Basically, a solar cell works by having two pieces of semiconductor material (commonly silicon) next to each other, one of the is p-type (excess holes, deficient in electrons) and the other is n-type (excess holes). As sunlight (photons) strikes the n-type semiconducter, electrons are ejected in accordance with the photoelectric effect to the p-type semicondutor and an emf is induced between these two semiconductor types, and if they are short circuited with an external circuit (load) then a current flows.
A photocell is basically a piece of semiconductor material that conducts better when in the presence of light, since the electrons are moved into the conduction band by the incoming photons as per the photoelectric effect.
Breathalysers contain a certain mixture of sulphuric acid, silver nitrate, potassium dichromate, and water. As alcohol mixes with these chemicals, they change colour from orange to green depending on the alcohol concentration that has been dissolved into it. A photocell is then used to measure this colour change, and report it on the display of the breathalyser.
For more info, check out these websites:
http://science.howstuffworks.com/breathalyzer.htm
http://science.howstuffworks.com/diode.htm
http://science.howstuffworks.com/solar-cell.htm
http://www.infoplease.com/ce6/sci/A0845833.html
http://www.infoplease.com/ce6/sci/A0838866.htm