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Copper indium gallium di-selenide (CIGS), a thin film solar cell material has its limitations with many vacancies and defects. It has been investigated for its effects on the radiation damage and its recovery mechanisms. The complex end materials of the CIGS such as CuInSe2 or CuGaSe2 has been studied in this article. In order to detect its defect level a piezoelectric photo-thermal spectroscopy (PPTS) has been developed to monitor its nonradiative relaxation pathway generated by impurity or defect level. Such thin films were studied using electron de-excitation processes to investigate the effect of the proton irradiation of the optical properties of very thin layer materials of CuInSe2 thin films.