Photodesorption from ultra-thin metal films – a comparison of SO<Subscript>2</Subscript> and NO<Subscript>2</Subscript> on Ag/Si(100)

The photochemistry of SO₂ on thin epitaxial Ag films (5–60 nm) deposited on Si(100) has been studied using laser light with the wavelengths of 266, 355, and 532 nm. SO₂ desorbs with cross sections of 1.7×10^-19,1.7×10^-20 and 2.9×10^-21 cm², respectively. The average translation energy, 〈E_trans/2k〉, is 440 K for 266 and 355 nm light, and 270 K for 532 nm light. Cross sections for a 60 nm thick Ag film are practically identical to the ones for Ag(111) as the substrate. An increase by a factor of ∼3.5 is observed when the film thickness is reduced to 5 nm for 266 and 355 nm light. No significant change is observed for 532 nm excitation. The film thickness has no significant influence on the translational energy of the photodesorbed molecules. The data are discussed in connection with the change of absorptivity of the metal film–semiconductor system. A model is put forward which takes into account the light absorption in the Si substrate and the reduced relaxation of excited electrons in Si. Modelling indicates that electrons excited in the Si substrate with energies and parallel momenta not allowed in Ag contribute to the surface chemistry after crossing the gap in the projected band structure of Ag(111). PACS 82.45.MP; 73.63.-b; 82.50.Bc     

Structuring of aluminum films by laser-induced local oxidation in water

A simple method for patterning of thin (15–650 nm) aluminum films on glass substrates by direct, low-power, laser-thermal oxidation in water under common laboratory conditions is demonstrated. Local heating of the metal film enhances the formation of aluminum oxide (hydrargillite, Al₂O₃–3H₂O) and provokes breakdown of the passivation layer followed by local corrosion at temperatures close to the boiling point of water. Moving the focus of an Ar-ion laser (λ=488 nm) over the aluminum film with a speed of several μm/s yields grooves flanked by hydrargillite. Upon through oxidation of the metal these structures act as electrically insulating domains. Depending on the film thickness, the minimum width of the line structures measures between 266 nm and 600 nm. The required laser irradiation power ranges from 1.7 mW to 30 mW. It is found that the photo-thermal oxidation process allows for writing of two-dimensional electrode patterns. Received: 16 July 2001 / Accepted: 23 July 2001 / Published online: 2 October 2001     

Laser ablation and deposition of wide bandgap semiconductors: plasma and nanostructure of deposits diagnosis

Nanostructured CdS and ZnS films on Si (100) substrates were obtained by nanosecond pulsed laser deposition at the wavelengths of 266 and 532 nm. The effect of laser irradiation wavelength on the surface structure and crystallinity of deposits was characterized, together with the composition, expansion dynamics and thermodynamic parameters of the ablation plume. Deposits were analyzed by environmental scanning electron microscopy, atomic force microscopy and X-ray diffraction, while in situ monitoring of the plume was carried out with spectral, temporal and spatial resolution by optical emission spectroscopy. The deposits consist of 25–50 nm nanoparticle assembled films but ablation in the visible results in larger aggregates (150 nm) over imposed on the film surface. The aggregate free films grown at 266 nm on heated substrates are thicker than those grown at room temperature and in the former case they reveal a crystalline structure congruent with that of the initial target material. The observed trends are discussed in reference to the light absorption step, the plasma composition and the nucleation processes occurring on the substrate.     

Molecular dynamics in thin films of isotactic poly(methyl methacrylate)

The molecular dynamics in thin films (18 nm-137 nm) of isotactic poly(methyl methacrylate) (i-PMMA) of two molecular weights embedded between aluminium electrodes are measured by means of dielectric spectroscopy in the frequency range from 50 mHz to 10 MHz at temperatures between 273 K and 392 K. The observed dynamics is characterized by two relaxation processes: the dynamic glass transition (α-relaxation) and a (local) secondary β-relaxation. While the latter does not depend on the dimensions of the sample, the dynamic glass transition becomes faster (≤2 decades) with decreasing film thickness. This results in a shift of the glass transition temperature T _g to lower values compared to the bulk. With decreasing film thickness a broadening of the relaxation time distribution and a decrease of the dielectric strength is observed for the α-relaxation. This enables to deduce a model based on immobilized boundary layers and on a region displaying a dynamics faster than in the bulk. Additionally, T _g was determined by temperature-dependent ellipsometric measurements of the thickness of films prepared on silica. These measurements yield a gradual increase of T _g with decreasing film thickness. The findings concerning the different thickness dependences of T _g are explained by changes of the interaction between the polymer and the substrates. A quantitative analysis of the T _g shifts incorporates recently developed models to describe the glass transition in thin polymer films. Received 12 August 2001 and Received in final form 16 November 2001     

