Excitation Wavelength Dependence of Laser Ablation Mechanism of Urethane-Urea Copolymer Film Studied by Time-Resolved Absorbance Measurements

The excitation wavelength dependence of laser ablation dynamics of an azobenzene-containing urethane-urea copolymer film was investigated by measuring the laser fluence dependence of etch depth, transient absorbance change at each excitation wavelength, and transient absorption spectra. Moreover expansion/contraction dynamics was studied by applying nanosecond time-resolved interferometry. The threshold was determined at several excitation wavelengths from etch depth measurement, while time-integrated absorbance was obtained under excitation conditions. The photon energy required to remove the topmost of surface layer of the film did not .depend on excitation wavelength, and the penetration depth of excitation pulse dominated the etch depth. When the excitation wavelength was longer than 500 nm, permanent swelling was clearly observed but not for shorter wavelength excitation. In the latter case, photoisomerization occurred during excitation and the following photoreduction may play an important role. On the basis of the observations made in this study, a photochemical and photothermal mechanisms can explain mostly the short and long wavelength excitation results, respectively.