Nano-roughness is one of the major factors degrading the emittance of electron beams that can be generated by high efficiency photocathodes, such as the thermally reacted alkali antimonide thin films. In this paper, we demonstrate a co-deposition based method for producing alkali antimonide cathodes that produce near atomic smoothness with high reproducibility. We calculate the effect of the surface roughness on the emittance and show that such smooth cathode surfaces are essential for operation of alkali antimonide cathodes in high field, low emittance radio frequency electron guns and to obtain ultracold electrons for ultrafast electron diffraction applications.