Laser-induced periodic surface structures on different poly-carbonate films

Laser-induced periodic surface structures (LIPSS) were generated on oriented and amorphous thick, as well as on spin-coated thin, poly-carbonate films by polarized ArF excimer laser light. The influence of the film structure and thickness on the LIPSS formation was demonstrated. Below a critical thickness of the spin-coated films the line-shaped structures transformed into droplets. This droplet formation was explained by the laser-induced melting across the whole film thickness and subsequent de-wetting on the substrate. The thickness of the layer melted by laser illumination was computed by a heat-conduction model. Very good agreement with the critical thickness for spin-coated films was found. The original polymer film structure influences the index of refraction of the thin upper layer modified by the laser treatment, as was proven by the dependence of the structure’s period on the angle of incidence both for ‘s’- and ‘p’-polarized beams. The effect of the original surface roughness – grains in thick films or holes in thin films – was studied using atomic force microscopy. It was shown that the oblique incidence of ‘s’-polarized beams results in an intensity confinement in the direction of the forward scattering and in asymmetrical interference pattern formation around these irregularities. A new, two-dimensional grating-like structure was generated on spin-coated films. These gratings might be used as a special kind of mask. Received: 10 July 2001 / Accepted: 23 July 2001 / Published online: 30 August 2001     

Growth and characteristics of reactive pulsed laser deposited molybdenum trioxide thin films

Molybdenum trioxide thin films were prepared by reactive pulsed laser deposition on Corning 7059 glass substrates. The influence of oxygen partial pressure and deposition temperature on the structure, surface morphology and optical properties of these films was studied to understand the growth mechanism of MoO₃ thin films. The films formed at 473 K in an oxygen partial pressure of 100 mTorr exhibited predominantly a (0k0) orientation, corresponding to an orthorhombic layered structure of α-MoO₃. The evaluated optical band gap of the films was 3.24 eV. The crystallite size increased with increase of deposition temperature. The films formed at an oxygen partial pressure of pO₂=100 mTorr and at a deposition temperature greater than 700 K exhibited both (0k0) and (0kl) orientations, representing α-β mixed phases of MoO₃. The films formed at an oxygen partial pressure less than 100 mTorr were found to be sub-stoichiometric with α-β mixed phases. The investigation revealed the growth of polycrystalline and single-phase orthorhombic-layered-structure α-MoO₃ thin films with composition nearly approaching the nominal stoichiometry at moderate substrate temperatures in an oxygen partial pressure of 100 mTorr. Received: 9 April 2001 / Accepted: 6 August 2001 / Published online: 17 October 2001     

Optical properties of new indotricarbocyanine dye as a limiter of laser radiation power

We present results of experimental and theoretical studies of the optical characteristics of a new indotricarbocyanine dye that is capable of effectively limiting the power of laser radiation in the visible spectral range. The spectral-luminescent and energy characteristics of the dye molecules and their absorption spectra from the excited state with nanosecond resolution are investigated experimentally. Quantum-chemical methods are used to calculate electronic absorption spectra from the ground (S₀ → S_n) and excited (S₁ → S_n) states and to determine the nature of electronic states of the molecule and the rate constants of intramolecular photophysical processes. The results of the theoretical research agree with experimental data. It is shown that the investigated dye has singlet-singlet absorption at 400–600 nm. Nonlinear absorption of the dye upon excitation by radiation of the second harmonic of a Nd:YAG laser is studied by z-scanning with an open diaphragm. The ratio of dye absorption cross sections from the excited and ground states at 532 nm is determined in the framework of a three-level model. The results are compared with those for previously studied compounds. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 4, pp. 473–480, July–August, 2007.     

