopy Anions are produced in the gas phase through the capture of electrons with energies of up to 15 eV by molecules via the resonance mechanism. The possible pathways of fragmentation of molecular anions and the times of electron retention by the test molecules at various incident electron energies are measured. The resonance states identified are interpreted with the help of quantum-chemical calculations. The possibility of applying the results obtained to molecular electronics is discussed.     

Dynamics of molecules excited by infrared laser radiation

The CF₂HCl and CF₂Cl₂ molecules upon multiphoton excitation are investigated by the method of Raman light scattering spectroscopy at frequencies of fundamental transitions. It is demonstrated that essentially nonequilibrium energy distribution of molecules is formed in the process of excitation. Physical parameters characterizing this distribution are determined.     

Stabilization of organic thin film transistors by ion implantation

We report on the effects of low energy ion implantation (N and Ne) in the reduction and control of the degradation of pentacene organic thin film transistors (OTFTs) due to the exposure to atmosphere (i.e. oxygen and water). We have observed that a controlled damage depth distribution preserves the functionality of the devices, even if ion implantation induces significant molecular structure modifications, in particular a combination of dehydrogenation and carbonification effects. No relevant changes in the pentacene thin film thickness have been observed. The two major transport parameters that characterize OTFT performance are the carrier mobility and the threshold voltage. We have monitored the effectiveness of this process in stabilizing the device by monitoring the carrier mobility and the threshold voltage over a long time (over 2000 h). Finally, we have assessed by depth resolved X-ray Photoemission Spectroscopy analyses that, by selectively implanting with ions that can react with the hydrocarbon matrix (e.g. N⁺), it is possible to locally modify the charge distribution within the organic layer.     

Oxidation of organic molecules by photoproduced holes of ZnO

The oxidation by ZnO holes of organic molecules has been examined to develop experimental methods to study such reactions and to identify what components are unstable against oxidation by holes. This is of interest in many systems, such as coatings, where semiconductors and organic components are in contact. Two methods were used that show consistent results. An electrochemical technique with a single crystal ZnO anode was used for quantitative comparisons, and electron spin resonance was used to study more practical powder/vehicle systems. Alcohols and dioxane were shown to be readily oxidized by ZnO holes, whereas acetonitrile, neopentane, and ethyl acetate were oxidation resistant. Some resistance to the photooxidation was provided by recombination centers.     

Micro-patterning for polymer electrolyte fuel cells: Single pulse laser ablation of aluminum films from glassy carbon

Microfuel cells are a possible replacement for batteries as energy sources in portable devices. At PSI a micropolymer electrolyte fuel cell was developed, whose flow fields consist of micro-structured glassy carbon plates. Micro-structuring of glassy carbon is carried out in a multi-step process. A sputtered aluminum mask is selectively removed by single pulse laser ablation from glassy carbon thereby defining micro-channels subsequently etched by reactive ion etching.A pulsed XeCl excimer laser (308 nm) is used for the single pulse patterning of a metal mask on the glassy carbon. The influence of the excimer laser typical pulse to pulse energy fluctuations on the micro-structuring process must be known to minimize defects during RIE etching of the micro-channels. To obtain a better understanding of the processes occurring during ablation, ns-shadowgraphy was performed. The formation of a shockwave was observed, followed by a similar but much slower perturbation, and the subsequent release of fragments. The calculated velocities can be correlated with the energy release during ablation. The post-ablation examination of the samples by profilometry, optical microscopy, SEM and EDX is used to measure the amount of removed material, the quality of the aluminum mask edges and aluminum residues on the glassy carbon surface. Such criteria allow us to classify the laser irradiation as a function of laser fluence: no ablation, partial ablation, complete ablation, and over-ablation.     

Orientation of polar molecules by laser induced adiabatic passage

We show that two overlapping linearly polarized laser pulses of frequencies omega and its second harmonic 2omega can strongly orient linear polar molecules, by adiabatic passage along dressed states. The resulting robust orientation can be interpreted as a laser-induced localization in the effective double well potential created by the fields, which induces a preliminary molecular alignment. The direction of the orientation can be selected by the relative phase of the fields.     

Ultrafast dissociation and electron excitation in polyatomic organic molecules upon multiple IR photon capture

We suggest a model that allows analysis of the photoprocesses in polyatomic organic molecules upon multiple IR photon capture. The dissociation and electron excitation of these molecules is shown to depend resonantly on the photon energy and intensity. The (CH₂)_n substructures of these molecules serve for IR photons as antennas that accumulate energy to values at which dissociation or electron excitation can be triggered. The model is applied to diphenylalkan molecules as an example.     

Chiral recognition of organic molecules by atomic kinks on surfaces

Two distinct non-mirror-symmetric conformations of D- and L-cysteine were found after adsorption on Au(17 11 9)S. This demonstrates chiral heterorecognition, i.e., enantioselectivity of S kinks on vicinal Au(111). The structures as determined by angle scanned x-ray photoelectron diffraction agree well with those from density functional theory calculations. The calculations predict adsorption energies of approximately 2 eV where D-cysteine binds 140 meV stronger than L-cysteine. The classical three point contact model for molecular recognition fails to explain these findings.