The dark exciton ground state promotes photon-pair emission in individual perovskite nanocrystals.

Cesium lead halide perovskites exhibit outstanding optical and electronic properties for a wide range of applications in optoelectronics and for light-emitting devices. Yet, the physics of the band-edge exciton, whose recombination is at the origin of the photoluminescence, is not elucidated. Here, we unveil the exciton fine structure of individual cesium lead iodide perovskite nanocrystals and demonstrate that it is governed by the electron-hole exchange interaction and nanocrystal shape anisotropy. The lowest-energy exciton state is a long-lived dark singlet state, which promotes the creation of biexcitons at low temperatures and thus correlated photon pairs. These bright quantum emitters in the near-infrared have a photon statistics that can readily be tuned from bunching to antibunching, using magnetic or thermal coupling between dark and bright exciton sublevels.

Dynamics of Photo-Generated Carriers across the Interface between CsPbBr3 Nanocrystals and Au-Ag Nanostructured Film, and Its Control via Ultrathin MgO Interface Layer.

The dynamics and control of charge transfer between optoelectronically interesting and size-tunable halide perovskite quantum dots and other juxtaposed functional electronic materials are important issues for the emergent device interest involving such a family of materials in heterostructure configurations. Herein, we have grown bimetallic Au-Ag thin films on glass by pulsed laser deposition at room temperature, which bear nanoparticulate character, and the corresponding optical absorption spectra reveal the expected surface plasmon resonance signature(s). Subsequently, spin-coated CsPbBr3 nanoparticle films onto the bimetallic Au-Ag films exhibit surface-enhanced Raman scattering as well as strong photoluminescence quenching, the latter reflecting highly efficient transfer of photo-generated carriers across the CsPbBr3/Au-Ag interface. Surprisingly, when an ultrathin MgO (insulating) layer of optimum thickness is introduced between the CsPbBr3 and Au-Ag films, the charge transfer is further facilitated with the average lifetime of carriers becoming even shorter. By changing the thickness of the thin MgO layer, the carrier lifetime can in fact be tuned; with the charge transfer getting fully blocked for thick enough MgO layers, as expected. Our study thus throws light on the charge-carrier dynamics in halide perovskites, which is of importance to emergent optoelectronic applications.

Postsynthesis Mn-doping in CsPbI3 nanocrystals to stabilize the black perovskite phase.

Long term stability of the black perovskite phase of CsPbI3 nanocrystals under ambient conditions is an important challenge for their optoelectronic applications in real life. The nanocrystalline size is found to improve the stability of the black phase at room temperature. Furthermore, doping Mn is proposed to improve the stability of the black perovskite phase of CsPbI3 nanocrystals (NCs). However, the undoped and Mn-doped CsPbI3 NCs are prepared in different batches under somewhat different synthesis conditions thus obliterating the role of Mn in the stability of the black phase of CsPbI3 NCs. Here, we elucidate the effect of Mn doping on the surface and lattice energy of CsPbI3 NCs, stabilizing the black phase. For this purpose, we employ a postsynthesis doping strategy which has an advantage that the initial host remains the same for both undoped and Mn-doped samples. Uncertainties in the size/shape, surface energy, and structure through direct synthesis of undoped and Mn-doped NCs in different batches can be neglected in our postsynthesis doping strategy, allowing us to study the effect of dopants in a more controlled manner. Our postsynthesis Mn-doping in CsPbI3 NCs shows that the black phase stability under ambient conditions improves from few days for the undoped sample to nearly a month's time for the Mn-doped sample. We found that though surface passivation with a dopant precursor improves both colloidal and phase stability of black CsPbI3 NCs, it is the contraction of the lattice upon Mn-doping that mainly stabilizes the films of black phase CsPbI3 NCs. Similarly, we found that Mn-doped CsPbBr3 NCs show improved ambient stability of photoluminescence compared to the undoped sample.

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

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.

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.

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.

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.

Electronic grade and flexible semiconductor film employing oriented attachment of colloidal ligand-free PbS and PbSe nanocrystals at room temperature.

Electronic grade semiconductor films have been obtained via the sintering of solution processed PbS and PbSe nanocrystals at room temperature. Prior attempts to achieve similar films required the sintering of nanocrystals at higher temperatures (>350 °C), which inhibits the processing of such films on a flexible polymer substrate, and it is also expensive. We reduced the sintering temperature by employing two important strategies: (i) use of ligand-free nanocrystals and (ii) oriented attachment of nanocrystals. Colloidal ligand-free PbS and PbSe nanocrystals were synthesized at 70 °C with high yield (∼70%). However, these nanocrystals start to agglomerate with time in formamide, and upon the removal of the solvation energy, nanocrystals undergo oriented attachment, forming larger elongated crystals. PbS and PbSe nanocrystal films made on both glass and flexible substrates at room temperature exhibit Ohmic behavior with optimum DC conductivities of 0.03 S m(-1) and 0.08 S m(-1), respectively. Mild annealing of the films at 150 °C increases the conductivity values to 1.1 S m(-1) and 137 S m(-1) for PbS and PbSe nanocrystal films, respectively. AC impedance was measured to distinguish the contributions from grain and grain boundaries to the charge transport mechanism. Charge transport properties remain similar after the repeated bending of the film on a flexible polymer substrate. Reasonably high thermoelectric Seebeck coefficients of 600 µV K(-1) and 335 µV K(-1) for PbS and PbSe nanocrystal pellets, respectively, were obtained at room temperature.

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).

Citrate-hydrazine hydrogen-bonding driven single-step synthesis of tunable near-IR plasmonic, anisotropic silver nanocrystals: implications for SERS spectroscopy of inorganic oxoanions.

A simplified, single-step aqueous synthesis route to tunable anisotropic silver nanocrystals (NCs) has been developed by tailoring the hydrogen-bonding interactions between a mild stabilizer, sodium citrate, and a mild reductant, hydrazine hydrate. The structure directing ability of the H-bonding interaction was harnessed by keeping a stoichiometric excess of hydrazine under ambient conditions (pH 7, 25 °C). Decreasing the synthesis temperature to 5 °C imparts rigidity to the citrate-hydrazine H-bonding network, and the plasmon peak moves from 500 to 550 nm (using 40 mM hydrazine). On lowering the pH from 7 to 5, the H-bonding is further strengthened due to partial protonation of citrate and the plasmon peak is tuned to 790 nm. Further, we found that, at 5 °C and pH 5, there also exists a sub-stoichiometric regime in which maximum tunability of the plasmon peak (790→1010 nm) is achieved with 1 mM hydrazine. HR-TEM reveals that the near-IR plasmonic NCs are nanopyramids having a pentagonal base with edge length varying from 15 nm to 30 nm. Through second derivative FTIR analysis, a correlation between hydrogen-bonded molecular vibrations and the plasmon tunability has been established. The anisotropic NCs exhibit significant Raman enhancement on the citrate molecules. Further, a solution-phase, non-resonant SERS spectroscopic detection method for an inorganic contaminant of ground water, arsenite, has also been developed.

Organic-free colloidal semiconductor nanocrystals as luminescent sensors for metal ions and nitroaromatic explosives.

Exposed surfaces of organic-free colloidal semiconductor nanocrystals act as generic luminescent sensors for multiple analytes. S(2-) capped CdSe/CdSeS/CdS core/gradient-shell/shell nanocrystals are turn-on sensors for Cd(2+) ions (110 pM) in an aqueous medium with physiological pH 7.4. A similar organic-free semiconductor nanocrystal shows luminescence turn-off sensing for 2,4,6-trinitrophenol, a known explosive.