Abstract. Laser-ionization Time-Of-Flight (TOF) massspectrometric studies have been carried out on the 532 nm and 1064nm laser ablation products from a nitrogen-rich polymer. The polymer used had an elemental composition of C6.oNs.9H3. 4 and consisted of C = N , C --N , and N --H chemical bonds. The TOF mass spectra observed were composed of various peaks (_< 150 amu) depending on the ablation laser wavelength. The primary peaks were assigned to C +, CN +, CH,N (n = 1 -3) and C2H2N ;-for 532 nm ablation, and C +, C~, HCN +, HCCN +, C H 2 N H +, HNCN +, H 3 N C N + and C4HgN~ -for 1064nm ablation. The flight velocity distributions with peak velocities ranging from ~8.6 x 103 cm/s to ~3.8 x 104 cm/s were measured for these products. The distinct velocity distributions observed between small and large products indicate the presence of two origins in the fragment ejection process from the polymer for both 532 nm and 1064 nm ablation. Furthermore, we suggest an importance of the translational energy of the fragments for the product generation in the laser plume. PACS: 81.15, 82.80, 42.62 Numerous gaseous and solid products are generated by ultraviolet laser ablation of organic polymers [1]. The feature and abundance of the products depends strongly on the kind of polymer used and laser irradiation conditions such as wavelength, fluence, and pulse repetition rate. By means of mass spectrometry, extensive characterization of ablated gaseous products from several polymers have been performed [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17]. Specifically, the primary products were identified and the flight velocity distribution of each product was determined. In addition, formation of large carbon clusters were detected and studied. The products detected were composed of both neutral and ionic species. The ratio of neutral to ionic species depended on the laser fluence at the polymer surface. At relatively lower fluences, most of the products were neutrals, which were characterized by quadrupole or laser-ionization Time-Of-Flight (TOF) mass spectrometry.The ablated neutral species from PolyMethylMethAcrylate (PMMA) have been measured with the use of a quadrupole mass spectrometer [2-4]. Danielzik et al.[2] have reported, for 193-nm ArF laser irradiation, the detection of MMA monomer with thermal MaxwellBoltzmann (fluence < 120 mJ/cm 2) and highly directional non Maxwell-Boltzmann (> 120 mJ/cm 2) velocity distributions. Estler and Nogar [3] have observed a dramatic change of ablation products from PMMA depending on the irradiation laser wavelength. At 266 nm and above, the products were dominated by monomer, CO2, and CO. At wavelengths below 266 nm, methyl formate appeared as a major product. Mass analysis was also carried out on the ablation products at 266 nm from tetrafluoroethylene, polycarbonate, and PolyStyrene (PS), in addition to PMMA [4]. Various small fragments and the PS monomer were detected.Laser-ionization TOF mass spectrometry has been employed to examine the ablation products from several polym...