Ionic conducting thin film amorphous electrolytes are promising candidates for microelectronics applications. This study presents an investigation into the structure and composition of lithium phosphorus oxynitride (LiPON) thin film electrolyte prepared using radio frequency (RF) sputtering on Li(3)PO(4) target. The ionic conductivity of LiPON thin films has been dramatically improved by decreasing N(2) pressure. X-ray photoelectron spectra (XPS) were used to determine the structure and composition of LiPON thin films. It was found that increasing the N(2) pressure during the deposition process resulted in a greatly decreased formation of triply coordinated -N <(N(t)) as compared to doubly coordinated -N=(N(d)) in LiPON thin films. These results indicate that the N(t) structural unit plays an important role in the improvement of ionic conductivity as compared to the N(d) structural unit. It also shows that PO(2)N(2) tetrahedra with two N(t) structural units exist in LiPON thin films at low N(2) pressures. Consequently, the improved ionic conductivity of the LiPON thin film deposited at low pressure results from the existence of PO(2)N(2) tetrahedra with two Nt structural units in LiPON thin film. PO(2)N(2) tetrahedra with two N(t) structural units provides higher cross-linking density of the glass network and lower electrostatic energy than with two N(d) structural units.