Direct observation of laser-induced crystallization of a-C:H films

The post-growth modification of diamond-like amorphous hydrogenated carbon a-C:H films by laser treatment has been studied by transmission electron microscopy and Raman spectroscopy. a-C:H films grown on Si substrates by benzene decomposition in a rf glow discharge were irradiated with 15 ns pulses of a KrF-excimer laser with fluences in the range of E=50–700 mJ/cm². At fluences below 100 mJ/cm² an increase in the number of graphitic clusters and in their ordering was evidenced from Raman spectra, while the film structure remained amorphous according to electron microscopy and electron diffraction observations. At higher fluences the appearance of diamond particles of 2–7 nm size, embedded into the lower crystallized graphitic matrix, was observed and simultaneously a progressive growth of graphite nanocrystals with dimensions from 2 nm to 4 nm was deduced from Raman measurements. The maximum thickness of the crystallized surface layer (400 nm) and the degree of laser annealing are limited by the film ablation which starts at E>250 mJ/cm². The laser-treated areas lose their chemical inertness. In particular, chemical etching in chromium acid becomes possible, which may be used for patterning the highly inert carbon films.     

Ultra fast melting process in femtosecond laser crystallization of thin a-Si layer

In this paper, we investigated the mechanism of crystallization induced by femtosecond laser irradiation for an amorphous Si (a-Si) thin layer on a crystalline Si (c-Si) substrate. The fundamental, SHG, THG wavelength of a Ti:Sapphire laser was used for the crystallization process. To investigate the processed areas we performed Laser Scanning Microscopy (LSM), Transmission Electron Microscopy (TEM) and Imaging Pump-Probe measurements. Except for 267 nm femtosecond laser irradiation, the crystallization occurred well. The threshold fluences for the crystallization using 800 nm and 400 nm femtosecond laser irradiations were 100 mJ/cm² and 30 mJ/cm², respectively. TEM observation revealed that the crystallization occurred by epitaxial growth from the boundary surface between the a-Si layer and c-Si substrate. The melting depths estimated by Imaging Pump-Probe measurements became shallower when the shorter wavelength was used.     

Direct laser interference patterning of poly(3,4-ethylene dioxythiophene)-poly(styrene sulfonate) (PEDOT-PSS) thin films

We have developed a patterning procedure based on selective ablation using interference patterns with ns-laser pulses to fabricate periodic arrays on large areas of poly(3,4-ethylene dioxythiophene)-poly(4-styrene sulfonic acid) (PEDOT-PSS) thin films over a metallic gold–palladium layer. Single pulse laser-ablation experiments were performed to study the ablation characteristics of the thin films as a function of the film thickness. The ablation threshold fluence of the PEDOT-PSS films was found to be dependent on thickness with values ranging from 43 mJ/cm² to 252 mJ/cm². Additionally, fluences at which the PEDOT-PSS films could be ablated without inducing damage in the underlying metallic films were observed (128 mJ/cm² and 402 mJ/cm² for film thicknesses of 70 nm and 825 nm, respectively). Linear periodic arrays with line spacings of 7.82 μm and 13.50 μm were also fabricated. The surface topography of these arrays was analyzed using scanning electron and atomic force microscopy. For thicker polymeric layers, several peeled sub-layers of the conjugated polymer with average thicknesses of about 165–185 nm were observed in the ablation experiments. The size and scale of structures produced by this technique could be suitable for several biomedical applications and devices in which controlling cell adhesion, promoting cell alignment, or improving biocompatibility are important.     

Tungsten silicide formation by XeCl excimer-laser irradiation of W/Si samples

We report a study of the formation of tungsten silicide at the W-Si interface, induced by multipulse (up to 300 shots) XeCl excimer-laser irradiation of W(150 nm)/Si and W(500 nm)/Si samples. Laser fluences ranging from 0.6 to 1.8 J/cm² were used. After laser treatment the samples were examined by different diagnostic techniques: Rutherford backscattering spectrometry, X-ray scattering, resistometry, and surface profilometry. Numerical computations of the evolution and depth profiles of the temperature in the samples as a consequence of a single 30 ns laser pulse were performed as well. The results indicate that it is possible to obtain a tungsten silicide layer at the W-Si interface at quite low fluences. The layer thickness increases with the number of laser pulses. Complete reaction of the 150 nm thick W film with silicon was obtained at the fluence of 1.2 J/cm² between 30 and 100 laser pulses and at 1.5 J/cm² after 30 laser pulses. The sheet resistance of these silicides was 5–10 . At the used fluences for the 500 nm thick W film only the onset of silicide synthesis at the W-Si interface was observed.     

