Unique Optical Properties of Methylammonium Lead Iodide Nanocrystals Below the Bulk Tetragonal-Orthorhombic Phase Transition

Methylammonium (MA) and formamidinium (FA) lead halides are widely studied for their potential as low-cost, high-performance optoelectronic materials. Here, we present measurements of visible and IR absorption, steady state, and time-resolved photoluminescence from 300 K to cryogenic temperatures. Whereas FAPbI₃ nanocrystals (NCs) are found to behave in a very similar manner to reported bulk behavior, colloidal nanocrystals of MAPbI₃ show a departure from the low-temperature optical behavior of the bulk material. Using photoluminescence, visible, and infrared absorption measurements, we demonstrate that unlike single crystals and polycrystalline films NCs of MAPbI₃ do not undergo optical changes associated with the bulk tetragonal-to-orthorhombic phase transition, which occurs near 160 K. We find no evidence of frozen organic cation rotation to as low as 80 K or altered exciton binding energy to as low as 3 K in MAPbI₃ NCs. Similar results are obtained in MAPbI₃ NCs ranging from 20 to over 100 nm and in morphologies including cubes and plates. Colloidal MAPbI₃ NCs therefore offer a window into the properties of the solar-relevant, room-temperature phase of MAPbI₃ at temperatures inaccessible with single crystals or polycrystalline samples. Exploiting this phenomenon, these measurements reveal the existence of an optically passive photoexcited state close to the band edge and persistent slow Auger recombination at low temperature

Violet-to-Blue Gain and Lasing from Colloidal CdS Nanoplatelets: Low-Threshold Stimulated Emission Despite Low Photoluminescence Quantum Yield

Amplified spontaneous emission (ASE) and lasing from solution-processed materials are demonstrated in the challenging violet-to-blue (430–490 nm) spectral region for colloidal nanoplatelets of CdS and newly synthesized core/shell CdS/ZnS nanoplatelets. Despite modest band-edge photoluminescence quantum yields of 2% or less for single excitons, which we show results from hole trapping, the samples exhibit low ASE thresholds. Furthermore, four-monolayer CdS samples show ASE at shorter wavelengths than any reported film of colloidal quantum-confined material. This work underlines that low quantum yields for single excitons do not necessarily lead to a poor gain medium. The low ASE thresholds originate from negligible dispersion in thickness, large absorption cross sections of 2.8 × 10^–14 cm^–2, and rather slow (150 to 300 ps) biexciton recombination. We show that under higher-fluence excitation, ASE can kinetically outcompete hole trapping. Using nanoplatelets as the gain medium, lasing is observed in a linear optical cavity. This work confirms the fundamental advantages of colloidal quantum well structures as gain media, even in the absence of high photoluminescence efficiency

Large Transient Optical Modulation of Epsilon-Near-Zero Colloidal Nanocrystals

Epsilon-near-zero materials may be synthesized as colloidal nanocrystals which display large magnitude subpicosecond switching of infrared localized surface plasmon resonances. Such nanocrystals offer a solution-processable, scalable source of tunable metamaterials compatible with arbitrary substrates. Under intraband excitation, these nanocrystals display a red-shift of the plasmon feature arising from the low electron heat capacities and conduction band nonparabolicity of the oxide. Under interband pumping, they show in an ultrafast blueshift of the plasmon resonance due to transient increases in the carrier density. Combined with their high-quality factor, large changes in relative transmittance (+86%) and index of refraction (+85%) at modest control fluences (<5 mJ/cm²) suggest that these materials offer great promise for all-optical switching, wavefront engineering, and beam steering operating at terahertz switching frequencies

Facile, Economic and Size-Tunable Synthesis of Metal Arsenide Nanocrystals

Synthesis of colloidal nanocrystals (NC) of important arsenide nanomaterials (e.g., InAs, Cd₃As₂) has been limited by the lack of convenient arsenic precursors. Here we address this constraint by identifying a convenient and commercially available As precursor, tris-dimethylaminoarsine (As­(NMe₂)₃), which can be used to prepare high quality InAs NCs with controlled size distributions. Our approach employs a reaction between InCl₃ and As­(NMe₂)₃ using diisobutylaluminum hydride (DIBAL-H) to convert As­(NMe₂)₃ in situ into reactive intermediates AsH_<i>x</i>(NMe₂)_3–<i>x</i>, where <i>x</i> = 1,2,3. NC size can be varied by changing DIBAL-H concentration and growth temperature, with colloidal solutions of InAs showing size dependent absorption and emission features tunable across wavelengths of 750 to 1450 nm. We also show that this approach works well for the colloidal synthesis of Cd₃As₂ NCs. By circumventing the preparation of notoriously unstable and dangerous arsenic precursors (e.g., AsH₃ and As­(SiMe₃)₃), this work improves the synthetic accessibility of arsenide-based NCs and, by extension, the potential of such NCs for use in infrared (IR) applications such as communications, fluorescent labeling and photon detection

Surface-Area-Dependent Electron Transfer Between Isoenergetic 2D Quantum Wells and a Molecular Acceptor

We report measurements of electron transfer rates for four isoenergetic donor–acceptor pairs comprising a molecular electron acceptor, methylviologen (MV), and morphology-controlled colloidal semiconductor nanoparticles of CdSe. The four nanoparticles include a spherical quantum dot (QD) and three differing lateral areas of 4-monolayer-thick nanoplatelets (NPLs), each with a 2.42 eV energy gap. As such, the measurements, performed via ultrafast photoluminescence, relate the dependence of charge transfer rate on the spatial extent of the initial electron–hole pair wave function explicitly, which we show for the first time to be related to surface area in this regime that is intermediate between homogeneous and heterogeneous charge transfer as well as 2D to 0D electron transfer. The observed nonlinear dependence of rate with surface area is attributed to exciton delocalization within each structure, which we show via temperature-dependent absorption measurements remains constant