Conventionally, thin film chalcogenide(chalcopyrite and kesterite) solar cells have been synthesized by evaporating or sputtering metals followed by sulfurization or selenization. More recently, potentially low-cost high-throughput approaches have been demonstrated that form the chalcogenide directly from nanoparticle or molecular inks.The first part of the presentation will focus on our progress to develop of a class of solution-phase routes to Cu(In,Ga)(S,Se)2 and Cu2ZnSn(S,Se)4 that do not use suspensions of nanoparticles or hydrazine. We have developed a DMSO/thiourea solvation/complexation chemistry that yields 11.8% efficient CZTSSe solar cells [1], 13.0% efficient CISSe and 14.7% efficient CIGSSe [2]. We have discovered new effects of alloying and doping using a combinatorial ultrasonic spray coater and high-throughput screening method to map the optoelectronic properties of the chalcogenide absorber. The presentation will focus on: (1) the formation of films and elimination of deleterious elements, (2) incorporation of group I dopants, particularly lithium, and their effects of absorber properties and grain boundaries[1], and (3) germanium alloying to form Cu2Zn(Sn,Ge)(S,Se)4 with record high open circuit voltage relative to the maximum theoretical open circuit voltage for the bandgap [3]. The second part of the presentation will focus on our progress to develop: (1) high bandgap stable hybrid perovskites as the absorber material for the top cell, (2) NIR transparent HP top cells, and (3) tandem solar cell architectures. We will show the results combinatorial experiments [4] and newer data that utilize hyperspectral maps of steady-state absolute intensity photoluminescence (AIPL) to determine the quasi-Fermi level splitting (QFLS) that reveal the effects of methylammonium, formamidinium, cesium, and other group I cations on the ability of the materials to sustain large QFLS at steady-state and the material stability. We will also show new data on the QFLS for some novel lead-free 3D perovskites.  [1] Xin, Vorpahl, Collord, Braly, Uhl, Krueger, Ginger, & Hillhouse, Phys. Chem. Chem. Phys. 17, 23859-23866 (2015).  [2] Uhl, Katahara, & Hillhouse, Energy & Environmental Science 9, 130-134 (2016). [3] Collord & Hillhouse, Chem. Mater.28, 2067-2073 (2016). [4] Braly&Hillhouse, "Optoelectronic Quality and Stability of Hybrid Perovskites from MAPbI3 to MAPbI2Br using Composition Spread Libraries," J. Phys. Chem. C 120, 893-902 (2016).  [5] Katahara & Hillhouse, “Quasi-Fermi level splitting and Sub-bandgap Absorptivity from Semiconductor Photoluminescence” J. Appl. Phys. 116, 173504 (2014).