N-tier is a generalization( and inclusive ) of three-tier architecture and I prefer using the former than latter. N-tier systems often extend the standard three-tiers by including additional resources such as leagacy systems(EIS), service-based components(EAI) etc.
Tiers not necessarily are aligned with physical boundaries. For instance, you can have a single instance of an app server host both the web tier and the
ejb tier. Tiers are conceptual architectural lines drawn mostly around the functionality provided by the components that make up the tier. Therefore, simply adding multiple web servers do not add additional tiers to the architecture.
Cheers,