Kinetic modeling of laser annealing processes in a-C:H films

In this research work, a nanosecond-pulsed YAG:Nd laser was used to modify the properties of an amorphous hydrogenated carbon film, which was deposited on c–Si substrate. Experimental examination has revealed that the primary effect of irradiation is diamond-to-graphite transformation or, more specifically, carbon sp³-to-sp² hybridization transition. These findings were qualitatively verified by numerical simulation of kinetic processes that proceed in the film under laser irradiation.     

Laser-induced transformation of a-C:H thin films

In this work, we report the laser irradiation effects on the properties of various types of amorphous hydrogenated carbon (a-C:H) films. The influence of the initial carbon film (hydrogen concentration, sp³/sp² ratio, and sp² clustering) is studied. The results show that a loss of hydrogen and an increase of the sp² phase are the main processes in the laser power range between 1.8 and 5 MW/cm². Only these processes are stronger for “more polymer-like” and “graphite-like” films than for “more diamond-like” films.     

Effect of a pulsed Nd:YAG laser irradiation on multi-walled carbon nanotubes film

Multi-walled carbon nanotubes (MWCNTs) film have been analyzed by Raman spectroscopy to clarify the effect of a pulsed Nd:YAG laser heating. The MWCNTs film surface was flashed with the fundamental harmonic (λ = 1064 nm) or the second harmonic (λ = 532 nm) of a single pulse of Nd:YAG laser in the air. The dynamics of pulsed nanosecond laser heating process was simulated by the solution of the one-dimensional heat conduction equation. At the laser fluence of 500 mJ/cm² with Nd:YAG laser (λ = 1064 nm), the surface reached the maximum temperature 1395 °C at 12 ns. Moreover, the Raman spectroscopy of MWCNTs films before and after irradiation were measured. The intensity of the two characteristic Raman shifts I_D (defect-mode) and I_G (graphite-mode) was measured by the Raman spectroscopy. The maximum surface temperature was calculated and compared with the I_G/I_D ratio of MWCNTs film. The graphitization occurred on the sample after irradiation.     

Improvement of physical properties of IGZO thin films prepared by excimer laser annealing of sol–gel derived precursor films

Indium gallium zinc oxide (IGZO) transparent semiconductor thin films were prepared by KrF excimer laser annealing of sol–gel derived precursor films. Each as-coated film was dried at 150 °C in air and then annealed using excimer laser irradiation. The influence of laser irradiation energy density on surface conditions, optical transmittances, and electrical properties of laser annealed IGZO thin films were investigated, and the physical properties of the excimer laser annealed (ELA) and the thermally annealed (TA) thin films were compared. Experimental results showed that two kinds of surface morphology resulted from excimer laser annealing. Irradiation with a lower energy density (≤250 mJ cm⁻²) produced wavy and irregular surfaces, while irradiation with a higher energy density (≥350 mJ cm⁻²) produced flat and dense surfaces consisting of uniform nano-sized amorphous particles. The explanation for the differences in surface features and film quality is that using laser irradiation energy to form IGZO thin films improves the film density and removes organic constituents. The dried IGZO sol–gel films irradiated with a laser energy density of 350 mJ/cm² had the best physical properties of all the ELA IGZO thin films. The mean resistivity of the ELA 350 thin films (4.48 × 10³ Ω cm) was lower than that of TA thin films (1.39 × 10⁴ Ω cm), and the average optical transmittance in the visible range (90.2%) of the ELA 350 thin films was slightly higher than that of TA thin films (89.7%).     

AgBr nanocrystal-dispersed silsesquioxane-titania hybrid films for holographic materials

AgBr-doped silsesquioxane-titania films with a thickness of approximately 5 μm were prepared using a sol-gel technique. The dopant AgBr crystals were converted into very small Ag nanoparticles (mainly several nanometers) upon blue laser irradiation, leading to an increase in the absorption of the film in the visible region. An excess of Ag⁺ ions in the film was required for the conversion of AgBr into Ag upon blue laser irradiation. A maximum diffraction efficiency of 0.03% was achieved after two-beam interference exposure with a blue laser for 1300 s. These results imply that the films are suitable for use as holographic materials.     

