Som Sarang

Nature inspiring processing route toward high throughput production of perovskite photovoltaics

We report our results of developing perovskite thin films with high coverage, improved uniformity and preserved crystalline continuity in a single pass deposition. This approach, inspired by the natural phenomena of tears of wine, works by regulating the hydrodynamics of the material comprising of droplets during spray-pyrolysis. In contrast to conventional spray-pyrolysis where droplets dry independently and form a rough morphology, the use of binary solvent system creates localized surface tension gradients that initiate Marangoni flows, thus directing the incoming droplets to spontaneously undergo coalescing, merging and spreading into a continuous wet films before drying. By systematically exploring the dynamics of spreading and drying, we achieve spray-coated perovskite photovoltaics with power conversion efficiency of 14.2%, a near two-fold improvement than that of the spray-pyrolysis counterpart. Of particular significance is the fact that the single pass deposition technique unveils novel inroads in efficient management of lead consumption during deposition.

Low temperature excitonic spectroscopy and dynamics as a probe of quality in hybrid perovskite thin films

We have developed a framework for using temperature dependent static and dynamic photoluminescence (PL) of hybrid organic-inorganic perovskites (PVSKs) to characterize lattice defects in thin films, based on the presence of nanodomains at low temperature. Our high-stability PVSK films are fabricated using a novel continuous liquid interface propagation technique, and in the tetragonal phase (T > 120 K), they exhibit bi-exponential recombination from free charge carriers with an average PL lifetime of ∼200 ns. Below 120 K, the emergence of the orthorhombic phase is accompanied by a reduction in lifetimes by an order of magnitude, which we establish to be the result of a crossover from free carrier to exciton-dominated radiative recombination. Analysis of the PL as a function of excitation power at different temperatures provides direct evidence that the exciton binding energy is different in the two phases, and using these results, we present a theoretical approach to estimate this variable binding energy. Our findings explain this anomalous low temperature behavior for the first time, attributing it to an inherent fundamental property of the hybrid PVSKs that can be used as an effective probe of thin film quality.

Plasmon-actuated nano-assembled microshells

We present three-dimensional microshells formed by self-assembly of densely-packed 5 nm gold nanoparticles (AuNPs). Surface functionalization of the AuNPs with custom-designed mesogenic molecules drives the formation of a stable and rigid shell wall, and these unique structures allow encapsulation of cargo that can be contained, virtually leakage-free, over several months. Further, by leveraging the plasmonic response of AuNPs, we can rupture the microshells using optical excitation with ultralow power (<2 mW), controllably and rapidly releasing the encapsulated contents in less than 5 s. The optimal AuNP packing in the wall, moderated by the custom ligands and verified using small angle x-ray spectroscopy, allows us to calculate the heat released in this process, and to simulate the temperature increase originating from the photothermal heating, with great accuracy. Atypically, we find the local heating does not cause a rise of more than 50 °C, which addresses a major shortcoming in plasmon actuated cargo delivery systems. This combination of spectral selectivity, low power requirements, low heat production, and fast release times, along with the versatility in terms of identity of the enclosed cargo, makes these hierarchical microshells suitable for wide-ranging applications, including biological ones.

Stabilization of the Cubic Crystalline Phase in Organometal Halide Perovskite Quantum Dots via Surface Energy Manipulation

Surface functionalization of nanoscale materials has a significant impact on their properties. We have demonstrated the effect of different passivating ligands on the crystal phase of organometal halide perovskite quantum dots (PQDs). Using static and dynamic spectroscopy, we studied phase transitions in CH3NH3PbBr3 PQDs ligated with either octylaminebromide (P-OABr) or 3-aminopropyl triethoxysilane (P-APTES). Around 140 K, P-OABr underwent a structural phase transition from tetragonal to orthorhombic, established by the emergence of a higher energy band in the photoluminescence (PL) spectrum. This was not observed in P-APTES, despite cooling down to 20 K. Additionally, time-resolved and excitation power-dependent PL, as well as Raman spectroscopy over a range of 300-20 K, revealed that recombination rates and types of charge carriers involved are significantly different in P-APTES and P-OABr. Our findings highlight how aspects of PQD phase stabilization are linked to nanoscale morphology and the crystal phase diagram.

Photovoltaic and optical properties of perovskite thin films fabricated using Marangoni flow assisted electrospraying.

We have developed an electrospraying technique inspired from Marangoni flow seen in nature. We demonstrate our ability to synthesise highly crystalline uniform perovskite thin films with enhanced coverage and high absorption. Due to a difference in the vapour pressure of DMSO and NMP, a gradient force is developed that helps in propagating the incoming precursor droplet to coalesce and merge with other droplets thus inducing a dynamic self-assembly within the thin film. This results in thin films with high uniformity and good morphological and topological characteristics, that collectivelty resulted in a respectable PCE of greater than 14%. Optical studies are conducted in parallel to better understand the energy phase space of perovskite crystals. The high temperature tetragonal phase showed a high recombination rate of 180 ns, ideal for photovoltaic performances, while the low temperature measurements reveal considerable complexity in spectral and dynamic properties that demand further invesgtiation.