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Photoshop can not create true vector images or files. This is a very common misunderstanding. What Photoshop creates are vector containers with raster content and always saves both vector and raster information.

What Photoshop does is, upon output, it recalculates the vector container but only scales the raster contents in the container. This can result in "stair stepping pixels" your seeing on magnification.

Here is a shape created with the Rectangle Tool at 300% zoom...

[ATTACH]55238[/ATTACH]

Here is the same shape rotated and at 300% zoom...

[ATTACH]55239[/ATTACH]

If you need cleaner lines than this...........you need to use Adobe Illustrator.