Direct 3D Patterning of TiO2 Using Femtosecond Laser Pulses

Two-photon polymerization of photosensitive materials irradiated by femtosecond laser pulses is now considered as an enabling technology for the fabrication of 3D structures, especially photonic crystals and photonic crystal templates. Depending on the topology and dielectric constant contrast of photonic crystals, their optical properties can be tailored in a desired manner. Since 1987, when the concept of 3D photonic crystal was introduced by Yablonovitch and John, photonic crystals have been a subject of intensive research. In spite of this, the fabrication of photonic crystals with a full 3D (or omni-directional) bandgap in the visible range is still a challenging task. To realize photonic crystals with a full photonic bandgap, 3D structuring of high refractive index materials is required. The high refractive index (ca. 2.4) and high transparency in the visible spectrum makes TiO2 a very promising photonic material. For many applications, it is desirable to have a simple technique for patterning this material in twoand even three dimensions. Conventionally, TiO2 is patterned by sputtering it onto a pre-patterned organic resist followed by lift-off. When thick films of TiO2 or complicated features are desired, the lift-off process does not work well. For 3D fabrication, the most attractive option so far has been to fabricate templates which were later infiltrated with a high refractive index material, followed by the removal of the original template structure. Another approach is to use inorganic–organic photosensitive materials (ormocers) for the fabrication of photonic crystals. In this case, there exists a possibility to skip the replication steps and to fabricate 3D inorganic structures directly. However, the inorganic content in these materials is not very high and the attempts to fabricate in three dimensions have resulted in porous structures. In order to eliminate the issue of making templates and their subsequent infiltration with a high refractive index material, a direct 3D fabrication of structures appears to be an attractive option. As2S3, a chalcogenide glass, was directly patterned in three dimensions by exploiting its photo-induced metastability. On the other hand, examples of direct patterning of oxides are nonexistent. In this paper, we will demonstrate a direct 3D patterning of TiO2 structures using femtosecond laser pulses. To enable such fabrication, a photosensitive sol– gel-based spin-coatable TiO2 resist was developed. The experimental setup used for the patterning is shown in Figure 1 and is similar to that used before. The TiO2 resist is transparent (refractive index = 1.68) to the femtosecond laser radiation of 780 nm wavelength, and therefore, allows focusing of laser pulses tightly into the material volume. In the focal area, where the intensity of femtosecond laser pulses is high enough to initiate multiphoton processes, bond-breaking in the TiO2 resist makes the irradiated regions insoluble in organic solvents such as acetone. This allows the fabrication of any computer-generated 3D structure by direct laser “recording” into the volume of the TiO2 resist. Because of the threshold behavior and nonlinear nature of this bond-breaking proC O M M U N IC A TI O N