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Surface coating of an integrating sphere is optimized for low losses. This white coating (barium sulfate or PTFE) acts like an ideal lambertian scatterer. all light is scattered (Ok, not 100%, but a very high percentage like 99,5%. See ressources) it is emitted in the hemisphere following the cosine law: perpendicular to the surface it's highest. ...
In a sphere, any light emitted from the center will reflect off the sides at normal incidence come back to the center. In a cube, some rays never return to the center, so you aren't measuring all of the light emitted, which defeats the purpose of the device.
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