Manipulation of cell membrane using carbon nanotube scaffold as a photoresponsive stimuli generator

We describe, for the first time, the perforation of the cell membrane in the targeted single cell based on the nanosecond pulsed near-infrared (NIR) laser irradiation of a thin film of carbon nanotubes that act as an effective photon absorber as well as stimuli generator. When the power of NIR laser is over 17.5 μJ/pulse, the cell membrane after irradiation is irreversibly disrupted and results in cell death. In sharp contrast, the perforation of the cell membrane occurs at suitable laser power (～15 μJ/pulse) without involving cell termination.     

Analysis of organometallics dispersed polymer composite irradiated with oxygen ions

Thin films of polymethyl methacrylate (PMMA) were synthesized. Ferric oxalate was dispersed in PMMA films. These films were irradiated with 80 MeV O⁶⁺ ions at a fluence of 1×10¹¹ ions/cm². The radiation induced changes in electrical conductivity, Mössbauer parameter, microhardness and surface roughness were investigated. It is observed that hardness and electrical conductivity of the film increases with the concentration of dispersed ferric oxalate and also with the fluence. It indicates that ion beam irradiation promotes (i) the metal to polymer bonding and (ii) convert the polymeric structure into hydrogen depleted carbon network. Thus irradiation makes the polymer harder and more conductive. Before irradiation, no Mössbauer absorption was observed. The irradiated sample showed Mössbauer absorption, which seems to indicate that there is significant interaction between the metalion and polymer matrix. Atomic force microscopy shows that the average roughness (R _a) of the irradiated film is lower than the unirradiated one.     

Adsorption and desorption properties on the fluorine-doped tin oxide film surface on a glass substrate under UV light irradiation in vacuum

Various functional metal-oxide coatings on glass substrate have the possibility to be used for many applications in these days. For keeping the high performance of these applications, it is very important to understand the adsorption property on those coating surfaces. However, there are few reports about such properties of metal-oxide film surface in vacuum state, especially the carbon adsorption property on fluorine-doped tin oxide (SnO₂:F) film in vacuum.In this study, we have investigated the chemical state on SnO₂:F film in vacuum with XPS analysis. From the results of the SnO₂:F film surface analysis, the adsorbed carbon (C1s orbit) on the SnO₂:F film surface and the adsorbed carbon dependence of heat treatment in vacuum were observed. Also, it was found that the adsorbed carbon distribution on the SnO₂:F film existed after the heat treatment at low temperature in vacuum, uniformly spread in large area with UV light irradiation. Besides, the influence of UV light irradiation with respect to the carbon contents in the SnO₂:F film was observed by SIMS analysis. As the result, it was implied that the carbon state in the SnO₂:F film remained unchanged under UV light irradiation and the carbon adsorption and desorption occurred only on the surface of the SnO₂:F film.     

Effects of Laser Irradiation on the Thermal Conductivity and Viscosity of Aqueous Multiwalled Carbon Nanotube Suspensions

The effects of KrF excimer laser irradiation (248 nm) on aqueous suspensions of multiwalled carbon nanotubes (MWCNTs) were experimentally examined. MWCNTs and sodium dodecyl sulfate were added to deionized water at a mass fraction of 0.5 %, and the suspension was ultrasonicated for 30 min. Transmission electron microscopy (TEM) images of the nanotube samples after laser irradiation indicated fractures and network disentanglement. The laser fluence affected the thermal conductivity and viscosity of the suspensions beyond a threshold of 50 mJ · cm⁻². As the irradiation time progressed at a laser fluence of 144 mJ · cm⁻², the thermal conductivity and viscosity decreased until they reached saturation. The thermal-conductivity enhancement decreased from 16 % to 5 %, and the low shear viscosity decreased dramatically to 1/200 the shear viscosity of the non-irradiated sample. Raman spectra and TEM images showed that the defects in the nanotubes increased upon laser irradiation. In conclusion, excimer laser irradiation of a suspension of MWCNTs provided an effective way to tune the heat transfer and rheological characteristics of suspensions.     

Modification of the properties of HTSC YBCO thin films on silicon by superfast laser annealing in oxygen with a CW CO2 Laser

The use of superfast CW CO₂ laser annealing in O₂ for modifying the properties of laser deposited Y₁Ba₂Cu₃O_{7 –x} thin films is described. The film resistivity could be controlled reversibly by laser irradiation at 40 W cm^–2. The resistivity was measuredin situ during the annealing process.     

