Development and properties of surfactant-free water-dispersible Cu2ZnSnS4 nanocrystals: a material for low-cost photovoltaics

A simple, yet novel hydrothermal method has been developed to synthesize surfactant-free Cu2ZnSnS4 nanocrystal ink in water. The environmentally friendly, 2-4 nm ultrafine particles are stable in water for several weeks. Detailed X-ray diffraction (XRD) and high-resolution transmission electron microscopy revealed the formation of single-crystalline-kesterite-phase Cu2ZnSnS4. Elemental mapping by scanning electron microscopy/energy dispersive spectrometry corroborated the presence of all four elements in a stoichiometric ratio with minor sulfur deficiency. Finally, Raman spectroscopy ruled out the possible presence of impurities of ZnS, Cu2SnS3, SnS, SnS2, Cu(2-x)S, or Sn2S3, which often interfere with the XRD and optical spectra of Cu2ZnSnS4. X-ray photoelectron spectroscopic studies of the as-synthesized samples confirmed that the oxidation states of the four elements match those of the bulk sample. Optical absorption analyses of thin film and solution samples showed high absorption efficiency (>10(4) cm(-1)) across the visible and near-infrared spectral regions and a band gap E(g) of 1.75 eV for the as-synthesized sample. A non-ohmic asymmetric rectifying response was observed in the I-V measurement at room temperature. The nonlinearity was more pronounced for this p-type semiconductor when the resistance was measured against temperature in the range 180-400 K, which was detected in the hot-point probe measurement.