ABSTRACT
Understanding the origin and distribution of electronic gap states in metal halide perovskite (MHP) thin films is crucial to the further improvement of the efficiency and long-term stability of MHP-based optoelectronic devices. In this work, the impact of Lewis-basic additives introduced in the precursor solution on the density of states in the perovskite bandgap is investigated. Ultraviolet photoemission spectroscopy and contact potential difference measurements are conducted on MHP thin films processed from dimethylformamide (DMF)-based solutions to which either no additive, dimethylsulfoxide (DMSO), or N-methylpyrrolidine-2-thione (NMPT) is added. The results show the presence of a density of states in the gap of methylammonium lead halide films processed from DMSO-containing solution. The density of gap states is either suppressed when the methylammonium concentration in mixed cation films is reduced or when NMPT is used as an additive, and eliminated when methylammonium (MA) is replaced with cesium or formamidinium (FA). These results are consistent with the notion that reaction products that result from DMSO reacting with MA+ in the precursor solution are responsible for the formation of gap states.
ABSTRACT
The hybrid methylammonium (MA) lead halide MAPbX3 perovskites present an appealing optoelectronic behavior with applications in high-efficiency solar cells. The orientation of the organic MA units may play an important role in the properties, given the degrees of freedom for internal motion of MA groups within the PbX6 network. The present neutron powder diffraction study reveals the dynamic features of the MA units in the hybrid perovskite series MAPb(Br1-x Clx )3 , with x=0, 0.33, 0.5, 0.67, and 1. From difference Fourier maps, the H and C/N positions were located within the PbX6 lattice; the refinement of the crystal structures unveiled the MA conformations. Three different orientations were found to exist as a function of the chlorine content (x) and, therefore, of the cubic unit-cell size. These conformations are stabilized by H-bond interactions with the halide ions, and were found to agree with those reported from theoretical calculations.
ABSTRACT
We report the electrical properties of rubidium-incorporated methylammonium lead iodide ((RbxMA1-x)PbI3) films and the photovoltaic performance of (RbxMA1-x)PbI3 film-based p-i-n-type perovskite solar cells (PSCs). The incorporation of a small amount of Rb+ (x = 0.05) increases both the open circuit voltage (Voc) and the short circuit photocurrent density (Jsc) of the PSCs, leading to an improved power conversion efficiency (PCE). However, a high fraction of Rb+ incorporation (x = 0.1 and 0.2) decreases the Jsc and thus the PCE, which is attributed to the phase segregation of the single tetragonal perovskite phase to a MA-rich tetragonal perovskite phase and a RbPbI3 orthorhombic phase at high Rb fractions. Conductive atomic force microscopic and admittance spectroscopic analyses reveal that the single-phase (Rb0.05MA0.95)PbI3 film has a high electrical conductivity because of a reduced deep-level trap density. We also found that Rb substitution enhances the diode characteristics of the PSC, as evidenced by the reduced reverse saturation current (J0). The optimized (RbxMA1-x)PbI3 PSCs exhibited a PCE of 18.8% with negligible hysteresis in the photocurrent-voltage curve. The results from this work enhance the understanding of the effect of Rb incorporation into organic-inorganic hybrid halide perovskites and enable the exploration of Rb-incorporated mixed perovskites for various applications, such as solar cells, photodetectors, and light-emitting diodes.
ABSTRACT
Given that the highest certified conversion efficiency of the organic-inorganic perovskite solar cell (PSC) already exceeds 22 %, which is even higher than that of the polycrystalline silicon solar cell, the significance of new scalable processes that can be utilized for preparing large-area devices and their commercialization is rapidly increasing. From this perspective, the electrodeposition method is one of the most suitable processes for preparing large-area devices because it is an already commercialized process with proven controllability and scalability. Here, a highly uniform NiOx layer prepared by electrochemical deposition is reported as an efficient hole-extraction layer of a p-i-n-type planar PSC with a large active area of >1â cm2 . It is demonstrated that the increased surface roughness of the NiOx layer, achieved by controlling the deposition current density, facilitates the hole extraction at the interface between perovskite and NiOx , and thus increases the fill factor and the conversion efficiency. The electrochemically deposited NiOx layer also exhibits extremely uniform thickness and morphology, leading to highly efficient and uniform large-area PSCs. As a result, the p-i-n-type planar PSC with an area of 1.084â cm2 exhibits a stable conversion efficiency of 17.0 % (19.2 % for 0.1â cm2 ) without showing hysteresis effects.