Nonlinear thickness dependence of two-photon absorptance in Al2O3 films

Linear and nonlinear absorptance in Al₂O₃ films of different optical thicknesses are investigated using an ArF laser calorimeter. While the linear absorptance at 193 nm shows the expected linear increase, nonlinear absorptance increases quadratically with increasing film thickness. Thus, it cannot be described by a constant nonlinear absorption coefficient β. The experimental findings are explained by a simple phenomenological approach using excited states with a finite interaction length longer than the actual film thickness. a new material constant Γ is introduced, which describes the nonlinear absorptance behavior correctly. Received: 19 May 2000 / Accepted: 22 May 2000 / Published online: 13 July 2000     

Resonant infrared pulsed laser deposition of thin biodegradable polymer films

Thin films of the biodegradable polymer poly(DL-lactide-co-glycolide) (PLGA) were deposited using resonant infrared pulsed laser deposition (RIR-PLD). The output of a free-electron laser was focused onto a solid target of the polymer, and the films were deposited using 2.90 (resonant with O-H stretch) and 3.40 (C-H) μm light at macropulse fluences of 7.8 and 6.7 J/cm², respectively. Under these conditions, a 0.5-μm thick film can be grown in less than 5 min. Film structure was determined from infrared absorbance measurements and gel permeation chromatography (GPC). While the infrared absorbance spectrum of the films is nearly identical with that of the native polymer, the average molecular weight of the films is a little less than half that of the starting material. Potential strategies for defeating this mass change are discussed. Received: 22 August 2001 / Accepted: 23 August 2001 / Published online: 17 October 2001     

Growth of completely (110)-oriented Pt film on Si (100) by using MgO as a buffer by pulsed laser deposition

(110)-textured MgO films were grown on Si (100) with etching and without etching by pulsed laser deposition. The deposited MgO films were shown to be droplets-free. The MgO film was used as a buffer layer to further grow Pt film on Si (100). A completely (110)-oriented Pt film was obtained on such a buffer layer and its surface is very smooth with a roughness of about 7.5 nm over 5×5 μm. This can be used as a new oriented Pt electrode on silicon for devices. Received: 23 January 2001 / Accepted: 27 April 2001 / Published online: 27 June 2001     

A microchip-laser-pumped DFB-polymer-dye laser

A miniaturized, high repetition rate, picosecond all solid state photo-induced distributed feedback (DFB) polymer-dye laser is described by applying a passively Q-switched and frequency-doubled Cr⁴⁺:Nd³⁺:YAG-microchip laser (pulse width Δτ=540 ps, repetition rate ν=3 kHz, pump energy E_pump=0.15 μJ) as a pump source. A poly-methylmethacrylate film doped with rhodamine B dye serves as active medium. The DFB-laser pulses are temporally and spectrally characterized, and the stability of the thin polymer/dye film at high repetition rates is analyzed. The shortest DFB-laser pulses obtained have a duration of 11 ps. After the emission of 350000 pulses the intensity of the DFB-laser output has decreased by a factor of two and the pulse duration has increased by a factor of 1.2. For single DFB-laser pulses of 20-ps duration the spectral bandwidth is measured to be Δλ=0.03 nm, which is only 0.005 nm above the calculated Fourier limit assuming a Gaussian profile for the temporal shape of the pulses. Coarse wavelength tuning of the DFB laser between 590 and 619 nm is done by turning the prism. Additionally, a fine tuning of the DFB-polymer-laser wavelength is achieved by changing the temperature of the polymer/dye layer (=-0.05 nm/°C) in the range from 20 to 40 °C. Received: 1 March 2001 / Revised version: 23 May 2001 / Published online: 18 July 2001     

Structural changes of thin films from recombinant spider silk proteins upon post-treatment

Engineering of spider silk proteins offers the possibility to control their molecular sequence and thus their material properties. Spin coating was used to prepare films of engineered spider silk protein derived from the garden spider’s (Araneus diadematus) dragline silk protein ADF-4. A conformational transition from α-helix to β-sheet-rich structures upon methanol treatment of the films was detected by external reflection IR spectroscopy. We present direct evidence for this structural transformation using grazing-incidence X-ray diffraction (GIXRD) and small-angle scattering (GISAXS). The protein film structure after the methanol treatment consists mainly of β-sheet polyalanine crystals dispersed in an amorphous protein matrix. The GIXRD intensity profiles show Bragg peaks from β-sheet polyalanine crystallites having an average size of 7.5 nm. The non-uniform and large crystal size distributions within the film were explained based on the protein composition. The effect of the chemical nature of the interface on the protein film structure was investigated as well. PACS 87.15.-v; 68.55.-a; 61.10.Eq     

