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.     

Growth of oriented Pb(ZrxTi1-x)O3 thin films on glass substrates by pulsed laser deposition

Oriented crystalline Pb(Zr_xTi_1-x)O₃ (x=0.53) (PZT) thin films were deposited on metallized glass substrates by pulsed laser deposition (1060-nm wavelength Nd:YAG laser light, 10-ns pulse duration, 10-Hz repetition rate, 0.35-J/pulse and 25-J/cm² laser fluence), from a commercial target at substrate temperatures in the range 380-400 °C. Thin films of 1-3 7m were grown on Au(111)/ Pt/NiCr/glass substrates with a rate of about 1 Å/pulse on an area of 1 cm². The deposited PZT films with perovskite structure were oriented along the (111) direction, as was revealed from X-ray diffraction spectra. Fourier transform infrared spectroscopy (FTIR) was performed on different PZT films so that their vibrational modes could be determined. Piezoelectric d₃₃ coefficients up to 30 pC/N were obtained on as-deposited films. Ferroelectric hysteresis loops at 100 Hz revealed a remanent polarization of 20 7C/cm² and a coercive field of 100 kV/cm.     

Time-resolved measurements during backside dry etching of fused silica

The laser-induced backside dry etching (LIBDE) investigated in this study makes use of a thin metal film deposited at the backside of a transparent sample to achieve etching of the sample surface. For the time-resolved measurements at LIBDE fused silica samples coated with 125 nm tin were used and the reflected and the transmitted laser intensities were recorded with a temporal resolution of about 1 ns during the etching with a ∼30 ns KrF excimer laser pulse. The laser beam absorption as well as characteristic changes of the reflection of the target surface was calculated in dependence on the laser fluence in the range of 250-2500 mJ/cm² and the pulse number from the temporal variations of the reflection and the transmission. The decrease of the time of a characteristic drop in the reflectivity, which can be explained by the ablation of the metal film, correlates with the developed thermal model. However, the very high absorption after the film ablation probably results in very high temperatures near the surface and presumably in the formation of an absorbing plasma. This plasma may contribute to the etching and the surface modification of the substrate. After the first pulse a remaining absorption of the sample was measured that can be discussed by the redeposition of portions of the ablated metal film or can come from the surface modification in the fused silica sample. These near-surface modifications permit laser etching with the second laser pulse, too.     

Direct joining of glass substrates by 1 kHz femtosecond laser pulses

When a femtosecond laser pulse is focused at the interface of two transparent substrates, localised melting and quenching of the two substrates occur around the focal volume, bridging them due to nonlinear absorption. The substrates can then be joined by resolidification of the materials. We investigate the optimum irradiation conditions needed to join borosilicate glass substrates and fused silica substrates using a 1 kHz 800 nm Ti:sapphire amplifier. We characterised the joint strength and the transmittance through joint volumes as a function of laser energy and translation velocity. We found that a joining strength as large as 14.9 MPa could be obtained in both fused silica and borosilicate glass. Annealing the joint samples led to an increase in the joint strength. PACS 42.65.Jx; 42.70.Ce; 81.20.Vj     

Acoustic substrate expansion in modelling dry laser cleaning of low absorbing substrates

Acoustic expressions have been derived for the thermal expansion of substrate surfaces due to irradiation by an exponential laser pulse. The result of acoustic effects on three substrates (silicon, glass and silica) with different absorptions has been calculated.It has been shown that for substrates having relatively low absorptions, like silica and glass, acoustic considerations substantially reduce thermal expansion of the substrate caused by irradiation by nanosecond laser pulses relative to a quasi-static expansion model. In particular, the expansion of the substrate occurs over a much longer time frame than when the quasi-static approximation holds. Consequently, acceleration of the substrate surface is greatly reduced and laser cleaning threshold fluences for particle removal are increased.The predictions of the model of Arnold et al. when developed for acoustic considerations give reasonable agreement with experimentally found threshold fluences for alumina particles on silica and glass substrates although it underestimates the ratio of the threshold cleaning fluences of silica and glass. This could be due to the model underestimating the contribution of surface expansion to the laser cleaning process. The influence of multiple reflections in the substrate and departure from one dimensionality in the heat conduction on the threshold fluence was found to be insignificant. Thermal contact between the particle and the substrate was also found to have little effect on laser cleaning threshold fluences. Another mechanism that may enhance surface expansion is the 3D focussing of radiation by the particles. PACS 42.62.Cf; 81.65.Cf; 42.55.Lt     

Nanosecond UV laser damage and ablation from fluoride crystals polished by different techniques

