SiO2 films fabricated by F2 laser-induced chemical deposition using silicone rubber

Silicon dioxide (SiO₂) films were selectively fabricated on a Si substrate at room temperature by illuminating both the silicone rubber target and the substrate with an F₂ laser (157 nm). The laser fluence was much less than the ablation threshold. Absorption due to absorbed water (H₂O) and hydrogen-bonded silanol (SiOH) groups were observed in addition to absorption due to Si-O-Si stretching mode in the Fourier transform infrared spectroscopy (FT-IR) spectra of the films. The illumination with higher laser fluence caused an increase of Si-O-Si/OH peak ratio in the FT-IR spectra, a decrease of etching rate in hydrofluoric acid (HF) solution, and an increase in the refractive index close to the value of a thermal SiO₂ film. These results indicate that the quality of the grown SiO₂ films was improved. The high photon energy of F₂ laser induced photodissociation of main chains and side chains of silicone and oxygen (O₂), and bonds between the ejected gaseous molecules including Si and O(¹D) to form SiO₂ films. PACS 61.80.Ba; 81.15.Fg; 82.50.Hp     

F2 laser induced oxidation of inorganic material

Transparent SiO₂ thin films were selectively fabricated on Si wafer by 157 nm F₂ laser in N₂/O₂ gas atmosphere. The F₂ laser photochemically produced active O(¹D) atoms from O₂ molecules in the gas atmosphere; strong oxidation reaction could be induced to fabricate SiO₂ thin films only on the irradiated areas of Si wafer. The oxidation reaction was sensitive to the single pulse fluence of F₂ laser. The irradiated areas were swelled and the height was approximately 500-1000 nm at the 205-mJ/cm² single pulse fluence for 60 min laser irradiation. The fabricated thin films were analytically identified to be SiO₂ by the Fourier-transform IR spectroscopy. The SiO₂ thin films could be also removed by subsequent chemical etching to fabricate micro-holes 50 nm in depth on Si wafer for microfabrication.     

F2-laser ablation patterning of dielectric layers

Spatially defined patterning of multi-layer dielectric optical systems by laser-induced ablation is demonstrated. A 49-layer high-reflectivity mirror for 193-nm light was irradiated with F₂-laser light through the CaF₂-substrate to cleanly remove the whole dielectric stack by rear-sided ablation. The 157-nm light is absorbed efficiently by dielectric layers such as SiO₂ and Al₂O₃ that are typically used for ultraviolet (UV) transmission at 193-nm and longer wavelengths. Thus it is possible to ablate highly reflective UV-laser mirrors (HR 193 nm) and to create dielectric masks that withstand high power levels at 193 nm. A single 157-nm pulse with a fluence of less than 500 mJ/cm² is sufficient to cleanly ablate the whole layer stack with sharp edges and without debris deposition. Received: 31 October 2000 / Accepted: 14 November 2000 / Published online: 10 January 2001     

Influence of laser fluence and irradiation timing of F2 laser on ablation properties of fused silica in F2-KrF excimer laser multi-wavelength excitation process

A collinear irradiation system of F₂ and KrF excimer lasers for high-quality and high-efficiency ablation of hard materials by the F₂ and KrF excimer lasers’ multi-wavelength excitation process has been developed. This system achieves well-defined micropatterning of fused silica with little thermal influence and little debris deposition. In addition, the dependence of ablation rate on various conditions such as laser fluence, irradiation timing of each laser beam, and pulse number is examined to investigate the role of the F₂ laser in this process. The multi-wavelength excitation effect is strongly affected by the irradiation timing, and an extremely high ablation rate of over 30 nm/pulse is obtained between -10 ns and 10 ns of the delay time of F₂ laser irradiation. The KrF excimer laser ablation threshold decreases and its effective absorption coefficient increases with increasing F₂ laser fluence. Moreover, the ablation rate shows a linear increase with the logarithm of KrF excimer laser fluence when the F₂ laser is simultaneously irradiated, while single KrF excimer laser ablation shows a nonlinear increase. The ablation mechanism is discussed based on these results. Received: 16 July 2001 / Accepted: 27 July 2001 / Published online: 2 October 2001     

Femtosecond uv excimer laser ablation

Experiments on the ablation of polymethylmethacrylate (PMMA) with 300 fs uv excimer laser pulses at 248 nm are reported for the first time. With these ultrashort pulses, ablation can be done at fluences up to five times lower than the threshold fluence for 16 ns ablation of PMMA, and the surface morphology is improved, also for several other materials. A model for ablation is proposed, assuming a non-constant absorption coefficient _eff depending on the degree of incubation of the irradiated material and the intensity of the incoming excimer laser pulse. The agreement between our model and our experimental observations is excellent for 16 ns excimer laser pulses, also predicting perfectly the shape of a pulse transmitted through a thin PMMA sample under high fluence irradiation. Qualitative agreement for 300 fs excimer laser pulses is obtained so far.     

