Selective ablation of thin SiO<Subscript>2</Subscript> layers on silicon substrates by femto- and picosecond laser pulses

The selective ablation of thin (∼100 nm) SiO₂ layers from silicon wafers has been investigated by applying ultra-short laser pulses at a wavelength of 800 nm with pulse durations in the range from 50 to 2000 fs. We found a strong, monotonic decrease of the laser fluence needed for complete ablation of the dielectric layer with decreasing pulse duration. The threshold fluence for 100% ablation probability decreased from 750 mJ/cm² at 2 ps to 480 mJ/cm² at 50 fs. Significant corruption of the opened Si surface has been observed above ∼1200 mJ/cm², independent of pulse duration. By a detailed analysis of the experimental series the values for melting and breaking thresholds are obtained; the physical mechanisms responsible for the significant dependence on the laser pulse duration are discussed.     

Processing of C<Subscript>60</Subscript> thin films by Matrix-Assisted Pulsed Laser Evaporation (MAPLE)

Thin films of fullerenes (C₆₀) were deposited onto silicon using matrix-assisted pulsed laser evaporation (MAPLE). The deposition was carried out from a frozen homogeneous dilute solution of C₆₀ in anisole (0.67 wt%), and over a broad range of laser fluences, from 0.15 J/cm² up to 3.9 J/cm². MAPLE has been applied for deposition of fullerenes for the first time and we have studied the growth of thin films of solid C₆₀. The fragmentation of C₆₀ fullerene molecules induced by ns ablation in vacuum of a frozen anisole target with C₆₀ was investigated by matrix-assisted laser desorption/ionization (MALDI). Our findings show that intact fullerene films can be produced with laser fluences ranging from 0.15 J/cm² up to 1.5 J/cm².     

High-vacuum time-resolved laser-induced incandescence of flame-generated soot

We have measured time-resolved laser-induced incandescence of flame-generated soot under high-vacuum conditions (4.1×10⁻⁶ mbar) at an excitation wavelength of 532 nm with laser fluences spanning 0.06–0.5 J/cm². We generated soot in an ethylene/air diffusion flame, introduced it into the vacuum system with an aerodynamic lens, heated it using a pulsed laser with a spatially homogeneous and temporally smooth laser profile, and recorded LII temporal profiles at 685 nm. At low laser fluences LII signal decay rates are slow, and LII signals persist beyond the residence time of the soot particles in the detection region. At these fluences, the temporal maximum of the LII signal increases nearly linearly with increasing laser fluence until reaching a plateau at ∼0.18 J/cm². At higher fluences, the LII signal maximum is independent of laser fluence within experimental uncertainty. At these fluences, the LII signal decays rapidly during the laser pulse. The fluence dependence of the vacuum LII signal is qualitatively similar to that observed under similar laser conditions in an atmospheric flame but requires higher fluences (by ∼0.03 J/cm²) for initiation. These data demonstrate the feasibility of recording vacuum LII temporal profiles of flame-generated soot under well-characterized conditions for model validation.     

Self-assembled organic monolayers as high-resolution resists in rapid nonlinear processing with single femtosecond laser pulses

Femtosecond laser patterning of alkanethiol monolayers on gold-coated silicon substrates at λ=800 nm, τ<30 fs and ambient conditions has been investigated. Single-pulse processing allows one to selectively remove the organic coating. Subsequently, pattern transfer into the gold film via wet etching in ferri-/ferrocyanide solution is achieved. As demonstrated, burr-free patterning can be carried out over an extremely wide range of laser pulse fluences from above 2 J/cm² down to 0.5 J/cm². Moreover, at low fluences, sub-wavelength processing down to λ/5 is feasible. In particular, at a 1/e laser spot diameter of about 1 μm, holes with diameters of 160 nm and step edges below 80 nm are fabricated. These results emphasize the prospects of organic monolayers as high-resolution resists in rapid nonlinear femtosecond laser processing.     

