Chris it is most unlikely photoshop will be the problem.
A common mistake is that the Alt key is not held down whilst the number keys are pressed.
It is possible that the font selected does not contain the required symbol.
Also check in Windows Control Panel - Keyboard settings - the Input Locales maybe set to some other langauge.
Another way to get a symbol is to copy and paste via Start Menu -> Programs -> Accessories -> System tools -> Character Map
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