Photochemical welding of silica microspheres to silicone rubber by ArF excimer laser

Transparent fused silica (SiO₂) microspheres 2.5 μm in diameter were photochemically welded to transparent, flexible silicone rubber ([SiO(CH₃)₂]_n) substrate by 193 nm ArF excimer laser induced photochemical modification of silicone into silicon oxide. Single layer of silica microspheres was easily formed on an adhesive silicone rubber before laser irradiation after dropping of silica microspheres dispersed in ethanol and subsequent tape peeling. The welding rate, the percentage of welded microspheres tested by ultrasonic cleaning with ethanol, was examined by varying the single pulse fluence and irradiation time of ArF excimer laser. The welding layer underneath microsphere, silicon oxide, was also found to emit white light of strong intensity under UV light illumination.     

Pulsed laser deposition: metal versus oxide ablation

We present experimental results of pulsed laser interaction with metal (Ni, Fe, Nb) and oxide (TiO₂, SrTiO₃, BaTiO₃) targets. The influence of the laser fluence and the number of laser pulses on the resulting target morphology are discussed. Although different responses for metal and oxide targets to repetitive laser irradiation could be expected due to the different band structures of metals and oxides, the optical response is quite similar for 248-nm laser irradiation. Therefore, the difference in response is largely caused by differences in thermal properties. Metal targets show periodic structures of the order of micrometers after consecutive pulses of laser radiation, while the SrTiO₃ and BaTiO₃ targets show a flat surface after ablation for relatively low fluences (1.0 Jcm^-2). The observed TiO₂ target ablation characteristics fall in between those of the ablated metals and perovskites, because ablation results in the presence of Ti-rich material, which shields the underlying stoichiometric target material from ablation. The final target morphology is dependent on fluence, number of pulses, and the movement of the target itself (rotating, scanning, or stationary). It can take between 15 and 75 pulses to reach a steady-state target morphology on a stationary target. PACS 79.20.Ds; 52.38.Mf; 81.15.Fg     

Morphology and composition on Al surface irradiated by femtosecond laser pulses

We study the surface chemicals and structures of aluminum plates irradiated by scanning femtosecond laser pulses in air for a wide range of laser fluence from 0.38 to 33.6 J/cm². X-ray photoelectron spectroscopy and X-ray diffraction analyses indicate clearly that crystalline anorthic Al(OH)₃ is formed under femtosecond laser pulse irradiation. Besides aluminum hydroxide, crystalline Al₂O₃ is also found in the samples irradiated at high laser fluence. Field emission scanning electron microscopy demonstrates that the surfaces of the samples irradiated with low laser fluence are colloidal-like and that nanoparticles with a few nanometers in size are embedded in glue-like substances. For high laser fluence irradiated samples, the surfaces are highly porous and covered by nanoparticles with uniform size of less than 20 nm.     

Dual-beam ablation of fused silica by multiwavelength excitation process using KrF excimer and F2 lasers

A new technique of dual-beam laser ablation of fused silica by multiwavelength excitation process using a 248-nm KrF excimer laser (ablation beam) coupled with a 157-nm F₂ laser (excitation beam) in dry nitrogen atmosphere is reported. The dual-beam laser ablation greatly reduced debris deposition and, thus, significantly improved the ablation quality compared with single-beam ablation of the KrF laser. High-quality ablation can be achieved at the delay times of KrF excimer laser irradiation shorter than 10 ns due to a large excited-state absorption. The ablation rate can reach up to 80 nm/pulse at the fluence of 4.0 J/cm² for the 248-nm laser and 60 mJ/cm² for the F₂ laser. The ablation threshold and effective absorption coefficient of KrF excimer laser are estimated to be 1.4 J/cm² and 1.2᎒⁵ cm^-1, respectively.     

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.     