Excimer-laser ablation and micro-patterning of ceramic Si3N4

3 N₄ has been investigated. The ablation threshold in air, Φ_th, is around 0.3±0.1 J/cm² with ArF- and 0.9±0.2 J/cm² with KrF-laser radiation. With fluences Φ_th<Φ<4 J/cm² the irradiated surface is either very flat or it exhibits a cone-type structure, depending on the number of laser pulses employed. With fluences of 5 to 10 J/cm², the sample surface becomes very smooth, much smoother than the original mechanically polished surface. Pores, scratches, and cracks observed on the non-irradiated surface are absent within the illuminated area. In this regime, the ablation rates are typically 0.1 to 0.2 μm/pulse. Received: 10 April 1997/Accepted: 11 April 1997     

Dynamics of phase transitions induced by femtosecond laser pulse irradiation of indium phosphide

The structural transformation dynamics of single-crystalline indium phosphide (InP) irradiated with 150 fs laser pulses at 800 nm has been investigated by means of time-resolved reflectivity measurements covering a time window from 150 fs up to 500 ns. The results obtained show that for fluences above a threshold of 0.16 J/cm² thermal melting of the material occurs on the timescale of 1–2 ps. The evolution of the reflectivity on a longer timescale reveals the reflectivity of the liquid phase and shows resolidification times typically around 10–30 ns after which an amorphous layer several tens of nanometers thick is formed on the surface. This amorphous layer significantly alters the optical properties of the surface and finally leads to a reduced ablation threshold for subsequent laser pulses. Single-pulse ablation at higher fluences (>0.23 J/cm²) is preceded by an ultrafast phase transition (non-thermal melting) occurring within 400 fs after the arrival of the pulse to the surface. PACS 79.20.Ds; 78.47.+p; 64.70.-p     

Surface micro/nanostructuring of titanium under stationary and non-stationary femtosecond laser irradiation

In this paper the surface topography of titanium samples irradiated by femtosecond laser pulses is described. When the fluence is about 0.5 J/cm² periodic ripples with a period of about 700 nm are formed. For fluences between 0.5 and 2 J/cm², a microcolumnar surface texture develops in the center of the irradiated spots and ripples are formed in the periphery of the spots. When experiments are performed with a non-stationary sample, the microcolumns exhibit ripples similar to those observed when the radiation fluence is about 0.5 J/cm² and in the outer regions of the irradiated areas for fluences between 0.5 and 2 J/cm². Since the energy distribution in the transverse cross-section of the laser beam is Gaussian, we conclude that the ripples form when the microcolumns are subjected to fluences near the melting threshold of the material at the trailing edge of the moving laser beam.     

Picosecond laser ablation of nickel-based superalloy C263

Picosecond laser (10.4 ps, 1064 nm) ablation of the nickel-based superalloy C263 is investigated at different pulse repetition rates (5, 10, 20, and 50 kHz). The two ablation regimes corresponding to ablation dominated by the optical penetration depth at low fluences and of the electron thermal diffusion length at high fluences are clearly identified from the change of the surface morphology of single pulse ablated craters (dimples) with fluence. The two corresponding thresholds were measured as F _th(D1)¹=0.68±0.02 J/cm² and F _th(D2)¹=2.64±0.27 J/cm² from data of the crater diameters D _1,2 versus peak fluence. The surface morphology of macroscopic areas processed with a scanning laser beam at different fluences is characterised by ripples at low fluences. As the fluence increases, randomly distributed areas among the ripples are formed which appear featureless due to melting and joining of the ripples while at high fluences the whole irradiated surface becomes grainy due to melting, splashing of the melt and subsequent resolidification. The throughput of ablation becomes maximal when machining at high pulse repetition rates and with a relatively low fluence, while at the same time the surface roughness is kept low.     

