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The system of amorphous arsenic chalcogenides exhibits excellent photoconductivity and thermoelectricity. Due to the lack of detailed knowledge about their conduction mechanism and well-controlled preparation condition, junction device fabrication of such materials is remote. However, recent investigations by the author and other workers suggest that although the majority conduction carriers are holes, the contribution of electrons is significant especially in the Te-rich compounds. Therefore, from conductivity and thermopower investigation it is suggested that when sample preparation condition is suitable, junction device fabrication using these materials is a possiblity even without the doping of impurities which usually produce uncompatible structural symmetry microdomains with the host lattice.