Sol-gel derived GeO 2 -doped silica thin films (x)GeO 2 :(1Ϫx)SiO 2 with x ϭ 5 to 40 mol % were studied for heat-treatments from 500 to 1000°C. In the conventional single component sol-gel process, temperature is the process parameter that controls the porosity of the film. However, our results revealed that by varying Ge-doping, the film porosity, as determined by spectroscopic ellipsometry, can be tailored across the temperature range studied. The mechanisms contributing to the quasi-linear compositionaldependent porosity are Ge precursor chemistry and viscous sintering. This technique can be versatile in applications such as III-V optoelectronic devices realized by quantum-well intermixing.In optoelectronics, porous dielectric materials have been used as a mean to promote quantum well intermixing ͑QWI͒ to tune the operating wavelength of the different integrated photonic devices via impurity-free vacancy diffusion ͑IFVD͒. 1 These dielectric materials are used in a form of capping layer that is deposited on top of a given quantum well ͑QW͒ structure. It has been found that group III and/or V elements out-diffuse into the dielectric cap layer creating vacancies in the lattice structure of the alloy. Such vacancies propagate into the QW region and activate interdiffusion of the different elements across the quantum well and its barrier leading to a change in the bandgap profile. 2 Previous works reported that porosity in the dielectric cap determine the wavelength shifts of the QW structure. 3,4 The sol-gel process is a commercially promising technology compared with other thin film technologies, with advantages such as low cost, ease of doping variation, and high homogeneity of multicomponent oxide films. It is well known that sol-gel derived films are porous under moderate heat-treatment temperatures. The porosity of the films can be controlled by subjecting the films to different heat-treatments. For certain applications, there can be various constraints on the allowable thermal treatment that can be performed on the film; hence, other parameters are desired to control the porosity of the films. For example, to promote QWI, Ga-As based QW structures can withstand annealing temperatures up to ϳ900°C without deterioration in optical performance; while the more prominent In-P based QW structures can only tolerate up to 600°C due to its poor thermal stability. 5 In the light of photonic integration, where multiple bandgaps across a single substrate are required, 6 controlling porosity in the sol-gel dielectric caps by only annealing temperature would be impractical.Alternatively, the effects of doped-SiO 2 caps ͑i.e., phosphorus 7-9 ͒ have been demonstrated with bandgap tuning results attributed to the different physical properties of the cap, namely, the film porosity. However, the doping level of phosphorous has been restricted to less than 10 mol % as the material otherwise becomes hygroscopic.In this paper, we show that, by increasing the amount of GeO 2 content in our binary GeO 2 :SiO 2 sol-gel material, the...