Electrically switchable reflection holograms formed using two-photon photopolymerization

Two-photon holographic photopolymerization was used to form switchable Bragg gratings composed of layers of phase-separated liquid-crystal (LC) domains interspersed with cured, crosslinked polymer. These holographic polymer-dispersed liquid crystals form a periodic structure which diffracts red light due to nanostructured planes ∼250 nm in spacing. These structures were formed by interfering two 90-fs pulses coherently upon a reactive syrup consisting of acrylate monomer, liquid crystal, and a two-photon dye. The large two-photon cross-section allows excitation of the two-photon dye that results in electron transfer between this dye and the monomer. Diffraction efficiencies of approximately 10% were obtained, which can be modulated using an electric field applied across the film. Switching speeds below 1 ms were observed due in part to the small size of the LC domains. Received: 10 April 2001 / Accepted: 1 July 2001 / Published online: 2 October 2001     

Z-scan determination of third-order nonlinear optical nonlinearity of three azobenzenes doped polymer films

The third-order nonlinear response of methyl red (MR), methyl orange (MO) and p-dimethylamino benzene arsenic acid (PDBAA) doped polyvinyl alcohol (PVA) films are studied by using the Z-scan technique under 532 nm and 1064 nm excitations. The larger third-order nonlinear refractive index of PDBAA doped PVA film is discussed in terms of fall of the energy level in excited state for the effect of heavy-atom arsenic. At the end, the second hyperpolarizabilities of the films are estimated and the figures of merit are evaluated for their value of applications in ultra-fast all-optical devices.     

Deposition and characterization of ITO films produced by laser ablation at 355 nm

Indium tin oxide (ITO) films have been deposited by pulsed laser deposition (PLD) at 355 nm. Even though the absorption of laser light at the wavelength 355 nm is much smaller than that of the standard excimer lasers for PLD at 248 nm and 193 nm, high-quality films can be produced. At high fluence and at high substrate temperatures, the specific resistivity of the films, 2–3×10^-4 Ω cm, is comparable to values obtained with excimer lasers, whereas the resistivities obtained at room temperature are somewhat higher than those of films produced by excimer lasers. The transmission coefficient of visible light, about 0.9, is also comparable to values for films deposited by excimer lasers. The crystalline structure of films produced at 355 nm is similar to that of samples produced by these lasers. Received: 16 January 2001 / Accepted: 24 July 2001 / Published online: 17 October 2001     

Nonlinear optical properties of an azo-based dye irradiated by picosecond and nanosecond laser pulses

The nonlinear optical properties of an azo-based dye were investigated using Z-scan technique employing 38 ps pulses at 532 and 1064 nm, and 6 ns laser pulses at 532 nm. Large nonlinear absorption and nonlinear refraction were observed at both ps and ns 532 nm in the azoic dye. When excited at ps 1064 nm, this dye displayed a large two-photon absorption cross-section (σ₂=1810 GM). Meanwhile, the optical nonlinearity mechanism was discussed in terms of molecular structure, excitation wavelength, and pulse width.     

Laser removal of copper particles from silicon wafers using UV, visible and IR radiation

Laser removal of small copper particles from silicon wafer surfaces was carried out using Nd:YAG laser radiation from near-infrared (1064 nm) through visible (532 nm) to ultraviolet (266 nm). It has been found that both 266 nm and 532 nm are successful in removing the particles from the surface whereas 1064 nm was shown to be ineffective in the removal of particles. The damage-threshold laser fluence at 266 nm was much higher than other wavelengths which provides a much wider regime for safe cleaning of the surface without causing any substrate damage. The cleaning efficiency was increased with a shorter wavelength. The effect of laser wavelength in the removal process is discussed by considering the adhesion force of the particle on the surface and the laser-induced cleaning forces for the three wavelengths. Received: 31 May 2000 / Accepted: 14 July 2000 / Published online: 20 June 2001     

Growth of thin, crystalline oxide, nitride, and oxynitride films on NiAl and CoGa surfaces

