Refractive indices of a chemically amplified photoresist were changed by femtosecond (fs) laser irradiation without post exposure bake (PEB) treatment. We have proposed a combined process of fs nonlinear lithography and plasma etching for the fabrication of functional photonic devices with 3-D surfaces of inorganic materials. In this study, we report the nonlinear lithographic properties using fs laser pulses focused by a low-NA objective lens. Diffraction gratings were written directly inside the pre-baked resists by fs laser nonlinear absorption. From diffraction efficiencies using He-Ne laser light, refractive indices were changed by 8 × 10-3 without PEB treatment which was required for cross-linking reaction. In contrast, no changes of refractive index were observed in the case of ultraviolet light exposure (i-line). Considering this large refractive index change and the threshold intensity of nonlinear absorption of the resist, self-guiding of fs laser pulses can occur due to the optical confinement in the radial direction. In fact, filamentary patterns which were optical-axially asymmetric and longer than the focal depth could be obtained without translating the focal spot using this lithographic property.
SiO2-based variable microfluidic lenses were fabricated by femtosecond laser lithography-assisted micromachining
(FLAM). Optofluidic devices have attracted much interest because the adaptive nature of liquids in microfluidics enables
unique optical performance that is not achievable within all solid state devices. SiO2-based microfluidic devices are,
particularly, attractive due to high transparency, physical and chemical stabilities. However, it is generally rather difficult
to form the microstructures in microchannels because photolithography process is limited to planar substrates. In our
study, we fabricated SiO2-based variable microfluidic lenses, which had micro-Fresnel lenses inside the channels, by
using FLAM, which was a combined process of nonlinear lithography and plasma etching. The resist patterns of the
Fresnel lenses were directly written inside chemically amplified negative-tone photoresist on SiO2-based microchannels
of 250 μm width and 6 μm depth using femtosecond laser-induced nonlinear optical absorption. Following that, the
patterns were transferred to the bottom of the channels by using CHF3 and O2 mixed plasma. SiO2-based Fresnel lenses
with smooth surface were formed on the bottoms. When the channel was filled with the air, the focal spot was observed
2020 μm from the lens surface. By injecting silicone oil into the channel, the incident light was switched to the
dispersed.
SiO2-based diffractive/refractive hybrid microlenses were fabricated by using femtosecond laser-induced nonlinear
optical processes. Recently, hybrid devices have received much attention as important components for optical pickup
systems and integrated sensors. SiO2-based devices are particularly promising because of high transparency, physical and
chemical stabilities. For these devices, microfabrication upon nonplanar substrates such as convex lenses, which is
difficult for the semiconductor processes, is required. In this study, microFresnel lens patterns were directly written
inside positive-tone resists upon convex microlenses of 240 μm diameters by using femtosecond laser-induced nonlinear
absorption. The spot diameters are primarily determined at any position inside the resist by the region volume at which
the nonlinear absorption occurs. Therefore, the precise patterns could be formed even upon the nonplanar substrates.
After post-exposure-bake and development treatment, the patterns were transferred onto underlying lenses by CHF3
plasma. Here, the etching depth was 1 μm. Consequently, SiO2-based hybrid lenses with smooth surfaces were obtained. When He-Ne laser of 632.8 nm wavelength was coupled to this hybrid lens, the focal spot was 630 μm from the lens
surfaces. This focal length agreed with theoretical value of 618 μm. More functional optical devices would be realized
by improvement of fabrication processes.
Silica-based nonplanar surface structures were fabricated by use of femtosecond laser lithography-assisted
micromachining (FLAM), which is a combined process of femtosecond laser lithography and plasma etching. Diffractive
optical elements (DOEs) are widely used for photonic applications such as optical pickup, interconnection and so forth.