Ablation thresholds and damage behavior of cleaved and polished surfaces of CaF₂, BaF₂, LiF and MgF₂ subjected to single-shot irradiation with 248 nm/14 ns laser pulses have been investigated using the photoacoustic mirage technique and scanning electron microscopy. For CaF₂, standard polishing yields an ablation threshold of typically 20 J/cm². When the surface is polished chemo-mechanically, the threshold can be raised to 43 J/cm², while polishing by diamond turning leads to intermediate values around 30 J/cm². Cleaved surfaces possess no well-defined damage threshold. When comparing different fluoride surfaces prepared by diamond turning it is found that the damage resistivity roughly scales with the band gap. We find an ablation threshold of 40 J/cm² for diamond turned LiF while the MgF₂ surface can withstand a fluence of more than 60 J/cm² without damage. The damage topography of conventionally polished surfaces shows flaky ablation across the laser-heated area with cracks along the cleavage planes. No ablation is observed in the case of chemo- mechanical polishing; only a few cracks appear. Diamond turned surfaces show small optical absorption but mostly cracks and ablation of flakes and, in some cases, severe damage in the form of craters larger than the irradiated area. The origin of such different damage behavior is discussed.     

Micromachining of quartz crystal with excimer lasers by laser-induced backside wet etching

We fabricated a well-defined pattern of lines and spaces on the surface of a quartz crystal plate (c-SiO₂) with micron-sized features, using laser-induced backside wet etching (LIBWE). The line patterns obtained using LIBWE showed a high aspect ratio of about 3. The etch rates of fused silica (a-SiO₂) ranged from 5 to 25 nm/pulse with KrF laser irradiation from 0.4-1.3 J/cm². Threshold fluences for a-SiO₂ and c-SiO₂ were 0.23 and 0.34 J/cm², respectively. The single-pulse etch depth was not affected by the repetition rates of laser pulses from 1-50 Hz.     

High-quality and high-efficiency machining of glass materials by laser-induced plasma-assisted ablation using conventional nanosecond UV, visible, and infrared lasers

This paper reports the micromachining of fused quartz and Pyrex glass by laser-induced plasma-assisted ablation (LIPAA) using a conventional nanosecond laser at wavelengths 266 nm, 532 nm, and 1064 nm, respectively. High-quality surface structuring can be achieved at each of these wavelengths. The micrograting formed has periods of 14 7m at 266 nm, 20 7m at 532 nm, and 30 7m at 1064 nm, respectively. The ablation rate using a 266 nm laser is much larger than that at longer wavelengths. The ablation thresholds of laser fluence are 0.7 J/cm² for 266 nm, 1.5 J/cm² for 532 nm and 3.7 J/cm² for 1064 nm, respectively. The 532 nm and 1064 nm lasers enable hole drilling in 0.5 and 2.0-mm thick fused quartz and Pyrex glass substrates of about 0.7-0.8 mm in diameter. However, the less destructive through channel can be only formed in Pyrex glass by using a 532 nm laser.     

Excimer laser ablation of thin titanium oxide films on glass

Thin titanium dioxide films are deposited on glass substrates by magnetron sputter deposition. They are irradiated in air, by means of a KrF excimer laser. The ablation rate is measured as a function of the laser fluence per pulse, F, and of the number of pulses, N. Above a fluence threshold, the films are partially ablated. The ablated thickness does not vary linearly with N. This is the signature of a negative feedback between the film thickness and the ablation rate. The origin of this negative feedback is shown to be due to either thermal or electronic effects, or both. At high F, the film detachs from the substrate.     

A novel laser transfer process for direct writing of electronic and sensor materials

MAPLE direct write (MAPLE DW) is a new laser-based direct-write technique which combines the basic approach employed in laser-induced forward transfer (LIFT) with the unique advantages of matrix-assisted pulsed-laser evaporation (MAPLE). MAPLE DW utilizes an optically transparent substrate coated on one side with a matrix consisting of the material to be transferred mixed with a polymer or organic binder. As in LIFT, the laser is focused through the transparent substrate onto the matrix. When a laser pulse strikes the matrix, the binder decomposes and aids the transfer of the material of interest to an acceptor substrate placed parallel to the matrix surface. MAPLE DW is a maskless deposition process which operates in air and at room temperature. Powders of Ag, BaTiO₃, SrTiO₃, and Y₃Fe₅O₁₂ with average diameters of 1 7m were transferred onto the surfaces of alumina, glass, silicon, and printed circuit board substrates. Parallel-plate and interdigitated capacitors and flat inductors were produced by MAPLE DW over Rogers RO4003 substrates. MAPLE DW was also used to transfer polymer composites for the fabrication of gas sensor chemoresistors. One such composite chemoresistor fabricated with polyepichlorohydrin/graphite was used to detect organic vapors with a sensitivity of parts per million.     

