What exactly is blocking voltage in relation with Metal-semiconductor junction diodes? Is it related to breakdown voltage?
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Welcome. They are one in the same. Normally you do not exceed 50% of a diodes PRV rating, unless you like to gamble... – Aug 14 '20 at 04:10
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Both are same at sometime like when reverse voltage is given to diode then and its exceeds the breakdown level then both are same but when diode is forward biased and it tries to reach threshold value until then its only blocking voltage.

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