Pulsed-laser crystallization and epitaxial growth of metal-organic films of Ca-doped LaMnO3 on STO and LSAT substrates

Ca-doped LaMnO₃ (LCMO) thin films have been successfully prepared on SrTiO₃ (STO) and [(LaAlO₃)_0.3-(SrAlTaO₆)_0.7] (LSAT) substrates using the excimer laser assisted metal-organic deposition (ELAMOD) process. The crystallization and the epitaxial growth of the amorphous metal-organic LCMO thin films have been achieved using a KrF excimer laser irradiation while the substrates were kept at constant temperature of 500 °C. Epitaxial films were obtained using laser fluence in the interval of 50-120 mJ/cm². The microstructure of the LCMO films was studied using cross-section transmission electron microscopy. High quality of LCMO films having smooth surfaces and sharp interfaces were obtained on both the STO and the LSAT substrates. The effect of the laser fluence on the temperature coefficient of resistance (TCR) was investigated. The largest values of TCR of the LCMO grown on the LSAT and the STO substrates of 8.3% K⁻¹ and 7.46% K⁻¹ were obtained at different laser fluence of 80 mJ/cm² and 70 mJ/cm², respectively.     

Femtosecond-laser-induced-crystallization and simultaneous formation of light trapping microstructures in thin a-Si:H films

We report the observation of crystallization and simultaneous formation of surface microstructures in hydrogenated amorphous silicon (a-Si:H) thin films as one step laser processing. Light trapping microstructures of around 300 nm in height were formed on a-Si:H films of thickness in the range of 1.5 μm to 2 μm deposited on soda lime glass after exposure to femtosecond laser pulses. Scanning electron microscope (SEM) images show the formation of spikes that are around 1 μm part and their heights could be controlled by the laser fluences. Atomic force microscope (AFM) images were taken to study the roughness created on the surface. The mean roughness of the textured surface increases with laser fluence at smaller power densities, and for power densities beyond 0.5 J/cm² the film removal deteriorates the texturing. X-ray diffraction results indicate the formation of a nano-crystalline structure with (111) and (311) crystal orientation after the laser treatment. The observed black color and enhanced optical absorption in the near infrared region in laser treated films may be due to a combined effect of light trapping in the micro-structured silicon surface because of multiple total internal reflections, phase change in the film, possible defect sites induced after laser treatment and formation of SiO_x. Demonstration of light trapping microstructures in thin a-Si:H films and simultaneous crystallization could provide new opportunities for optoelectronic devices. PACS 42.55.Px; 42.62.Cf; 81.05.Ge     

Morphological characteristics of amorphous Ge2Sb2Te5 films after a single femtosecond laser pulse irradiation

The morphology of materials resulting from laser irradiation of the single-layer and the multilayer amorphous Ge₂Sb₂Te₅ films using 120 fs pulses at 800 nm was observed using scanning electron microscopy and atomic force microscopy. For the single-layer film, the center of the irradiated spot is depression and the border is protrusion, however, for the multilayer film, the center morphology changes from a depression to a protrusion as the increase of the energy. The crystallization threshold fluence of the single-layer and the multilayer film is 22 and 23 mJ/cm², respectively.     

Low-temperature growth of SnO2 film prepared by XeCl excimer laser MOD process

A SnO₂ film has been prepared by an excimer laser metal organic deposition (ELMOD) process using an XeCl laser. The effects of the laser fluence, shot number, and the pretreatment temperature of the Sn acetylacetonate (Sn-acac) on the crystallization of the SnO₂ film were investigated by X-ray diffraction and infrared spectroscopy. When the MO spin-coated film preheated at room temperature on a Si substrate was irradiated by the laser at a fluence of 100 mJ/cm² and at a repetition rate of 10 Hz for 5 min, a crystallized SnO₂ film was successfully obtained without heat treatment. At a fluence of 260 mJ/cm², the highest crystalline film was formed. On the other hand, when the amorphous SnO₂ film was irradiated by the laser at 260 mJ/cm², the crystallinity of the SnO₂ film was improved. SnO₂ films were also prepared by conventional thermal MOD in a temperature range from 300 to 900 °C. The crystallinity of the SnO₂ films prepared by the ELMOD process at room temperature was higher than that of the films prepared by heating at 900 °C for 60 min. PACS 81.15.Fg; 81.15.-z; 81.16.Mk; 82.50.Hp; 73.61.Le     

