TECHNOLOGY FOCUS - IMAGING AND COMMUNICATION - Preferred Method: The step of deposition is done by spraying, spray coating, spray deposition, spray pyrolysis, printing, screen printing, inkjet printing, ink printing, stamp printing, transfer printing, pad printing, flexographic printing, gravure printing, contact printing, reverse printing, thermal printing, lithography, electrophotographic printing, electrodepositing, electroplating, electroless plating, bath deposition, coating, wet coating, dip coating spin coating, knife coating, roller coating, rod coating, slot die coating, meyerbar coating, lip direct coating, capillary coating, liquid deposition, solution deposition, layer-by-layer deposition, spin casting, and/or solution casting.    TECHNOLOGY FOCUS - INORGANIC CHEMISTRY - Preferred Method: The method (M1) involves, repeating steps f) and g). The step of heating is performed at 100-450 degrees C. The step of annealing is performed at 450-650 or at 450-650 degrees C in the presence of selenium vapor. In the method (M2), steps b) and/or c) are repeated at least one time in any order, where the additional layers have a concentration of the Group 13 the same or different as any of the previous layers. The steps b) and/or c) are repeated at least one time in any order and any of the layers are annealed after being formed. The steps b) and c) are repeated at least one time in any order, thereby forming at least two sodium-free layer. The first material is annealed before step c). The second material is annealed after being formed. In the method (M2), any of the layers is annealed in the presence of selenium vapor. The layer is formed by depositing an ink containing at least one polymeric precursor compounds. The layer is formed by chemical vapor deposition, metal-organic chemical vapor deposition, plasma enhanced chemical vapor deposition, atomic layer deposition, plasma-enhanced atomic layer deposition, sputtering, RF sputtering, DC sputtering, magnetron sputtering, evaporation, co-evaporation, electron beam evaporation, and/or laser ablation. Preferred Components: The ink layer is free from alkali ions, or free from sodium ions. The Group 13 atom is indium, gallium, or aluminum. The Group 13 atom is Ga and the concentrations are each a percentage that Ga atoms represent of the total of In plus Ga atoms, Ga/(In+Ga). The percentage that Ga atoms represent of the total of In plus Ga atoms, Ga/(In+Ga), within the gradient varies from 0-100%. The portion of the gradient is step-up gradient, step-down gradient, step-up-hold-step-down gradient, step-down-hold-step-up gradient, continuous gradient, downhill gradient, uphill gradient, depletion layer gradient, and/or enrichment layer gradient. The portion of the gradient has a steepness of greater than or equal to 20% per micrometer, where the percentage represents the increase or decrease in the concentration that Ga atoms represent of the total of In plus Ga atoms, Ga/(In+Ga). The substrate is selected from semiconductor, doped semiconductor, silicon, gallium arsenide, insulators, glass, molybdenum glass, silicon dioxide, titanium dioxide, zinc oxide, silicon nitride, a metal, metal foil, molybdenum, aluminum, beryllium, cadmium, cerium, chromium, cobalt, copper, gallium, gold, lead, manganese, molybdenum, nickel, palladium, platinum, rhenium, rhodium, silver, stainless steel, steel, iron, strontium, tin, titanium, tungsten, zinc, zirconium, metal alloy, metal silicide, metal carbide, polymer, plastic, conductive polymer, copolymer, polymer blend, polyethylene terephthalate, polycarbonate, polyester, polyester film, mylar, polyvinyl fluoride, polyvinylidene fluoride, polyethylene, polyetherimide, polyethersulfone, polyetherketone, polyimide, polyvinylchloride, acrylonitrile butadiene styrene polymer, silicone, and/or epoxy. The precursor inks contain a copper indium gallium selenium (CIGS) polymeric precursor compound. The precursor inks contain a copper indium selenium (CIS), aluminum indium selenium (AIS), aluminum indium gallium selenium (AIGS), copper aluminum indium selenium (CAIS), copper aluminum indium gallium selenium (CAIGS), copper indium gallium aluminum selenium (CIGAS), aluminum indium gallium aluminum selenium (AIGAS) or copper aluminum indium gallium aluminum selenium (CAIGAS) polymeric precursor compound. The precursor inks contain a compound of formula M'b(ER)3. The precursor inks contains a compound of formula M'a(ER). The precursor ink contains sodium ions (0.01-2%). The final film material on the substrate is a CIGS photovoltaic material. The final film material on the substrate is a CIS, AIS, AIGS, CAIS, CAIGS, CIGAS, AIGAS or CAIGAS material. The photovoltaic absorber material on the substrate is a CIGS photovoltaic material. The photovoltaic absorber material on the substrate is a CIS, AIS, AIGS, CAIS, CAIGS, CIGAS, AIGAS or CAIGAS material.M'b=Al, Ga, or In;M'a=Cu, Ag, or Au;E=S or Se;R=alkyl, aryl, heteroaryl, alkenyl, amido, or silyl. EXAMPLE - No suitable example given.