In the code below, I create a new command, \mbeq (short for "must be equal"...), which is a "math relational" operator (same type as the "ordinary" equal sign). Using the \overset command in the definition of the \mbeq operator automatically makes the new command "inherit" the type of the second argument of the \overset command; hence, it's not necessarily to assign the type "mathrel" explicitly.
\documentclass{article}
\usepackage{amsmath}
% "mbeq": must be equal
\newcommand{\mbeq}{\overset{!}{=}}
\begin{document}
$ a\mbeq b$, $x\xrightarrow{n\to 0}\infty$
\end{document}

Finally, I'm not aware of a commonly used term for the "must be equal" symbol (exclamation mark set over equality symbol). I searched detexify, and no predefined symbol came up.
\stackrelI'd recommend\overset– egreg Oct 21 '11 at 22:42\stackreland\overset. I guess the only motivation behind it is that it has an\undersetcounterpart which makes it more generic in terms of usage. – Werner Oct 21 '11 at 22:58\stackrel{!}{x}and you'll see the difference. Besides,\oversettries to guess the nature of the main symbol (relation or operation), so using the correct spacing; conversely,\stackrelalways creates a relation. – egreg Oct 21 '11 at 23:05