Polarized-thermoreflectance study of the band-edge transitions in Cu(Al_05In_05)S_2 solar-energy related crystal

Polarization dependence of band-edge excitonic transitions in Cu(Al(0.5)In(0.5))S(2) [denoted as Cu(AlIn)S(2)] has been characterized using polarized-thermoreflectance (PTR) measurements with E || <111 > and E perpendicular <111 > polarizations in the temperature range between 30 and 320 K. The measurements were done on as-grown {112} surface of the chalcopyrite crystal. The polarization dependence of the band-edge transitions of Cu(AlIn)S(2) clearly showed that the E(A) exciton is present prominently with E || <111 > polarization while the E(B) exciton appears significantly only in the E perpendicular <111 > polarized spectra. For the unpolarized spectra, both E(A) and E(B) features were combined. The E(A) feature is closely related to the E(0) transition, while the E(B) feature is that of E(0) + Delta(0) transition in the chalcopyrite. The crystal-field splitting energy of Delta(0) of Cu(AlIn)S(2) at the valence-band top is determined accurately by PTR experiments. Temperature dependences of transition energies of E(A) and E(B) transitions were analyzed. The band-edge excitons reveal an anomalous temperature-energy shift with increasing the temperatures from 30 to 320 K due to the variation of Cu d electrons' contribution to valence band that affected by the native defects inside Cu(AlIn)S(2). The PTR technique is more effective in studying the band-edge structure of the chalcopyrite crystal.