Effects of laser irradiation energy density on the properties of pulsed laser deposited ITO thin films

The properties of indium tin oxide (ITO) thin films, deposited at room temperature by simultaneous pulsed laser deposition (PLD), and laser irradiation of the substrate are reported. The films were fabricated from different Sn-doped In₂O₃ pellets at an oxygen pressure of 10 mTorr. During growth, a laser beam with an energy density of 0, 40 or 70 mJ/cm² was directed at the middle part of the substrate, covering an area of ∼1 cm². The non-irradiated (0 mJ/cm²) films were amorphous; films irradiated with 40 mJ/cm² exhibited microcrystalline phases; and polycrystalline ITO films with a strong 〈111〉> preferred orientation was obtained for a laser irradiation density of 70 mJ/cm². The resistivity, carrier density, and Hall mobility of the ITO films were strongly dependent on the Sn doping concentration and the laser irradiation energy density. The smallest resistivity of ∼1×10^-4 Ω cm was achieved for a 5 wt % Sn doped ITO films grown with a substrate irradiation energy density of 70 mJ/cm². The carrier mobility diminished with increasing Sn doping concentration. Theoretical models show that the decrease in mobility with increasing Sn concentration is due to the scattering of electrons in the films by ionized centers. PACS 81.15.Fg; 73.61.-r; 73.50.-h     

Pulsed 532 nm laser wirestripping: Removal of dye-doped polyurethane insulation

Removal of rhodamine 6G doped polyurethane insulation coated onto 50 m diameter wire is shown to proceed efficiently and cleanly by irradiation with 532 nm Q-switched pulses from a Nd:YAG laser. The stripping action produced by this method is similar in quality to excimer laser wirestripping. Several experimental parameters were explored including fluence, pulse duration, dye concentration, and the number of incident pulses. Acceptable stripping conditions were obtained for a 3–5 s exposure at 10 Hz, using a dye concentration of 10% by weight, and 12 n pulses at 650 mJ/cm². Nearly 0.5 m/pulse is removed at this fluence, which exceeds the threshold fluence of 600 mJ/cm² by only 50 mJ/cm². The measured 532 nm absorption coefficient of the 10% dye-doped polyurethane was 4×10⁴ cm^–1. Lower fluences and/or dye concentrations produced inadequate stripping, while shorter duration pulses caused unacceptable melting of the thin gold layer which covered the copper core of the wire. Pulse-by-pulse photographs of the stripping action clearly show melting of the dye/polymer insulation, and thermal rollback of the insulation near the stripped end. Regardless, excellent edge definition is obtained by this method.     

Study of laser fragmentation process of silver nanoparticles in aqueous media

Laser fragmentation of Ag nanoparticles in Ag hydrosol was studied by simultaneous measurements of the transmitted fluence of the incident laser beam and the time evolution of the surface plasmon extinction (SPE) spectra. The experiments showed that the laser fragmentation in a small volume of hydrosol proceeds during first 20 pulses and then reaches saturation. The value of the transmitted fluence corresponding to saturation increases with incident pulse fluence, but the impact of the first pulse applied to the hydrosols shows an optical limitation. Fluences above 303 mJ/cm² cause the formation of less stable, aggregating nanoparticles, while fluences below 90 mJ/cm² do not provide sufficient energy for efficient fragmentation. The interval of fluences between 90–303 mJ/cm² is optimal for fragmentation, since stable hydrosols constituted by small, non-aggregated nanoparticles are formed.     

ArF laser CVD of hydrogenated amorphous silicon: The role of buffer gases

ArF laser-induced CVD has been employed to generate hydrogenated amorphous silicon (a-Si:H) from Si₂H₆ gas dilute with He, Ar, or H₂. The formation of amorphous films or powder is found to depend critically on the kind of buffer gas, the stationary total and partial gas pressures, and the substrate temperature. These dependences have been investigated in the 1–5 Torr pressure and 100–400 °C temperature ranges. They are semiquantitatively discussed in terms of ArF laser photolysis of disilane, gas heating by heat flow from the substrate and laser irradiation, diffusion, and gas phase polymerization. Furthermore, photo ionization has been observed but found irrelevant for the a-Si:H layer properties. The photo and dark conductivities ( _ph, _d) of the semiconductor layers are determined by the substrate temperature. The _ph values range between 10^–7 and 10^{–4 –1} cm^–1 and the _d values between 10^–11 and 10^{–8 –1} cm^–1. The maximum ratio _ph/ _d amounts to 4×10⁴. The layers are further characterized by their optical band gap and activation energy. The layer properties are compared to literature values of amorphous films prepared by various photo, HOMO, and plasma CVD methods.     

