On the whole this is a big ask!
The issue with any speech recognition system is that it functions best after training. It needs context (what words to expect) and some kind of audio benchmark (what does each voice sound like). This might be possible in some cases, such as a TV series if you wanted to churn through hours of speech -separated for each character- to train it. There's a lot of work there though. For something like a film there's probably no hope of training a recogniser unless you can get hold of the actors.
Most film and TV production companies just hire media companies to transcribe the subtitles based on either direct transcription using a human operator, or converting the script. The fact that they still need humans in the loop for these huge operations suggests that automated systems just aren't up to it yet.
In video you have a plethora of things that make you life difficult, pretty much spanning huge swathes of current speech technology research:
-> Multiple speakers -> "Speaker Identification" (can you tell characters apart? Also, subtitles normally have different coloured text for different speakers)
-> Multiple simultaneous speakers -> The "cocktail party problem" - can you separate the two voice components and transcribe both?
-> Background noise -> Can you pick the speech out from any soundtrack/foley/exploding helicopters.
The speech algorithm will need to be extremely robust as different characters can have different gender/accents/emotion. From what I understand of the current state of recognition you might be able to get a single speaker after some training, but asking a single program to nail all of them might be tough!
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There is no "subtitle" format that I'm aware of. I would suggest saving an image of the text using a font like Tiresias Screenfont that's specifically designed for legibility in these circumstances, and use a lookup table to cross-reference images against video timecode (remembering NTSC/PAL/Cinema use different timing formats).
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There's a bunch of proprietary speech recognition systems out there. If you want the best you'll probably want to license a solution off one of the big boys like Nuance. If you want to keep things free the universities of RWTH and CMU have put some solutions together. I have no idea how good they are or how well they might be suited to the problem.
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The only solution I can think of similar to what you're aiming at is the subtitling you can get on news channels here in the UK "Live Closed Captioning". Since it's live, I assume they use some kind of speech recognition system trained to the reader (although it might not be trained, I'm not sure). It's got better over the past few years, but on the whole it's still pretty poor. The biggest thing it seems to struggle with is speed. Dialogue is normally really fast, so live subtitling has the extra issue of getting everything done in time. Live closed captions quite frequently get left behind and have to miss a lot of content out to catch up.
Whether you have to deal with this depends on whether you'll be subtitling "live" video or if you can pre-process it. To deal with all the additional complications above I assume you'll need to pre-process it.
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As much as I hate citing the big W there's a goldmine of useful links here!
Good luck :)