Carbon nitride films deposited by reactive sputtering and pulsed laser ablation

Carbon nitride films were deposited by reactive sputtering process and by pulsed laser ablation process with substrate bias. By applying the RF bias, it enables the ion irradiation on to the depositing film surface continuously. ECR plasma source was used for reactive sputtering. Nd:YAG laser (λ=532 nm, 210 mJ) was used to ablate a graphite target in the nitrogen atmosphere. The film properties were examined by XPS, Raman, nanoindentation measurement, and FE-SEM. It was shown that the films deposited by reactive sputtering had smooth surface and its hardness of approximately 30 GPa. However, the films deposited by pulsed laser ablation had uneven surface and low hardness. Both processes, the atomic composition ratio of N/C and sp³ bonding ratio increased with ion bombardment energy up to 100-150 eV, and level off above it. The maximum atomic composition ratio of N/C was 0.35 for reactive sputtering and 0.24 for laser ablation.     

Effect of electron beam irradiation on structure and properties of SiCN thin films prepared by plasma assisted radio frequency magnetron sputtering

Silicon carbon nitride thin films were deposited on Si (100) substrate at room temperature by plasma assisted radio frequency magnetron sputtering. The bonding structure and properties of SiCN films irradiated by pulsed electron beams were studied by means of X-ray photoelectron spectroscopy and nano-indentation. The results showed that electron beam irradiation had a great effect on the structure and property of the films. Under sputtering gas pressure of 3.7 Pa, a transition from the (Si,C)N_x bonded structure to the (Si,C)₃N₄ bonded structure was found in the SiCN thin film with electron beam irradiation. At sputtering gas pressure of 6.5 Pa, the enhancement of hardness in the SiCN film after treatment with electron beam irradiation resulted from the promotion of the sp³-hybridization of carbons bonds.     

The influence of nanosecond pulse laser irradiation on the properties of a-C:H films

Plasma-deposited amorphous hydrogenated carbon (a-C:H) films are determined both by the carbon sp³/sp² bonding ratio and the hydrogen content. As the energy of the bonds C-H (C-C) is considerably smaller than that of CC or CC bonds, so the hydrogen concentration and the physical properties of a-C:H films can be varied by laser irradiation. The properties of produced films were investigated by Rutherford backscattering (RBS) and elastic recoil detection (ERD) spectroscopy, null-ellipsometry, and Raman spectroscopy (RS). It was found that films with higher hydrogen concentration are more sensitive to nanosecond pulse laser irradiation.     

Effect of electron beam irradiation on structure and properties of SiCN thin films prepared by plasma assisted radio frequency magnetron sputtering

Silicon carbon nitride thin films were deposited on Si (100) substrate at room temperature by plasma assisted radio frequency magnetron sputtering. The bonding structure and properties of SiCN films irradiated by pulsed electron beams were studied by means of X-ray photoelectron spectroscopy and nano-indentation. The results showed that electron beam irradiation had a great effect on the structure and property of the films. Under sputtering gas pressure of 3.7 Pa, a transition from the (Si,C)N_x bonded structure to the (Si,C)₃N₄ bonded structure was found in the SiCN thin film with electron beam irradiation. At sputtering gas pressure of 6.5 Pa, the enhancement of hardness in the SiCN film after treatment with electron beam irradiation resulted from the promotion of the sp³-hybridization of carbons bonds.     

Irradiation induced texturing in the Mg0.95Mn0.05Fe2O4 ferrite thin film

We present a study on the effect of swift heavy ions irradiation on the structural and magnetic properties of Mg_0.95Mn_0.05Fe₂O₄ ferrite thin film grown by pulsed laser deposition technique. X-ray diffraction (XRD) pattern of the as-deposited film reveals a cubic spinel structure with an intermediate phase of α-Fe₂O₃. This impurity phase completely dissolves upon irradiation with 200 MeV Ag¹⁵⁺-ions and it exhibits a strong crystallographic texture along the (440) plane. The magnetization values start increasing systematically with irradiation at lower fluence values, whereas decrease for higher one. This decrease in magnetic signal can be attributed to partial amorphization caused by irradiation in agreement with XRD and atomic/magnetic force microscopic images.     