Direct observation of phase transitions by time-resolved pyro/reflectometry of KrF laser-irradiated metal oxides and metals

New experimental results are obtained by coupling both time-resolved reflectivity and rapid infrared pyrometry under a hemispherical reactor. The heating source KrF laser beam (28 ns, 248 nm) is homogenized and as for probing, a CW He-Ne laser beam (10 mW, 633 nm) is used.Using both methods infrared pyrometry with an IR detector cooled with liquid nitrogen and sensitive in the spectral range 1-12 μm, and time-resolved reflectivity with a rapid photodiode, we were able to study complex thermodynamic transitions with nanosecond time resolution. Three different materials are studied by varying the KrF fluence (energy/surface) from 100 to 2000 mJ/cm²: thin films melting (Au/Ni), the threshold of plasma formation (Ti), and complex liquid phase segregation under semi-conductor state (ZnO). The formation of a liquid Zn film induced by temperature gradient is well evidenced by our signals. Also melting of thin films irradiated by low laser fluences (less than 500 mJ/cm²) translates the typical thermodynamic behavior. Finally, wide fluence dynamic (400-2000 mJ/cm²) is analyzed in the case of Ti surface, and results show two distinguished regimes: first one bellow 1000 mJ/cm² corresponding to the early stage plasma initiation, and second one over 1000 mJ/cm² to the dynamics of plasma expansion.     

Laser surface treatment of screen-printed carbon nanotube emitters for enhanced field emission

This paper investigates the surface treatment of screen-printed carbon nanotube (CNT) emitters using a 248 nm (KrF) excimer laser. The field emission characteristics of the CNT emitters are measured following irradiation using laser fluences ranging from 80 to 400 mJ/cm². The results show that the turn-on electric field, the current density, and the distribution of the emission sites are highly dependent on the value of the laser fluence and are optimized at a fluence of 150 mJ/cm². Two distinct laser fluence regimes are identified. In the low fluence regime, i.e. 80-150 mJ/cm², the surface treatment process is dominated by a photo ablation mechanism, which results in the gradual removal of the binding material from the cathode surface and leads to an improvement in the emission characteristics of the CNT cathodes with an increasing fluence. However, in the high fluence regime, i.e. 150-400 mJ/cm², the thermal ablation mechanism dominates; resulting in a removal of the CNTs from the cathode surface and a subsequent degradation in the emission characteristics.     

Sub-picosecond UV-laser ablation of Ni films

Laser ablation of thin Ni films on fused silica by 0.5 ps KrF-excimer-laser pulses at 248 nm is reported. The onset of material removal from different film thicknesses (0.1, 0.3, 0.6 and 1.0 m) was measured in a laser ionization time-of-flight mass spectrometer by the amount of Ni atoms vs laser fluence. Significant amounts of metal atoms are already evaporated at laser fluences around 20 mJ/cm², a threshold up to 100 times smaller compared to the one for 14 ns pulses. In contrast to ns laser pulses, the ablation threshold for 0.5 ps pulses is independent of the film thickness. These results reflect the importance of thermal diffusion in laser ablation of strongly absorbing and thermally good conducting materials and prove that for ablation with short pulses, energy loss to the bulk is minimized.     

Excimer-laser-induced permanent electrical conductivity in solid C60 films

After being irradiated in air by a XeCI (308 nm) excimer laser, the electrical conductivity of solid thin-film C₆₀ has been improved by more than six orders of magnitudes. The products resulting from laser irradiation of C₆₀ films have been investigated by Raman scattering and the onset of conductivity can be attributed to laser-induced oxygenation and disintegration of the fullerene. Irradiated by 40 ns laser pulses with different fluence, products with different microstructure were observed. At lower fluence, the Raman features of microcrystalline graphite and fullerene polymer were observed. At a fluence just below the ablation threshold (36 mJ/cm²), the fullerene molecules in the film were disintegrated completely and transformed to amorphous graphite.     

