TECHNOLOGY FOCUS - METALLURGY - Preferred Components: The mixture of the first film is a stable mixture such that the molar ratio of all group IB-VIA1 and/or group IIIA-VIA1 alloys to all group IB-IIIA-VIA1 ternary alloy remains constant. The metal film is provided on a substrate optionally coated with a metal layer. The metal layer is molybdenum layer. The metal film comprises a mixture of copper, indium and/or gallium. It is copper-indium-gallium alloy metal film, or copper-indium alloy metal film. The group VIA1 element is selenium (Se). A source of the group VIA1 element is a gaseous mixture of hydrogen selenide and at least one inert gas such as argon. The binary alloy consists of indium selenide, copper selenide, or gallium selenide. The ternary alloy consists of copper indium selenide, or copper gallium selenide. The group IB element is copper, the group IIA1 is indium, the group IIIA2 is gallium, and the group VIA2 is sulfur. The pentenary alloy is of formula: Cu(In1-xGax)(Se1-ySy)2 (I). A source of sulfur is gaseous mixture of hydrogen sulfide and inert gas, where the molar ratio concentration of S to the inert gas is 0.1-10 molar%. The quat. alloy is of formula Cu(InGa)Se2 (II) or CuIn(Se1-ySy)2 (III). Preferred Compositions: The molar concentration of Se relative to the inert gas is 0.01-15 (preferably 0.05-0.3) molar percent. The first film has below 50 atomic % Se. Preferred Method: The metal film is heated rapidly to a reaction temperature of 300-500 (preferably 350-450)degreesC within 5 minutes. During the first heat treating step, the metal film is exposed to the source of VIA1 for 10-120 (preferably 30-60) minutes. The source of the V1A1 element is removed to maintain the stability of the mixture of the binary alloy and the group IB-IIIA-VIA1 ternary alloy. The first film is exposed to an inert atmosphere for 5-20 minutes, or cooled to below 200degreesC. The second film is heated at 450-600 (preferably 500-550)degreesC to form a third film. The third film is annealed at 500-600 (preferably 520-580)degreesC for 15-90 minutes. The first film is heat-treated at 400-500 (preferably 450)degreesC for 5-10 minutes. The first film is first annealed in the presence of inert gas at 100-600degreesC.