Chemical, morphological and chromatic behavior of mural paintings under Er:YAG laser irradiation

Several pigments (malachite CuCO₃⋅Cu(OH)₂, azurite 2CuCO₃⋅Cu(OH)₂, yellow ochre (goethite α-FeOOH, gypsum CaSO₄⋅2H₂O), St. John’s white CaCO₃ formed from slaked lime) and respective mural paintings specimens were subjected to the free-running Er:YAG laser radiation in order to study their damage thresholds, in a broad range of laser fluences, both in dry and wet conditions. The specimens’ damage thresholds were evaluated by spectroscopic methods, colorimetric measurements and microscopic observation. The pigments containing –OH groups were found to be more sensitive than St. John’s white; hence the most sensitive paint layers in dry conditions are those containing malachite, azurite (both 1.3 J/cm²) and yellow ochre (2.5 J/cm²) as compared to the ones containing St. John’s white (15.2 J/cm²). The presence of wetting agents (w.a.) attenuated the pigments chemical alteration. The damage thresholds of all the paint layers, in presence of w.a., were found to be around 2.5 J/cm². The alteration was caused by thermo-mechanical damage and by binding medium ablation of a fresco and a secco prepared specimens, respectively.     

Femtosecond laser ablation characteristics of nickel-based superalloy C263

Femtosecond laser (180 fs, 775 nm, 1 kHz) ablation characteristics of the nickel-based superalloy C263 are investigated. The single pulse ablation threshold is measured to be 0.26±0.03 J/cm² and the incubation parameter ξ=0.72±0.03 by also measuring the dependence of ablation threshold on the number of laser pulses. The ablation rate exhibits two logarithmic dependencies on fluence corresponding to ablation determined by the optical penetration depth at fluences below ∼5 J/cm² (for single pulse) and by the electron thermal diffusion length above that fluence. The central surface morphology of ablated craters (dimples) with laser fluence and number of laser pulses shows the development of several kinds of periodic structures (ripples) with different periodicities as well as the formation of resolidified material and holes at the centre of the ablated crater at high fluences. The debris produced during ablation consists of crystalline C263 oxidized nanoparticles with diameters of ∼2–20 nm (for F=9.6 J/cm²). The mechanisms involved in femtosecond laser microprocessing of the superalloy C263 as well as in the synthesis of C263 nanoparticles are elucidated and discussed in terms of the properties of the material.     

Ablation of silicon suboxide thin layers

We investigate the ablation of SiO _x thin films on fused silica substrates using single-pulse exposures at 193 nm and 248 nm. Two ablation modes are considered: front side (the surface of a film is irradiated from above) and rear side (a film is irradiated through its supporting substrate). Fluence is varied from below 200 mJ/cm² to above 3 J/cm². SiO _x films of thickness 200 nm, 400 nm, and 600 nm are ablated. In the case of rear-side illumination, at moderate fluences (around 0.5 mJ/cm²) the ablation depth corresponds roughly to the film thickness, above 1 J/cm² part of the substrate is ablated as well. In the case of front-side ablation the single-pulse ablation depth is limited for all film thicknesses to less than 200 nm even at fluences up to 4 J/cm². Experimental results are discussed in relation to film thickness, fluence, and ablation mode. Simple numerical calculations are performed to clarify the influence of heat transport on the ablation process.     

Ultra-short pulse laser ablation of metals: threshold fluence, incubation coefficient and ablation rates

In this paper we present femtosecond laser ablation studies of the metals copper, silver and tungsten. Measurements of the threshold fluence determined from the hole diameters versus fluence provide incubation coefficients of the three materials, which are found to be equal within one standard deviation. Furthermore, we have determined the single-shot threshold fluences to be 1.7±0.3 J/cm², 1.5±0.4 J/cm² and 0.44±0.02 J/cm² for copper, silver and tungsten, respectively. These are in good agreement with theoretical values calculated neglecting heat diffusion.     

