Synthesis and characterization of electrodeposited copper indium selenide and copper (indium, gallium) selenide thin films

Electrodeposition is a cost effective method for growing polycrystalline thin films which is not limited by substrate/superstrate size and does not require the use of a vacuum. In this research, CuInSe2 and Cu(In,Ga)Se 2 polycrystalline thin films have been synthesized by electrodeposition. Both of these materials have very high absorption coefficients when compared to Si and GaAs, and can have their band gaps adjusted through the control of their stoichiometries. Both CuInSe2 and Cu(In,Ga)Se2 are direct band gap semiconductors with the chalcopyrite crystal structure. Therefore, these materials are important for use in high efficiency photovoltaic solar cells.; In an attempt to understand how the composition, morphology and crystallinity depend on electrodeposition conditions, various thin films of CuInSe2 and Cu(In,Ga)Se2 were grown by electrodeposition. These films were then characterized by a number of characterization techniques which include (1) scanning electron microscopy, (2) scanning tunneling microscopy, (3) energy dispersive spectroscopy, (4) X-ray diffraction, and (5) Auger electron spectroscopy. Results based on this research indicate two main conclusions. (1) Modulated or layered films of CuInSe2 can be grown by electrodeposition. Measurements made by Scanning Tunneling Microscopy of cleaved cross sections of the CuInSe2 layered films indicate the successful formation of layers. (2) Cu(In,Ga)Se2 thin films can be electrodeposited by a two-step process with minimal post treatment steps. The process developed here can be done at room temperature. Two electrochemical baths are used, one to electrodeposit a CuGa2 binary alloy, followed by the electrodeposition of a CuInSe2 thin film from another bath. The resulting bilayer film is then annealed in flowing argon at an elevated temperature to form the CIGS compound. Characterization results from measurements made by X-ray diffraction show that the resulting films maintain the basic chalcopyrite structure while the Bragg peaks shift to larger diffraction angles with increasing gallium content in the film. This is evidence to support the successful formation of CIGS films. This data is further corroborated by the energy dispersive spectroscopy and Auger electron spectroscopy data.