This article reviews the various hole transporting materials (HTMs) used in perovskite solar cells (PSCs) in achieving high photo conversion efficiency (PCE) and operational stability. The PSCs are the latest development in solution processable solar cells offering PCE (~22%) on a par with that of practically deployed silicon and thin film solar cells. HTMs and electron transporting materials (ETMs) are important constituents in PSCs as they selectively transport charges within the device, influence photovoltaic parameters, determine device stability and also influence its cost. This article critically approaches role of structure, electrochemistry, and physical properties of varied of choice of HTMs categorized diversely as small and long polymers, organometallic, and inorganic on the photovoltaic parameters of PSCs conceived in various device configurations. Achievements in tailoring the properties of HTMs to best fit for PSCs are detailed; a well designed HTM suppresses carrier recombination by facilitating the passage of holes but blocking electrons at the HTM/perovskite interface. Moreover, in many PSCs the HTM acts as the first line of defense to external degrading factors such as humidity, oxygen and photon dose, the extent of which depends on its hydrophobicity, permeability, and density.
Despite the high efficiency of over 21% reported for emerging thin film perovskite solar cells, one of the key issues prior to their commercial deployment is to attain their long term stability under ambient and outdoor conditions. The instability in perovskite is widely conceived to be humidity induced due to the water solubility of its initial precursors, which leads to decomposition of the perovskite crystal structure; however, we note that humidity alone is not the major degradation factor and it is rather the photon dose in combination with humidity exposure that triggers the instability. In our experiment, which is designed to decouple the effect of humidity and light on perovskite degradation, we investigate the shelf-lifetime of CH3NH3PbI3 films in the dark and under illumination under high humidity conditions (Rel. H. > 70%). We note minor degradation in perovskite films stored in a humid dark environment whereas upon exposure to light, the films undergo drastic degradation, primarily owing to the reactive TiO2/perovskite interface and also the surface defects of TiO2. To enhance its air-stability, we incorporate CH3NH3PbI3 perovskite in a polymer (poly-vinylpyrrolidone, PVP) matrix which retained its optical and structural characteristics in the dark for ∼2000 h and ∼800 h in room light soaking, significantly higher than a pristine perovskite film, which degraded completely in 600 h in the dark and in less than 100 h when exposed to light. We attribute the superior stability of PVP incorporated perovskite films to the improved structural stability of CH3NH3PbI3 and also to the improved TiO2/perovskite interface upon incorporating a polymer matrix. Charge injection from the polymer embedded perovskite films has also been confirmed by fabricating solar cells using them, thereby providing a promising future research pathway for stable and efficient perovskite solar cells.
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