Morphological evolution of individual microrods to self-assembled 3D hierarchical flower architectures of CuBixIn1−xSe2 for photo response applications

Abstract

CuInSe₂ and CuInGaSe₂ are extremely promising materials for solar cell applications, wherein bandgap shrinkage is highly desirable for manufacturing transparent/semitransparent layers. In this work, this shrinkage was achieved by replacing In with Bi, and the change in current–voltage responses for photodetector applications was further studied. CuBi_xIn_1−xSe₂ microrod (MR) flowers (x = 0, 0.2, 0.4, 0.6, and 0.8) were synthesized via microwave synthesis using different Bi/In concentrations. The variation in the composition of Bi/In caused alteration in structural, morphological, and optical behaviors. CuInSe₂ showed a polycrystalline nature, while Bi incorporation led to the appearance of a Bi₂Se₃ phase. Raman peaks corresponding to different vibrational bonds shifted with change in Bi/In content, indicating that the composition variation induced structural transformation inside the matrix. Morphological analysis showed a transition from MRs to MR-based flowers with the introduction of bismuth. Optical absorption was enhanced with an increase in Bi content due to a change in the MR size, forming a flower-like architecture. This reduced the optical bandgap by increasing defects and disorders in the forbidden gap. At 532 nm excitation, broad photoluminescence band emission was observed for all samples. Each spectrum showed three deconvoluted peaks, which were attributed to a transition among localized states over the forbidden gap region. The MRs demonstrated good photo response towards white light. Their photocurrent reduced from the μA to the nA range with varying compositions. The observed optical and electrical properties of the MRs are most suitable for various optoelectronic device applications.