Guidelines for efficient direct ablation of dielectrics with single femtosecond pulses

We provide guidelines to femtosecond laser users to select ad hoc laser parameters, namely the fluence and pulse duration, in the context of the development of ablation processes at the surface of dielectrics using single femtosecond pulses. Our results and discussion are based on a comprehensive experimental and theoretical analysis of the energy deposition process at the surface of fused silica samples and of their postmortem ablation characteristics, in the range of intensities from 10¹³ to 10¹⁵ W/cm². We show experimentally and numerically that self-induced plasma transient properties at the pulse timescale dramatically determine the efficiency of energy deposition and affect the resulting ablation morphology. In practice, we determine that the precise measurement of two characteristic fluence values, namely the laser-induced ablation threshold F _th,LIAT and the fluence F _opt for maximum ablation efficiency, are only required to qualify the outcomes of laser ablation at the surface of a dielectric in an extended range of applied fluence.     

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.     

Comparison of the transmission behavior of a triazeno-polymer with a theoretical model

The threshold fluence,F _Th, of ablation of a triazeno-polymer was measured in the low fluence range for thin films using conventional UV-spectroscopy. It was found that there is a clearly definedF _Th for 308 nm irradiation between 20 and 25 mJ cm^–2. In the case of 248 nm irradiation, a threshold fluence range between 16 and 32 MJ cm^–2 was found. The ablation rate for both irradiation wavelengths depends on film-thickness. For the XeCl excimer-laser, the point at which the rate becomes independent of thickness was observed to lie at a value which did not correspond to the calculated laser penetration depth, whereas for the KrF laser the independence was not reached within the applied thickness range (up to 0.35 m). Additional transmission measurements have been performed showing that the target transmission at 248 nm increases only slightly, whereas for 308 nm the transmission increases by a factor of approximately 4. This result shows that dynamic target absorption properties are very important for describing the ablation process. The results derived from the transmission studies and etch rates were analyzed theoretically with a two-level model of chromophore absorption. For 248 nm irradiation this model can describe the transmission behavior and the ablation rate. In the case of 308 nm irradiation, it was only possible to match one data set. A good agreement with the experimental transmission ratio does not match the ablation rate and vice versa.     

Patterned laser annealing of silicon oxide films

UV-absorbing silicon monoxide (SiO _x , x≈1) thin films on fused silica substrates are irradiated by an ArF excimer laser (wavelength 193 nm) in the sub-ablation threshold regime. Multi-pulse irradiation of films with ∼200-nm thickness at a fluence of about 100 mJ/cm² leads to a significant increase of the UV transmission, indicating the oxidation of SiO _x to SiO₂. The quality of the obtained films after this laser annealing process depends on the oxygen content of the environment. Irradiation in air at atmospheric pressure leads to the formation of sub-micron-sized oxide particles on top of the film. Structured illumination is applied either to form areas of the film with changed transmission and refractive index, or for the formation of regular particle patterns with sub-micron periods. These processes can be utilized for the fabrication of phase masks or for various types of surface functionalization.     

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.     

Synthesis and characterization of platinum nano sized particles by laser ablation in C<Subscript>2</Subscript>H<Subscript>6</Subscript>O<Subscript>2</Subscript> solution

Platinum nano sized particles (Pt NPs) are superior catalysts for many intentions, such as glucose sensors, cancer therapy, gas sensors, etc. Here, Pt NPs were produced by pulsed laser ablation in C₂H₆O₂ solution using Q-switched Nd:YAG laser, for the first time. Then, the influence of the laser fluence during synthesis of them was investigated; and they were characterized by UV–vis spectroscopy, TEM, FE-SEM, XRD, FT-IR, and Raman spectroscopy. The results showed that with increasing laser fluence, the mean particle size of the spherical NPs enhanced. Meanwhile, they had a polycrystalline cubic structure. Correspondingly, the plasmon peak position of generated NPs in the absorption spectra shifted from 257 to 266 nm, with a rise of laser fluence. The IR and Raman spectroscopy was used to achieve the information about the surface state of Pt NPs. We propose that the optimum adjusted laser fluence is an important factor to increase the ablation efficiency.     

