The combination of angle-resolved laser ablation with the use of a collimated beam is presented as a new approach to increase the depth-resolved capabilities of laser-induced breakdown spectrometry (LIBS). The effect of beam conditioning and the reduction of the effective sampling depth due to the angular dependence of laser ablation allow ablation rates lower than 2 nm/pulse for coated materials (Sn-coated steels and Cr-coated samples). Spectral information is obtained on a single-laser-shot basis. The effect of incidence angle has been examined from differentiated emission profiles, demonstrating the beneficial effect of working at incidence different from normal. A compromise between depth resolution and emission signal must be found at large angles due to the lower irradiance resulting from the increase in beam size at the interface for large angles of incidence. A comparison of the proposed approach with the analysis provided by a commercial glow-discharge device [glow discharge optical emission spectroscopy (GD-OES)] demonstrated quite satisfactory results.

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