In addition to the basic hiragana sounds, other sounds can be made by combining two characters.

The two groups of characters that can be combined are the characters ending in 'i' and the characters beginning with 'y'.

An 'i' character is written normally, with a small 'y' character next to it.

It seems that the resultant sound contains a 'y' only if a character already exists that is the same as the combination without the 'y'.

For example, "sha" is written by combining the "shi" and "ya" characters. (しゃ)
"Cho" is written by combining the "chi" and "yo" characters. (ちょ)
"Ryu" is written by combining the "ri" and "yu" characters. (りゅ)