| The source of 9.3 mum absorption in silver selenogallate, AgGaSe 2 was investigated. Infrared spectrophotometric analysis of two as-received, reportedly stoichiometric, single crystals found 9.3 mum absorption coefficients of 0.109 and 0.101 cm-1. Infrared transmission of the slabs was otherwise uniform at 0.007 cm-1 through the range 6--12 gym. X-ray fluorescence measurements did not indicate an extrinsic impurity was responsible for the absorption. Intrinsic defect reactions were investigated and a Brouwer diagram was constructed to determine probable native defects. Analysis of the Brouwer diagram led to the hypothesis that the 9.3 mum absorption was caused by a native selenium vacancy. A series of heat treatments were conducted at 790°C with selenium partial pressures of 0.026, 0.040, 0.057, 0.138, and 0.243 atmospheres. Heat treatments below 0.060 atmospheres selenium partial pressure resulted in null or increased absorption at 9.3 mum up to 0.128 cm-1. Heat treatment at 0.243 atmospheres selenium partial pressure resulted in a decrease of the 9.3 mum absorption coefficient of 63% to 0.037 cm-1.A linear least-squares regression of the 9.3 mum absorption coefficient versus selenium partial pressure during heat treatment resulted in an equation for the absorption coefficient. alpha9.3mum = -0.4048 (PSe) atm -1cm-1 + 0.1322cm -1.The highest electrical resistivity of AgGaSe2 was measured at 7.6 x 1011 Ocm for a crystal with a 9.3 mum absorption coefficient of 0.037 cm-1. A linear least-squares regression of the 9.3 mum absorption coefficient versus bulk electrical resistivity resulted in an equation for the resistivity: rho = -7 x 1012 alpha9.3mumO cm2 + 1 x 1012 O cm. Thus, the electrical resistivity increases as the stoichiometric composition is approached and may be used as a measure of stoichiometry.The deleterious 9.3 mum absorption has not been entirely eliminated however, the reduction in the 9.3 mum absorption coefficient from greater than 0.100 cm-1 to 0.037 cm-1 will allow nonlinear optical devices to more than double the power handling of AgGaSe2 at 9.3 mum. |