Most DOEs have been produced by semiconductor fabrication process. Although this process is useful to form
complicated fine structures, there exist two problems. First, it is rather difficult to fabricate nonplanar surfaces including
slopes and curves, which is effective to enhance diffraction efficiencies of DOEs. Second, microstructures cannot be
fabricated onto nonplanar substrates. In the FLAM, nonplanar patterns are directly written inside resists by use of
femtosecond laser-induced nonlinear optical absorption. Then, the patterns are transferred to underlying silica glasses by
CHF3 plasma. By use of FLAM, we successfully fabricated silica-based microFresnel lenses including curves and slopes
on planar substrates and cross-grating structures onto a convex microlens. In particular, as for the latter, uniform grating
structures with smooth surfaces were observed even at top and curved regions of the lenses. The FLAM is expected to be
useful for the fabrication of highly functional DOEs such as diffractive/refractive hybrid microlenses.
High-temperature-resistant laser-induced Bragg gratings were formed in Ge-B-SiO2 thin glass films fabricated by the plasma enhanced chemical vapor deposition method. Such gratings were induced by exposure of an interference pattern with KrF excimer laser and subsequently annealing at 600°C. The SEM observation of the grating after HF etching revealed that the origin of the grating was the periodic precipitation of crystalline 20 - 40 nm-diameter Ge nanoparticles. Nanoparticles precipitated predominantly in the unirradiated region after laser-induced refractive index change completely erased after annealing up to 500°C. The maximum value of refractive index modulation Δn was 6.8 x 10-3 at 632.8 nm, which corresponds to the Δn nearly 10 times as large as that before annealing. A channel waveguide with high-temperature-resistant-grating exhibited high diffraction efficiency and excellent thermal stability.
Waveguide filters with extremely thermally stabilized KrF laser-induced gratings were fabricated in the highly photosensitive Ge-B-SiO2 thin films. It was discovered that a completely new-type grating with high diffraction efficiency and thermal stability could be formed by annealing a conventional laser-induced grating at 600°C. Such thermally induced gratings couldn't be erased after repeated heat treatment alternating between room temperature and 600°C. We printed a grating in slab waveguide by irradiation with a KrF excimer laser followed by the annealing at 600°C, and then formed the channel in the region of the grating using standard photolithography process. The diffraction peak of 17 dB in depth at 1535.04 nm wavelength was observed after repeated heat treatment alternating between room temperature and 400°C. These thermally stabilized waveguide filters are promising candidate for the highly reliable optical and sensing devices.
We found out that GeO2-B2O3-SiO2 thin films fabricated by plasma enhanced chemical vapor deposition method exhibited not only large photo-induced but also thermo-induced refractive index increases, both of which were above 10-3. The former was observed after irradiation with KrF excimer laser, and the latter was induced by annealing at 600°C. The thermo-induced refractive index increase was closely related to the formation of thermo-induced absorption bands during the annealing, and could be suppressed by the laser irradiation prior to the annealing. Bragg gratings were printed in the films by the laser irradiation through the phase mask without H2 loading. The diffraction efficiency decreased rapidly by the annealing up to 500°C, but drastically increased after the annealing at 600°C. The thermo-induced gratings couldn’t be erased by the repeated heat treatments between room temperature and 600°C at all. Considering the suppression of thermo-induced index increase by the laser irradiation, this grating was expected to have the reverse pattern of refractive index compared to that of the as-printed one, and might be applicable to the highly reliable optical and sensing devices.
GeO2-B2-O3-SiO2 thin films were fabricated by plasma enhanced chemical vapor deposition method. Boron codoping into a GeO2-SiO2 thin film induced large absorption in the vicinity of 240nm, and OH absorption decreased compared to GeO2-SiO2 films. These films of 5 micrometers in thickness exhibited large positive refractive index change without hydrogen loading by irradiation with ArF (193nm) excimer laser pulses. Induced refractive index change was approximately 0.002 which was measured by the prism coupling method. A waveguide was written in this high photosensitive glass film by UV irradiation. The guided mode of the waveguide seems to be single and estimated refractive index change was approximately from 0.003 to 0.004. Three unique phenomena were found in 0.2micrometers thick films on Si substrate. First, these films exhibited large negative refractive index and positive thickness changes by irradiation with ArF laser pulses. Induced negative index change was larger than 0.02 and thickness change was more than 1%. Silica films doped only boron or germanium didn't exhibit such negative index changes. Second, the annealing before laser irradiation decreased the photosensitivity of these films remarkably. Third, these induce refractive index and thickness changes were decreased with time rapidly. These mechanisms were under investigation.
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