A study of potential laser-induced degradation in remote standoff Raman spectroscopy for wall paintings

A mobile remote standoff Raman spectroscopy system operational at typical distances of 10 m was developed specifically for research of historical sites and wall paintings recently. Here we present an upgrade to that system informed by a thorough experimental investigation of the relevant laser-induced degradation issues. Reflectance spectroscopy as a more sensitive technique than Raman spectroscopy was used for monitoring and a new phenomenon of reversible alterations was detected in many paint samples at very low laser intensities of less than 1 W/cm² when Raman measurements detected no changes. Contrary to conventional wisdom, the intensity threshold for safe operation was found to decrease significantly for larger incident irradiation area in the case of a vermilion oil paint sample. Damage threshold in intensity for each material needs to be determined for different spot sizes, which can be orders of magnitude lower for 1 mm spot size compared with micro-Raman. Results from this study is also relevant to portable Raman systems which use similarly large spot sizes. However, the larger spot size still generates more Raman photons overall under safe operation than micro-Raman systems. Continuous-wave (CW) lasers are found to be best suited to efficient, that is more Raman signal detected over a given measurement time, and safe Raman operation than ns-pulse lasers at the same wavelength. While the damage threshold in intensity for ns-pulse lasers is much higher than that of CW lasers, the pulse energy allowed in one pulse for safe operation is still too low to allow detection of Raman signal, and the need for multiple pulses makes pulse laser inefficient owing to the low repetition rate necessary to ensure adequate heat dissipation between pulses. The safety of the upgraded system was evaluated and found that no permanent laser-induced degradation was detected within 60 s of laser irradiation for any of the paint samples.