Influence of Different Substrates on Laser Induced Damage Thresholds at 1064nm of Ta2O5 Films

Ta2O5 films are prepared on Si, BK7, fused silica, antireflection （AR） and high reflector （HR） substrates by electron beam evaporation method, respectively. Both the optical property and laser induced damage thresholds （LIDTs） at 1064 nm of Ta2O5 films on different substrates are investigated before and after annealing at 673 K for 12 h. It is shown that annealing increases the refractive index and decreases the extinction index, and improves the O/Ta ratio of the Ta2O5 films from 2.42 to 2.50. Moreover, the results show that the LIDTs of the Ta2O5 films are mainly correlated with three parameters： substrate property, substoichiometry defect in the films and impurity defect at the interface between the substrate and the films. Details of the laser induced damage models in different cases are discussed.     

Influence of thermal diffusion on the laser ablation of thin polymer films

The laser ablation of a photosensitive triazene polymer was investigated with a ns XeCl excimer laser over a broad range of thicknesses (10–400 nm). We found that the ablation threshold fluence increased dramatically with decreasing film thickness for films thinner than 50 nm. Ablation on substrates with different thermal properties (sapphire, fused silica, PMMA) was investigated as well, and a clear influence of the substrate material was obtained. A mathematical model combining thermal diffusion and absorption effects was used to explain the experimental data. The model is in good agreement with the experimental data and shows that heat diffusion into the substrate plays a crucial role for the ablation process of very thin films. PACS 52.38.Mf; 44.05.+e; 81.05.Lg     

Structural and electrical properties of La0.5Sr0.5CoO3 films on SrTiO3 and porous a-Al2O3 substrates

Films of La_0.5Sr_0.5CoO₃ (LSCO) have been deposited on specially treated TiO₂-terminated (001) SrTiO₃ substrate surfaces and on macroporous polycrystalline !-Al₂O₃ substrates, having a mean pore diameter of 80 nm, by pulsed laser deposition. The films deposited on SrTiO₃ are good conducting, (001) textured, and exceptionally smooth (1-2 Å for 100 nm thick films). LSCO films deposited on porous !-Al₂O₃ are polycrystalline and exhibit good crystallographic and electrical properties despite the large substrate roughness and the differences in lattice parameters and crystal structure between the film and the substrate. Different growth modes have been observed on the porous !-Al₂O₃ substrates depending on the oxygen pressure during film deposition. Films grown at an oxygen pressure of 10^-1 mbar are macroporous, whereas films grown at 10^-2 mbar completely cover the substrate pores. In the latter case, strain effects lead to film cracking.     

Nanocrystalline growth and diagnostics of TiC and TiB2 hard coatings by pulsed laser deposition

Nanocrystalline coatings of TiC and TiB₂ were grown by pulsed laser deposition on Si(100) and on X155 steel at low substrate temperatures ranging from 40 °C to 650 °C. A pulsed KrF excimer laser was used with the deposition chamber at a base pressure of 10^-6 mbar. The morphology and structure of the films, studied with SEM, XRD, and TEM, showed that nanocrystalline films with a fine morphology of TiC and TiB₂ were deposited with a grain size of 10 nm-70 nm at all substrate temperatures. The growth of the polycrystalline coatings possessed a columnar morphology with a 𘜄¢ preferred orientation. The hardness of the coatings was determined to be 40 GPa and the elastic modulus, 240 GPa. The composition and the kinetics of the plume produced during the pulsed laser deposition of TiC and TiB₂ was studied under film growth conditions. The mass analysis of ions of the ejected material was performed by time-of-flight mass spectroscopy (TOF-MS) and showed the presence of Ti⁺ and C⁺ during TiC ablation and B⁺, B₂⁺, and Ti⁺ during TiB₂ ablation. The kinetic energies (KE) of the ions depended on the laser fluence which was between 0.5 eV and 340 eV. The kinetic energy and the evolution of the plasma was studied with a streak camera. The velocity of the plasma was of the order of 10⁶ cm/sec and was linearly dependent on the energy fluence of the laser. The emission spectroscopy of the plasma plume confirmed the atomic neutral and single excited species of Ti. These results show that coating growth basically occurs by the recombination of the ionic species at the surface of the substrate.     

Nd3+-doped LiYF4 thin films prepared by pulsed laser deposition

Nd:LiYF₄ (YLF) thin films were prepared on CaF₂ or YLF substrates by pulsed laser deposition, using a KrF laser for ablation of Nd:LiYF₄ single-crystal targets. For 10 J/cm², 450 °C and about 10^-6 mbar pressure, transparent and crystalline, highly textured, YLF films were obtained, without oxyfluoride or YF₃ contamination. High surface roughness is shown by optical microscopy and interface ion diffusion between film and substrate is evidenced by Rutherford backscattering spectroscopy. Fluorescence properties of the films are quite similar to those of bulk Nd:YLF crystal, which confirms the pure YLF composition and shows good conservation of Nd³⁺ ion doping rate. PACS 81.15.Fg; 68.55.Jk; 78.55.Hx     

Viscous flow and MOS properties of CaF2-B2O3-GeO2-SiO2 glasses with ionic bonds

The capacitance and voltage (C-V) characteristics of Metal-Oxide-silicon (MOS) capacitors passivated by CaF₂-B₂O₃-GeO₂-SiO₂ glasses with OH^m ions, water and fluoride contents were investigated. As the OH^m absorption coefficients of the glass increased, adverse effects on the recovery of hysteresis C-V curve shifts was observed. The content of OH^m ions is closely related to the fluoride content in the CaF₂-B₂O₃-GeO₂-SiO₂ glass. The viscous-flow point of the glass was lowered with increasing degree of ionic character obtained from Hannay's equation.     

