Just drag the library from your Pictures folder onto the external HD to make a copy there. The library should be located in your Pictures folder that's in your Home folder.
If you want to make your Home/Library folder (not the iPhoto Library folder) permanently visible do this:
In Lion the Library folder is now invisible. To make it permanently visible enter the following in the Terminal application window: chflags nohidden ~/Library and hit the Enter button - 10.7: Un-hide the User Library folder.
Most Simple Back Up
Drag the iPhoto Library from your Pictures Folder to another Disk. This will make a copy on that disk.
Slightly more complex:
Use an app that will do incremental back ups. This is a very good way to work. The first time you run the back up the app will make a complete copy of the Library. Thereafter it will update the back up with the changes you have made. That makes subsequent back ups much faster. Many of these apps also have scheduling capabilities: So set it up and it will do the back up automatically. Examples of such apps: Chronosync or DejaVu . But are many others. Search on MacUpdate