Photoinduced characteristics in La<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> film

A systematic investigation of photoinduced properties is carried out in La_0.67Ca_0.33MnO₃ film prepared on LaAlO₃ (100) substrate by magnetron sputtering method. At T < 270 K, the resistivity of film induced by laser increases because of the demagnetization effect of manganites. The photoinduced relaxation character of film indicates that the time constant increases with increasing temperature, which is attributed to the growing thermal fluctuation. After laser irradiation, the resistivity returns to the original value and the relaxation time seems to be independent of temperature. In insulating state, laser irradiation induces the reduction in resistivity of film due to the excitation of small polarons.     

Pulsed Laser Processing of Carbon and Silicon Clusters and Thin Films

Abstract

Several new processes have been developed for the preparation of fullerenes and thin films by using a pulsed excimer laser. The irradiation of a pulsed KrF excimer laser beam onto a C₆₀ powder target produced single phase C₆₀ thin films when the laser energy fluence was in the range between 40 and 50mJ/cm². By atomic force microscopy, the laser-deposited C₆₀ thin film was verified to have a surface far smoother that the surfaces of films produced by the conventional evaporation method. The stainless steel rods coated with this film exhibited an excellent tribological property. Cluster formation from SiC and other carbides MC_n(M=Ti,W,B) was investigated by laser desorption time-of-flight mass spectrometry. No clear indication was observed for the production of such clusters as (SiC)₆₀ and (M_xC_60-x) from the sintered targets directly as well as from the films laser deposited from the targets. However, C₆₀ and C₇₀ were found to exists in the laser-deposited films, indicating a new applicability of pulsed laser processing for segregative cluster synthesis from solid solution. Preliminiary results on thin film deposition via pulsed ablation of (Ba,Na)_xSi₄₆ clathrate were also presented.     

Thickness dependence of electrical properties of PZT films deposited on metal substrates by laser-assisted aerosol deposition

Dependence of electrical properties-dielectric, ferroelectric, and piezoelectric properties-on film thickness was studied for lead-zirconate-titanate (PZT) thick films directly deposited onto stainless-steel (SUS) substrates in actuator devices by using a carbon dioxide (CO₂), laser-assisted aerosol deposition technique. Optical spectroscopic analysis data and laser irradiation experiments revealed that absorption at a given wavelength by the film increased with increasing film thickness. Dielectric constant epsiv, remanent polarization value P_r, and coercive field strength E_c of PZT films directly deposited onto a SUS-based piezoelectric actuator substrate annealed by CO₂ laser irradiation at 850degC improved with increasing film thickness, and for films thicker than 25 mum, e > 800, Pr > 40 muC/cm², and E_c < 45 kV/cm. In contrast, the displacement of the SUS-based actuator with the laser-annealed PZT thick film decreased with increasing film thickness.     

Growth of thin metallic films on insulating substrates in the presence of electron irradiation

The condensation parameters for Ag and Sb films on amorphous dielectric substrates have been studied under electron irradiation conditions (J = 400 μcm^-2, V_e = 1 kV). With the help of Auger spectroscopy it was shown that the irradiation activated additional condensation centres, whose lifetimes on Sitall substrates were 1 h or more. Optimum doses of irradiation were determined (14 × 10^-3 A s cm^-2).From critical flux measurements for Ag condensation on polymeric surfaces, it was determined that irradiation increased the number of condensation centres by 2–2.5 times without influencing the film formation energy. It was shown that irradiation changed the process of Ag film condensation, causing earlier coalescence.     

Simultaneous recrystallization, phosphorous diffusion and antireflection coating of silicon films using laser treatment

Laser technique application to polycrystalline silicon thin-film solar cell fabrication on glass substrates has received appreciable attention. In this paper, a laser-doping technique is developed for plasma-deposited amorphous silicon film. A process involving recrystallization, phosphorous diffusion and antireflection coating can be achieved simultaneously using the laser annealing process. The doping precursor, a phosphorous-doped titanium dioxide (TiO₂) solution, is synthesized using a sol-gel method and spin-coated onto the sample. After laser irradiation, the polycrystalline silicon grain size was about 0.5∼1.0 μm with a carrier concentration of 2 × 10¹⁹ cm^− 3 and electron mobility of 92.6 cm²/V s. The average polycrystalline silicon reflectance can be reduced to a value of 4.65% at wavelengths between 400 and 700 nm, indicating the upper TiO₂ film of antireflection coating.