Inorganic semiconductor compounds, e.g., CIGS and CZTS, are promising materials for thin film solar cells because of their high light absorption coefficient and stability. Research on thin film solar cells using this compound has made remarkable progress in the last two decades. Vacuum-based processes, e.g., co-evaporation and sputtering, are well established to obtain high-efficiency CIGS and/or CZTS thin film solar cells with over 20% of power conversion. However, because the vacuum-based processes need high cost equipment, they pose technological barriers to producing low-cost and large area photovoltaic cells. Recently, non-vacuum based processes, for example the solution/nanoparticle precursor process, the electrodeposition method, or the polymer-capped precursors process, have been intensively studied to reduce capital expenditure. Lately, over 17% of energy conversion efficiency has been reported by solution precursors methods in CIGS solar cells. This article reviews the status of non-vacuum techniques that are used to fabricate CIGS and CZTS thin films solar cells.

The effect of a sputter deposition sequence of Cu, Zn, and Sn metal layers on the properties of Cu2ZnSnS4 (CZTS) was systematically studied for solar cell applications. The set of Cu/Sn/Zn/Cu multi metal films was deposited on a Mo/SiO2/Si wafer using dc sputtering. CZTS films were prepared through a sulfurization process of the Cu/Sn/Zn/Cu metal layers at 500˚C in a H2S gas environment. H2S (0.1%) gas of 200 standard cubic centimeters per minute was supplied in the cold-wall sulfurization reactor. The metal film prepared by one-cycle deposition of Cu(360 nm)/Sn(400 nm)/Zn(400 nm)/Cu(440 nm) had a relatively rough surface due to a well-developed columnar structure growth. A dense and smooth metal surface was achieved for two- or three-cycle deposition of Cu/Sn/Zn/Cu, in which each metal layer thickness was decreased to 200 nm. Moreover, the three-cycle deposition sample showed the best CZTS kesterite structures after 5 hr sulfurization treatment. The two- and three-cycle Cu/Sn/Zn/Cu samples showed high-efficient photoluminescence (PL) spectra after a 3 hr sulfurization treatment, wheres the one-cycle sample yielded poor PL efficiency. The PL spectra of the three-cycle sample showed a broad peak in the range of 700-1000 nm, peaked at 870 nm (1.425 eV). This result is in good agreement with the reported bandgap energy of CZTS.