I know this question is somewhat unclear since the word shi 是 never only meant this, but carries (and has done so for a long time) several meanings. The Gu Hanyu da cidian (via Pleco) lists some of them (not a direct quote; the numbers denote the century of the sources that the example sentences were taken from):
正確(5);訂正(3);以爲是(-4);表示肯定或加強肯定之詞(-3) etc.
But very generally speaking, shi was used in the language of the Lunyu (which I call here Classical Chinese) to denote »this« rather than any of its other meanings.
But when did shi start to mainly have the meaning as a copula that it has today, to be, as in »She is a student«, »Those are books«?