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We present a strategy for label-free biosensing using porous silicon diffraction gratings. The gratings are fabricated using a cost-effective, high-throughput stamping technique. Unlike traditional diffraction-based biosensors that rely on microcontact printing or lithography to create gratings for the localization of analytes on the top surface of the grating, in our structure analytes are free to infiltrate the porous network and increase the effective refractive index of the grating. The large surface area of porous silicon available for molecular binding offers the potential for enhanced diffraction response compared to nonporous gratings with limited surface area. Small molecule detection of 3-aminopropyltriethoxysilane is demonstrated.