DarkWeb markets are by far the largest users of bitcoin by volume. anything you can not find on clear web will be available on dark markets. simple!
but extreme caution is needed when doing business on darkweb. always use VPN when accessing TOR and buy from trusted sellers with some reputation so that you dont end up exposed to feds or get scammed. still there will be no guarantee that the seller will be keeping log of his customers which may lead to disaster.