| Description |
Cu2ZnSnSe4 (CZTSe) possess highly suitable optical and electronic properties for use as an absorber layer in thin film solar cells. CZTSe also has potential to achieve terawatt level solar energy production due to its inexpensive and abundant material constituents. Currently, fabricating CZTSe devices with the expected theoretical performance has not been achieved, making the growth and formation of CZTSe an interesting topic of research. In this work, a two-step vacuum fabrication process consisting of RF co-sputtering followed by reactive annealing was explored as a viable technique for synthesizing CZTSe thin films. Furthermore, the enhancement of the fabrication process by the incorporation of sodium during annealing was studied using a combinatorial approach. Film composition was analyzed using electron dispersive spectroscopy. Structure, phase morphology, and formation were determined using scanning electron microscopy, x-ray diffraction, atomic force microscopy and raman spectroscopy. Optical and electronic properties were characterized using UV-Vis and Voc were measurements under a one sun solar simulator. RF co-sputtering CuSe, ZnSe, and SnSe precursors produced films with good thickness uniformity, adhesion and stoichiometry control over 3 x 3 in2 substrates. Composition measurements showed that the precursor films maintained stability during an annealing process of 580o C for 20 minutes producing near stoichiometric CZTSe. However, grain size was small with an average diameter of 350 nm. The CZTSe film produced by this process exhibited a suitable absorption coefficient of > 104 cm-1 and aband gap near 1.0 eV. The film also produced an XRD pattern consistent with tetragonal CZTSe with no secondary phase formation with the exception of approximately 12.5 nm of interfacial MoSe2 formation at the back contact. The combinatorial investigation of the influence of sodium on CZTSe growth and morphology was achieved using a custom built constant withdraw shutter to evaporate NaF with a 0-60 nm thickness spread on the substrate prior to precursor sputtering. This experiment showed that the incorporation of NaF did enhance grain size; however, there was little correlation with initial NaF composition observed. It is concluded that NaF undergoes high degree of vapor transport and readily distributes nonuniformly throughout the film during the annealing process and also potentially escapes the annealing environment if not properly contained. An experiment on achieving Na incorporation by diffusion from a soda lime glass substrate resulted in a far more uniform enhancement of grain growth. The experiment also revealed that NaF greatly reduced precursor film adhesion to the substrate due to the hygroscopic nature of NaF. X-ray diffraction measurements also showed that the addition of the NaF layer was could potentially suppress the formation of MoSe2. |
