In 1978 it was reported [1] that laser light counterpropagating in a glass optical fiber could inscribe a Bragg diffraction grating, ostensibly by altering the local refractive index of the glass in a periodic manner through an optical damage mechanism. Now, 20 years later, this discovery underscores a global multi-million-dollar activity in the manufacture of Bragg fiber gratings for the emerging photonics industry. Indeed, fiber optic gratings have asserted themselves as key elements in Mach±Zehnder interferometers for dense wavelength division multiplexing (DWDM) systems that enable fibers to carry more channels (wavelengths) of information. DWDM, in turn, has blossomed into a multi-billion-dollar optical bandwidth solution to fiber saturation created by burgeoning Internet traffic. In a broader context, Bragg gratings find widespread use in integrated optics devices such as distributed feedback lasers, filters, compensators, and mirrors for optical interconnects. Of course, this simple optical element can also find application across the entire field of spectroscopy, but the present trend toward miniaturization has created a new impetus for developing materials and methods to implement Bragg gratings in semiconductor and dielectric micro-optoelectronic benches for chemical sensing (biochips). Optical methods are among the preferred techniques for fabricating Bragg gratings. Ironically, there is as yet a rather incomplete understanding of the mechanisms used to create physical or refractive index gratings by photoinscription into glasses. [2] In this communication, we describe the preparation of acrylate-modified silica±titania sol-gel glass thin films and their use in direct optical ªself-processingº of micro-optical diffractive elements. For some time, we have been exploring the chemistry and photoprocessing of hybrid organic±inorganic sol-gel glasses for integrated optics device fabrication. [3,4] In this context, we were motivated to examine the potential of these materials for optical data storage and grating fabrication. Hybrid glass media would be particularly attractive for these purposes if a single-step photoprocess were involved. While investigating a variety of multinary hybrid glasses, we discovered that the incorporation of simple titanium alkoxide precursors yielded a particularly responsive glass for grating fabrication. We have shown previously that photoresponsive hybrid glasses can be used to record microscopic volume (refractive index) gratings in ridge waveguides by irradiation with an ArF + laser (193 nm) through a phase mask. [5] To create surface-relief gratings (SRGs) from hybrid glasses, a different procedure is required. Earlier research by our group [6] showed that volume compaction occurs during photoinduced acrylate monomer polymerization in families of hybrid glasses. Densification occurs by carbon±carbon bond formation during polymer chain growth, which induces collateral structural relaxation and condensation reactions in the metastable silica network. Since spatially resolved ...