Abhishek Swarnkar

Quantum dot–induced phase stabilization of α-CsPbI3 perovskite for high-efficiency photovoltaics

Maintaining a stable phase For solar cell applications, all-inorganic perovskite phases could be more stable than those containing organic cations. But the band gaps of the former, which determine the electrical conductivity of these materials, are not well matched to the solar spectrum. The cubic structure of CsPbI3 is an exception, but it is stable in bulk only at high temperatures. Swarnkar et al. show that surfactant-coated α-CsPbI3 quantum dots are stable at ambient conditions and have tunable band gaps in the visible range. Thin films of these materials can be made by spin coating with an antisolvent technique to minimize surfactant loss. When used in solar cells, these films have efficiencies exceeding 10%, making them promising for light harvesting or for LEDs. Science, this issue p. 92 The cubic crystalline phase of CsPbI3, which has a more favorable band gap for solar cells, is stabilized as a nanomaterial. We show nanoscale phase stabilization of CsPbI3 quantum dots (QDs) to low temperatures that can be used as the active component of efficient optoelectronic devices. CsPbI3 is an all-inorganic analog to the hybrid organic cation halide perovskites, but the cubic phase of bulk CsPbI3 (α-CsPbI3)—the variant with desirable band gap—is only stable at high temperatures. We describe the formation of α-CsPbI3 QD films that are phase-stable for months in ambient air. The films exhibit long-range electronic transport and were used to fabricate colloidal perovskite QD photovoltaic cells with an open-circuit voltage of 1.23 volts and efficiency of 10.77%. These devices also function as light-emitting diodes with low turn-on voltage and tunable emission.

Colloidal CsPbBr3 Perovskite Nanocrystals: Luminescence beyond Traditional Quantum Dots

Traditional CdSe-based colloidal quantum dots (cQDs) have interesting photoluminescence (PL) properties. Herein we highlight the advantages in both ensemble and single-nanocrystal PL of colloidal CsPbBr3 nanocrystals (NCs) over the traditional cQDs. An ensemble of colloidal CsPbBr3 NCs (11 nm) exhibits ca. 90 % PL quantum yield with narrow (FWHM=86 meV) spectral width. Interestingly, the spectral width of a single-NC and an ensemble are almost identical, ruling out the problem of size-distribution in PL broadening. Eliminating this problem leads to a negligible influence of self-absorption and Förster resonance energy transfer, along with batch-to-batch reproducibility of NCs exhibiting PL peaks within ±1 nm. Also, PL peak positions do not alter with measurement temperature in the range of 25 to 100 °C. Importantly, CsPbBr3 NCs exhibit suppressed PL blinking with ca. 90 % of the individual NCs remain mostly emissive (on-time >85 %), without much influence of excitation power.

Terahertz Conductivity within Colloidal CsPbBr3 Perovskite Nanocrystals: Remarkably High Carrier Mobilities and Large Diffusion Lengths.

Colloidal CsPbBr3 perovskite nanocrystals (NCs) have emerged as an excellent light emitting material in last one year. Using time domain and time-resolved THz spectroscopy and density functional theory based calculations, we establish 3-fold free carrier recombination mechanism, namely, nonradiative Auger, bimolecular electron-hole recombination, and inefficient trap-assisted recombination in 11 nm sized colloidal CsPbBr3 NCs. Our results confirm a negligible influence of surface defects in trapping charge carriers, which in turn results into desirable intrinsic transport properties, from the perspective of device applications, such as remarkably high carrier mobility (∼4500 cm(2) V(-1) s(-1)), large diffusion length (>9.2 μm), and high luminescence quantum yield (80%). Despite being solution processed and possessing a large surface to volume ratio, this combination of high carrier mobility and diffusion length, along with nearly ideal photoluminescence quantum yield, is unique compared to any other colloidal quantum dot system.

Origin of Unusual Excitonic Absorption and Emission from Colloidal Ag2S Nanocrystals: Ultrafast Photophysics and Solar Cell.

Colloidal Ag2S nanocrystals (NCs) typically do not exhibit sharp excitonic absorption and emission. We first elucidate the reason behind this problem by preparing Ag2S NCs from nearly monodisperse CdS NCs employing cation exchange reaction. It was found that the defect-related midgap transitions overlap with excitonic transition, blurring the absorption spectrum. On the basis of this observation, we prepared nearly defect-free Ag2S NCs using molecular precursors. These defect-free Ag2S NCs exhibit sharp excitonic absorption, emission (quantum yield 20%) in near-infrared (853 nm) region, and improved performance of Ag2S quantum-dot-sensitized solar cells (QDSSCs). Samples with lower defects exhibit photoconversion efficiencies >1% and open circuit voltage of ∼0.3 V, which are better compared with prior reports of Ag2S QDSSCs. Femtosecond transient absorption shows pump-probe two-photon absorption above 630 nm and slow-decaying excited state absorption below 600 nm. Concomitantly, open-aperture z-scan shows strong two-photon absorption at 532 nm (coefficient 55 ± 3 cm/GW).

Excellent green but less impressive blue luminescence from CsPbBr3 perovskite nanocubes and nanoplatelets.

Green photoluminescence (PL) from CsPbBr3 nanocubes (∼11 nm edge-length) exhibits a high quantum yield (>80%), narrow spectral width (∼85 meV), and high reproducibility, along with a high molar extinction coefficient (3.5 × 10(6) M(-1) cm(-1)) for lowest energy excitonic absorption. In order to obtain these combinations of excellent properties for blue (PL peak maximum, λ max < 500 nm) emitting samples, CsPbBr3 nanocubes and nanoplatelets with various dimensions were prepared. Systematic increases in both the optical gap and transition probability for radiative excitonic recombination (PL lifetime 3-7 ns), have been achieved with the decreasing size of nanocubes. A high quantum yield (>80%) was also maintained, but the spectral width increased and became asymmetric for blue emitting CsPbBr3 nanocubes. Furthermore, PL was unstable and irreproducible for samples with λ max ∼ 460 nm, exhibiting multiple features in the PL. These problems arise because smaller (<7 nm) CsPbBr3 nanocubes have a tendency to form nanoplatelets and nanorods, eventually yielding inhomogeneity in the shape and size of blue-emitting nanocrystals. Reaction conditions were then modified achieving nanoplatelets, with strong quantum confinement along the thickness of the platelets, yielding blue emission. But inhomogeneity in the thickness of the nanoplatelets again broadens the PL compared to green-emitting CsPbBr3 nanocubes. Therefore, unlike high quality green emitting CsPbBr3 nanocubes, blue emitting CsPbBr3 nanocrystals of any shape need to be improved further.