At 300 K, an amorphous Al-oxide film is formed on NiAl(001) upon oxygen adsorption. Annealing of the oxygen-saturated NiAl(001) surface to 1200 K leads to the formation of thin well-ordered θ-Al₂O₃ films. At 300 K, and low-exposure oxygen atoms are chemisorbed on CoGa(001) on defects and on step edges of the terraces. For higher exposure up to saturation, the adsorption of oxygen leads to the formation of an amorphous Ga-oxide film. The EEL spectrum of the amorphous film exhibits two losses at ≈400 and 690 cm^-1. After annealing the amorphous Ga-oxide films to 550 K thin, well-ordered β-Ga₂O₃ films are formed on top of the CoGa(001) surface. The EEL spectrum of the β-Ga₂O₃ films show strong Fuchs-Kliewer (FK) modes at 305, 455, 645, and 785 cm^-1. The β-Ga₂O₃ films are well ordered and show (2×1) LEED pattern with two domains, oriented perpendicular to each other. The STM study confirms the two domains structure and allows the determination of the two-dimensional lattice parameters of β-Ga₂O₃. The vibrational properties and the structure of β-Ga₂O₃ on CoGa(001) and θ-Al₂O₃ on NiAl(001) are very similar. Ammonia adsorption at 80 K on NiAl(111) and NiAl(001) and subsequent thermal decomposition at elevated temperatures leads to the formation of AlN. Well-ordered and homogeneous AlN thin films can be prepared by several cycles of ammonia adsorption and annealing to 1250 K. The films render a distinct LEED pattern with hexagonal [AlN/NiAl(111)] or pseudo-twelve-fold [AlN/NiAl(001)] symmetry. The lattice constant of the grown AlN film is determined to be a_AlN= 3.11 Å. EEL spectra of AlN films show a FK phonon at 865 cm^-1. The electronic gap is determined to be E_g= 6.1±0.2 eV. GaN films are prepared by using the same procedure on the (001) and (111) surfaces of CoGa. The films are characterized by a FK phonon at 695 cm^-1 and an electronic band gap E_g= 3.5±0.2 eV. NO adsorption at 75 K on NiAl(001) and subsequent annealing to 1200 K leads to the formation of aluminium oxynitride (AlON). An oxygen to nitrogen atomic ratio of ≈2:1 was estimated from the analysis of AES spectra. The AlON films shows a distinct (2×1) LEED pattern and the EEL spectrum exhibits characteristic Fuchs-Kliewer modes. The energy gap is determined to be E_g= 6.6±0.2 eV. The structure of the AlON film is derived from that of θ-Al₂O₃ formed on NiAl(001). Received: 21 March 1997/Accepted: 12 August 1997     

Photophysical and laser characteristics of pyrromethene 567 dye: Experimental and theoretical studies

Narrow-band laser performance of alcohol solutions of pyrromethene 567 (PM567) and rhodamine 6G (RH6G) dye was investigated using a home-made GIG-configured dye laser, excited by the second-harmonic radiation (at 532 nm) of a pulsed Nd:YAG laser. Higher laser efficiency was observed with PM567 dye (∼23% peak) in comparison to the commonly used RH6G dye (16.5%), in spite of much lower fluorescence quantum efficiency of the PM567 (0.83) vis-à-vis RH6G (0.98) dye solutions in ethanol. First principle-based electronic structure calculations were performed on PM567 dye in the ground (S ₀) and excited states (S ₁) using density functional theory to elucidate the structure and photophysical properties of the dye.     

Langmuir–Blodgett films and optical second-harmonic generation of a crowned [60]fulleropyrrolidine

The Langmuir and Langmuir–Blodgett (LB) films of a novel crowned [60]fullero-pyrrolidine (CFP) were produced in different conditions. Macroscopic second-harmonic generation of the LB film was investigated by means of AM1 Hamiltonian as well as experiments. The monolayer LB film displayed a periodic fringe pattern. A linear dependence of second-harmonic intensity on the number of layers was observed. The second-order molecular susceptibility χ⁽²⁾ and hyperpolarizability β were evaluated to be 3.2×10⁻⁸ and 8.3×10⁻²⁹ esu. Received: 21 October 1999 / Revised version: 30 March 2000 / Published online: 2 August 2000