Excimer laser patterned dielectric masks for the fabrication of diffractive optical elements by laser ablation

Masks for laser processing are generated by laser ablation patterning of dielectric layer systems. The application of these masks for the rapid fabrication of diffractive optical elements (DOEs) is presented. The diffractive optical elements are designed as phase-only elements, assuming an illumination with a plane wave. A continuous phase function is calculated using an iterative Fourier transform algorithm (IFTA). This continuous phase function is reduced to two or four levels by an iterative Fourier quantisation algorithm (IFQA) that is able to include focal power. The fabrication of the DOE is performed in a two-step process. First, a binary amplitude mask (or a set of masks for multi-level DOEs) is made by structured ablation of a highly reflective dielectric coating (HR 248 nm) from a fused silica substrate. This is accomplished by using an ArF excimer laser emitting at 193 nm, a wavelength that is sufficiently absorbed in the HfO₂/SiO₂-dielectric layer system, leading to precisely ablated mask structures. In the second step, this mask is used in a 4:1 projection configuration to generate a surface profile in a polymer substrate by ablation at 248 nm. The depth modulation can be defined by adjusting laser fluence and pulse number. Examples of DOEs ablated in polycarbonate are shown and their performance is characterised.     

Mo Back Contact for Flexible Polyimide Substrate Cu（In,Ga）Se2 Thin-Film Solar Cells

A dc magnetic sputtering process is applied to growth of a Mo back. contact layer onto the flexible polyimide （PI） and rigid soda-lime glass （SLC） substrates. The structural and electrical properties of the Mo layer coated on the two kinds of substrates are investigated by x-ray diffraction （XRD） and Hall effect measurements. The results show that the Mo layer on SLG indicate more better crystal quality and lower resistivity than that on the PI sheets. In contrast to the SLG substrate, the resistivity of the Mo layer on PI is increased by the vacuum annealing process at the substrate temperature of 450℃ under Se atmosphere, which is attributed to the cracked Mo layer induced by the mismatch of the coefficient of thermal expansion between PI and Mo material. The Cu（In,Ga）Se2 （CIGS） solar cells based on the PI and SLO substrates show the best conversion efficiencies of 8.16% and 10.98% （active area, 0.2cm^2）, respectively. The cell efficiency of flexible CIGS solar cells on PI is limited by its relatively lower fill factor caused by the Mo back contact.     

Pulse laser-induced particle separation from polymethyl methacrylate: a mechanistic study

The separation mechanism of opaque and transparent model micro-particles, graphite and polystyrene copolymer spheres, respectively, from polymethyl methacrylate (PMMA) substrates were investigated employing a ns-pulse laser radiating at 532 nm. The particles transparent in the visible wavelength range could be removed from PMMA efficiently in a very narrow fluence range between 1 and 2 J/cm² according to a simple 1D thermal expansion model. Above this fluence region, with single pulses, the transparent microspheres caused local ablation of the PMMA substrate in the optical microlens nearfield. This process led to removal of the particles themselves due to the expansion of the ablation plasma. The irregularly shaped graphite particles shaded the underlying substrate from the incoming radiation so that no optical nearfield damage mechanism could be observed. Therefore, a substantial cleaning window between 0.5 and more than 16 J/cm² was provided. The graphite data suggest an ablation mechanism of the particulates themselves due to a high optical absorption coefficient.     

Upconversion Luminescence of Er3+ Ions in Transparent Germanate Glass Ceramics Containing CaF2 Nanocrystals

The visible upconversion and near-infrared luminescence of Er3＋ ions in germanate glass ceramics containing GaF2 nanocrystals are investigated. The nanocrystals are characterized by x-ray diffraction （XRD） and transmission electron microscopy, showing their mean sizes less than 20hm. High transmittance of the glass ceramics is displayed by absorption spectra. The upconversion luminescence intensity in the glass ceramics increases significantly with increasing temperature. Both the shifts of the XRD peaks and the Stark-split shown in the luminescence spectra indicate the entrance of the Er3＋ ions into the CaF2 nanocrystals, which is confirmed by a Judd-Ofelt analysis. Possible mechanisms of the upconversion luminescence are analyzed.