XPS studies of short pulse laser interaction with copper

The effect of laser ablation on copper foil irradiated by a short 30 ns laser pulse was investigated by X-ray photoelectron spectroscopy. The laser fluence was varied from 8 to 16.5 J/cm² and the velocity of the laser beam from 10 to 100 mm/s. This range of laser fluence is characterized by a different intensity of laser ablation. The experiments were done in two kinds of ambient atmosphere: air and argon jet gas.The chemical state and composition of the irradiated copper surface were determined using the modified Auger parameter (α′) and O/Cu intensity ratio. The ablation atmosphere was found to influence the size and chemical state of the copper particles deposited from the vapor plume. During irradiation in air atmosphere the copper nanoparticles react with oxygen and water vapor from the air and are deposited in the form of a CuO and Cu(OH)₂ thin film. In argon atmosphere the processed copper surface is oxidized after exposure to air.     

Ablation induced by single-and multiple-femtosecond laser pulses in lithium niobate

We present results on the surface-damage threshold of lithium niobate after single-and multiple-femtosecond laser pulse irradiation at the pulse duration of 80 fs, with a 800-nm wavelength, and a repetition rate of 1 kHz. The surface-ablation threshold was found to decrease significantly with an increase in the pulse number applied to the surface until reaching an almost constant level due to an incubation effect, which is attributed to the laser-induced defect formation. The threshold of lithium niobate under a single shot is found to be 2.82 J/cm², and the threshold fluence for an infinite number of pulses F _th(∞) converges to a common value of 0.52 ± 0.06 J/cm² for N > 80. The results have the potential for application in laser micromachining and the fabrication of related optical devices and applications in frequency conversion by a femtosecond laser in lithium niobate.     

UV laser micromachining of piezoelectric ceramic using a pulsed Nd:YAG laser

UV laser (=355 nm) ablation of piezoelectric lead zirconate titanate (PZT) ceramics in air has been investigated under different laser parameters. It has been found that there is a critical pulse number (N=750). When the pulse number is smaller than the critical value, the ablation rate decreases with increasing pulse number. Beyond the critical value, the ablation rate becomes constant. The ablation rate and concentrations of O, Zr and Ti on the ablated surface increase with the laser fluence, while the Pb concentration decreases due to the selective evaporation of PbO. The loss of the Pb results in the formation of a metastable pyrochlore phase. ZrO₂ was detected by XPS in the ablated zone. Also, the concentrations of the pyrochlore phase and ZrO₂ increase with increasing laser fluence. These results clearly indicate that the chemical composition and phase structure in the ablated zone strongly depend on the laser fluence. The piezoelectric properties of the cut PZT ceramic samples completely disappear due to the loss of the Pb and the existence of the pyrochlore phase. After these samples were annealed at 1150 °C for 1 h in a PbO-controlled atmosphere, their phase structure and piezoelectric properties were recovered again. Finally, 1–3 and concentric-ring 2–2 PZT/epoxy composites were fabricated by UV laser micromachining and their thickness modes were measured by impedance spectrum analysis and a d₃₃ meter. Both composites show high piezoelectric properties. PACS 81.40.Gh; 77.84.-s     

Investigations on hydrophilic and hydrophobic silicon (100) wafer surfaces by X-ray photoelectron and high-resolution electron energy loss-spectroscopy

The paper reports on surface spectroscopy measurements of silicon single-crystal wafers which have been treated in order to obtain hydrophilic and hydrophobic surfaces, respectively. The wafers are characterized in terms of the oxidation behaviour in air (native oxides), their surface chemical composition and the chemical bonds involved. It is shown that the oxide on hydrophilic wafers mainly grows in the cleaning agent and consists of hydrated SiO₂ through all stages of the growth. On a hydrophobic surface, however, the oxidation begins with the formation of a lower oxidation state which turns into SiO₂ on storage in air. The thickness of the oxides on both surface types reaches 1.4–1.5 nm. Both the chemical shift in photoelectron spectroscopy and the frequency of the asymmetric Si-O-Si vibration in electron energy loss spectroscopy support the assumption of a reduced bonding angle of the oxygen bridge.Hydrophilicity is caused by singular and associated OH groups on the surface. Singular groups could be detected up to 700 K. There are hints that OH groups stabilize the oxide during heating. The hydrophobic state is mainly characterized by Si-H and Si-CH _x groups on the surface, whereas Si-F exists only in minor quantities. Si-H groups were stable up to approximately 900 K in UHV. Si-CH _x dehydrogenizes at temperatures between 500 and 700 K leaving SiC on the surface.