Structural changes induced on strontium barium niobate glass by femtosecond laser irradiation

Localized modification of the optical properties of erbium doped strontium barium niobate (SBN) glass has been performed using femtosecond laser irradiation. The samples, with composition SrO–BaO–Nb₂O₅–B₂O₅ and doped with 5%mol of Er³⁺, were fabricated using a melt-quenching method. The samples were irradiated with different number of pulses per spot (1–50 pulses) at two different laser fluences (2.6 and 5.6 J/cm²) by using an fs laser amplifier operating at 800 nm and generating pulses with a duration of 120 fs. Micro-luminescent microscopy, using an Ar⁺ laser as excitation source, has been used to analyze the modifications of the luminescent properties of the sample upon fs laser exposure. The emissions of the Er³⁺: ⁴I_11/2→⁴I_15/2 and ⁴I_13/2→⁴I_15/2 transitions allow appreciating the structural modifications caused by femtosecond laser exposure. The lifetimes of the levels involved in these transitions were measured inside and outside the laser irradiated region. These measurements have been compared with those obtained in bulk glass ceramic sample, which is obtained from the glass precursor by a thermal treatment in order to estimate the optimal conditions to produce nanocrystals in a localized region by ultrafast laser irradiation.     

Pulsed laser synthesis of titanium silicides using a Q-Switched Nd: Glass laser

Titanium films 120 nm thick deposited on single-crystalline silicon (c-Si) as well as poly-Si/SiO₂/c-Si substrates were subjected to Nd: glass laser irradiation. Laser fluences of 1,1.5, and 2 J/cm² were used at the pulse duration of 30 ns. From RBS analysis it follows that on c-Si substrate titanium suicide is formed using one pulse of 1.5 J/cm² energy density. On the substrate with surface overlayers lower fluence (1 J/cm²) was sufficient. Under these conditions the sheet resistance of the samples decreased from the initial value 5 / to 2–3 /. The smaller threshold density of energy for suicide formation in Ti/polySi/SiO₂/c-Si structure is shown to be a consequence of the SiO₂ underlayer, which is a poorer heat conductor than silicon. The experimental results of the suicide synthesis are in semi-quantitative accordance with the numerical computations of the temperature vs time evolution and depth temperature distribution in our samples.     

Simple fabrication of hexagonally well-ordered AAO template on silicon substrate in two dimensions

In this study, thin anodic aluminum oxide (AAO) templates both on silicon substrates (AAO template/SiO₂/Si) and Ti-coated silicon substrates (AAO template/Ti/SiO₂/Si) were developed for design of magnetic, electronic and optoelectronic devices, chemical sensors and chip-scale lithium-ion rechargeable microbatteries. Two types of AAO template were prepared by using a two-step anodization procedure. The templates were characterized by scanning electron microscopy and energy dispersive X-ray spectroscopy. The obtained thin AAO templates were approximately 50 nm in diameter and 700 nm in length with 80-nm interpore distances in a relatively large area of 6 cm². A barrier layer of the AAO templates was removed by a cathodic polarization method in KCl solution for several seconds. The current–time transient during removing the alumina barrier layer of the thin AAO template and the mechanism of electrochemical dissolution of the barrier layer are given in detail.     

Effect of the ceramic grain size and concentration on the dynamical mechanical and dielectric behavior of poly(vinilidene fluoride)/Pb(Zr<Subscript>0.53</Subscript>Ti<Subscript>0.47</Subscript>)O<Subscript>3</Subscript> composites

Laser-induced backside wet and dry etching (LIBWE and LIBDE) methods were developed for micromachining of transparent materials. Comparison of these techniques is helpful in understanding the etching mechanism but was not realized due to complications in setting up comparable experimental conditions. In our comparative investigations we used a solid tin film for dry and molten tin droplets for wet etching of fused-silica plates. A tin–fused-silica interface was irradiated through the sample by a KrF excimer laser beam (λ=248 nm, FWHM=25 ns); the fluence was varied between 400 and 2100 mJ/cm². A significant difference between the etch depths of the two investigated methods was not found. The slopes of the lines fitted to the measured data (sl_LIBDE=0.111 nm/mJ cm⁻², sl_LIBDE=0.127 nm/mJ cm⁻²) were almost similar. Etching thresholds for LIBDE and LIBWE were approximately 650 and 520 mJ/cm², respectively. To compare the dependence of etch rates on the pulse number, target areas were irradiated at different laser fluences and pulse numbers. With increasing pulse number a linear rise of depth was found for wet etching while for dry etching the etch depth increase was nonlinear. Secondary ion mass spectroscopic investigations proved that this can be due to the reconstruction of a new thinner tin-containing surface layer after the first pulse.     