Deposition of aluminum nitride thin film on Si(1 1 1) by KrF excimer laser and its characterizations

We present the deposition of aluminum nitride (AlN) thin film by KrF excimer laser sputtering and the study of the effects of substrate temperature and laser fluences. Deposition rate of AlN thin film at 0.3 Å/pulse has been achieved with laser fluence of 1500 mJ/cm² and at substrate temperature of 250 K, and this shows the enhancement of the deposition rate at low substrate temperature. Surface morphology of the deposited films is characterized by atomic force microscopy (AFM). In addition, the electrical performance of the MIS devices with AlN thin films prepared in this experiment has been characterized.     

Influence of the laser wavelength on the epitaxial growth and electrical properties of La0.8Sr0.2MnO3 films grown by excimer laser-assisted MOD

Epitaxial La_1−xSr_xMnO₃ (LSMO) films were prepared by excimer laser-assisted metal organic deposition (ELAMOD) at a low temperature using ArF, KrF, and XeCl excimer lasers. Cross-section transmission electron microscopy (XTEM) observations confirmed the epitaxial growth and homogeneity of the LSMO film on a SrTiO₃ (STO) substrate, which was prepared using ArF, KrF, and XeCl excimer lasers. It was found that uniform epitaxial films could be grown at 500 °C by laser irradiation. When an XeCl laser was used, an epitaxial film was formed on the STO substrate at a fluence range from 80 to 140 mJ/cm² of the laser fluence for the epitaxial growth of LSMO film on STO substrate was changed. When the LaAlO₃ (LAO) substrate was used, an epitaxial film was only obtained by ArF laser irradiation, and no epitaxial film was obtained using the KrF and XeCl lasers. When the back of the amorphous LSMO film on an LAO substrate was irradiated using a KrF laser, no epitaxial film formed. Based on the effect of the wavelength and substrate material on the epitaxial growth, formation of the epitaxial film would be found to be photo thermal reaction and photochemical reaction. The maximum temperature coefficient of resistance (TCR) of the epitaxial La_0.8Sr_0.2MnO₃ film on an STO substrate grown using an XeCl laser is 4.0%/K at 275 K. XeCl lasers that deliver stabilized pulse energies can be used to prepare LSMO films with good a TCR.     

Preparation of the La0.8Sr0.2MnO3 films on STO and LAO substrates by excimer laser-assisted metal organic deposition using the KrF laser

La_0.8Sr_0.2MnO₃ films were prepared on SrTiO₃ (STO) and LaAlO₃ (LAO) substrates using excimer laser-assisted metal organic deposition (ELAMOD). For the LAO substrate, no epitaxial La_0.8Sr_0.2MnO₃ film was obtained by laser irradiation in the fluence range from 60 to 110 mJ/cm² with heating at 500 °C. On the other hand, an epitaxial La_0.8Sr_0.2MnO₃ film on the STO substrate was formed by laser irradiation in the fluence range from 60 to 100 mJ/cm² with heating at 500 °C. To optimize the electrical properties for an IR sensor, the effects of the laser fluence, the irradiation time and the film thickness on the temperature dependence of the resistance and temperature coefficient of resistance (TCR: defined as 1/R·(dR/dT)) of the LSMO films were investigated. An LSMO film on the STO substrate that showed the maximum TCR of 3.9% at 265 K was obtained by the ELAMOD process using the KrF laser.     

Analyses of surface coloration on TiO2 film irradiated with excimer laser

TiO₂ film of around 850 nm in thickness was deposited on a soda-lime glass by PVD sputtering and irradiated using one pulse of krypton-fluorine (KrF) excimer laser (wavelength of 248 nm and pulse duration of 25 ns) with varying fluence. The color of the irradiated area became darker with increasing laser fluence. Irradiated surfaces were characterized using optical microscopy, scanning electron microscopy, Raman spectroscopy and atomic force microscopy. Surface undergoes thermal annealing at low laser fluence of 400 and 590 mJ/cm². Microcracks at medium laser fluence of 1000 mJ/cm² are attributed to surface melting and solidification. Hydrodynamic ablation is proposed to explain the formation of micropores and networks at higher laser fluence of 1100 and 1200 mJ/cm². The darkening effect is explained in terms of trapping of light in the surface defects formed rather than anatase to rutile phase transformation as reported by others. Controlled darkening of TiO₂ film might be used for adjustable filters.