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They are both identical in structure. Both have a big "I" (intrinsic) region of lightly doped material sandwiched between to heavily doped regions.
The microwave PIN diode is used with a forward AND reverse DC current applied, to switch between an open and closed "switch" state. When reverse biased, the I region has no charge carriers, and looks like a very small RF Capacitance. The RF voltage is not big enough to cause charge carriers to be formed in the I region. RF PIN diodes are usually silicon.
The optical PIN dioide is always reversed biased. It is packaged so that light can shine onto the I region. When a photon of light impinges on the I region, an electron is generated and is accelerated toward postively biased side. If enough photons hit the I region, then an appreciable current flows across the I region. Optical PIN diodes are made of various compounds, usually containing GaAs. The type of compound has to be matched to the wavelength of light being detected.
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