Silicon substrate temperature effects on surface roughness induced by ultrafast laser processing

We report the effect of substrate temperature (T_sub) in the range 300-900 K on the surface roughness of silicon wafer resulted from femtosecond laser ablation. The surface roughness observed at the laser fluences less then 0.3 J/cm² increases with increasing T_sub. However, the surface roughness decreases with increasing T_sub for the laser fluences between 0.5 and 1.0 J/cm². If the laser fluence is higher than 2.0 J/cm², the surface roughness is independent of T_sub. The effect of T_sub on the surface roughness can be understood in terms of the temperature dependence of optical absorption coefficient of silicon substrate, which eventually alters a mechanism underlying the fs-laser-material ablation process between optical penetration and thermal diffusion processes.     

Caries resistance of lased human root surface with 10.6 μm CO2 laser-thermal,morphological, and microhardness analysis

Although the cariostatic effects of CO₂ laser on enamel have been shown, its effects on root surface demineralization remains uncertain. The objectives of this in vitro research was to establish safe parameters for a pulsed 10.6 μm CO₂ laser and to evaluate its effect on morphological features of the root surface, as well as on the reduction of root demineralization. Ninety-five human root surfaces were randomly divided into five groups: G1-No treatment (control); G2—2.5 J/cm²; G3—4.0 J/cm²; G4—5.0 J/cm²; and G5—6.0 J/cm². Intrapulpal temperature was evaluated during root surface irradiation by a thermocouple and morphological changes were evaluated by SEM. After the surface treatment, the specimens were submitted to a 7-day pH-cycling model. Subsequently, the cross-sectional Knoop microhardness values were measured. For all irradiated groups, intrapulpal temperature changes were less than 1.5°C. Scanning electron microscopy images indicated that fluences as low as 4.0 J/cm² were sufficient to induce morphological changes in the root surface. Additionally, for fluences reaching or exceeding 4.0 J/cm², laser-induced inhibitory effects on root surface demineralization were observed. It was concluded that laser energy density in the range of 4.0 to 6.0 J/cm² could be applied to a dental root to reduce demineralization of this surface without compromising pulp vitality.     

Oxygen isotope separation utilizing two-frequency infrared multiphoton dissociation of 2,3-dihydropyran

Oxygen isotope separation has been examined by utilizing the two-frequency infrared multiphoton dissociation (IRMPD) of 2,3-dihydropyran (DHP). The two-frequency IRMPD reduces the required laser fluences to those lower than the damage threshold of optical windows. For example, dissociation probability of DHP containing ¹⁸O (D(¹⁸O)) and enrichment factor (S) were obtained to be 1.6×10⁻³/pulse and 316, respectively, by the simultaneous irradiation with 1052.2 cm⁻¹ photons at 0.45 J/cm² and 1031.5 cm⁻¹ photons at 1.06 J/cm². These are comparable with D(¹⁸O)=2.2×10⁻³/pulse and S=391 obtained by the single-frequency irradiation of 1033.5 cm⁻¹ photons at 2.2 J/cm². Therefore, the production rate of an ¹⁸O enriched dissociation product has been increased to four times or more, compared with the single-frequency IRMPD, and this two-frequency method would promise a practical large scale separation.     

KrF pulsed laser ablation of polyimide

In the present paper, polyimide surfaces were processed with pulsed KrF laser radiation at fluences near the ablation threshold. The morphology of the processed surfaces was studied by scanning electron microscopy and chemical analyses performed by electron dispersive spectroscopy. The formation of conical structures was observed for radiation fluences lower than 0.5 J/cm². The areal density of cones increases with the number of pulses and decreases with the radiation fluence. At low fluences (<150 J/cm²), cones are formed due to shadowing by calcium phosphate impurities while for higher fluences the main mechanism of cones formation is believed to be radiation hardening.