You cannot make sure the button is only clicked once, as you have no control over user's browser. What you can do, though, is to add a hidden field, a token to your forms so that if you see a token you've already seen, you'll be able to return an already-calculated answer.
Update: In case of payment processing, it's not even a technique for preventing double submission—it's a technique protecting your clients from fraud. Check out OWASP's A5: Cross-Site Request Forgery (CSRF):
Preventing CSRF requires the inclusion of a unpredictable token in the body or URL of each HTTP request. Such tokens should at a minimum be unique per user session, but can also be unique per request.
The preferred option is to include the unique token in a hidden field. This causes the value to be sent in the body of the HTTP request, avoiding its inclusion in the URL, which is subject to exposure.
The unique token can also be included in the URL itself, or a URL parameter. However, such placement runs the risk that the URL will be exposed to an attacker, thus compromising the secret token.
Basically, each time you receive a payment form, you want to make sure it's a legitimate response to the form you've shown. Handling double submission comes free with security—a rare case indeed! ;)