Exciton-photocarrier interference in mixed lead-halide-perovskite nanocrystals.

The use of semiconductor nanocrystals in scalable quantum technologies requires characterization of the exciton coherence dynamics in an ensemble of electronically isolated crystals in which system-bath interactions are nevertheless strong. In this communication, we identify signatures of Fano-like interference between excitons and photocarriers in the coherent two-dimensional photoluminescence excitation spectral lineshapes of mixed lead-halide perovskite nanocrystals in dilute solution. Specifically, by tuning the femtosecond-pulse spectrum, we show such interference in an intermediate coupling regime, which is evident in the coherent lineshape when simultaneously exciting the exciton and the free-carrier band at higher energy. We conclude that this interference is an intrinsic effect that will be consequential in the quantum dynamics of the system and will thus dictate decoherence dynamics, with consequences in their application in quantum technologies.

Growth and Self-Assembly of CsPbBr3 Nanocrystals in the TOPO/PbBr2 Synthesis as Seen with X-ray Scattering.

Despite broad interest in colloidal lead halide perovskite nanocrystals (LHP NCs), their intrinsic fast growth has prevented controlled synthesis of small, monodisperse crystals and insights into the reaction mechanism. Recently, a much slower synthesis of LHP NCs with extreme size control has been reported, based on diluted TOPO/PbBr2 precursors and a diisooctylphosphinate capping ligand. We report new insights into the nucleation, growth, and self-assembly in this reaction, obtained by in situ synchrotron-based small-angle X-ray scattering and optical absorption spectroscopy. We show that dispersed 3 nm Cs[PbBr3] agglomerates are the key intermediate species: first, they slowly nucleate into crystals, and then they release Cs[PbBr3] monomers for further growth of the crystals. We show the merits of a low Cs[PbBr3] monomer concentration for the reaction based on oleate ligands. We also examine the spontaneous superlattice formation mechanism occurring when the growing nanocrystals in the solvent reach a critical size of 11.6 nm.

Quantum Dot Metal Salt Interactions Unraveled by the Sphere of Action Model.

Postsynthetic metal salt treatments are frequently employed in the luminescence enhancement of quantum dots (QDs); however, its microscopic picture remains unclear. CsPbBr3-QDs, featuring strong excitonic absorption and high photoluminescence (PL) quantum yield, are ideal QDs to unravel the intricate interaction between QDs and such surface-bound metal salts. Herein, we study this interaction based on the controlled PL quenching of CsPbBr3-QDs with BiBr3. Upon the addition of BiBr3, an instant and complete PL quenching is observed, which can be fully recovered after the addition of an excess of PbBr2. This, together with the complete preservation of the excitonic absorption suggests a surface-driven adsorption equilibrium. Additionally, time-resolved studies reveal a non-homogeneous surface trap formation. Based on the so-called sphere of action model for the adsorption process, we show that already a single BiBr3 adsorption suffices to completely quench a QD's luminescence. This approach is expanded to analyze size-, ligand-, and metal-dependent quenching dynamics. Facet junctions are identified as regions of enhanced surface reactivity. A Langmuir-type ligand coverage is exposed with a strong impact on adsorption. Our results provide a detailed mechanistic insight into postsynthetic interaction of QDs with metal salts, opening pathways for future surface manipulations.

Spheroidal Cesium Lead Chloride-Bromide Quantum Dots and a Fast Determination of Their Size and Halide Content.

Lead halide perovskite (LHP) quantum dots (QDs), with their bright and narrow emission, are promising candidates for LEDs, lasers, and quantum light sources. However, current methods to synthesize monodisperse CsPb(Cl:Br)3 and CsPbCl3 QDs exhibiting multiple sharp absorption resonances are not as well developed compared to CsPbBr3. Furthermore, both quantum confinement and the halide ratio in CsPb(Cl:Br)3 QDs strongly influence the bandgap, making it impossible to optically determine their size. In this work, monodisperse spheroidal CsPb(Cl:Br)3 QDs are synthesized in the 4-10 nm range, at any Cl:Br ratio, with up to five excitonic absorption transitions. Furthermore, in situ spectroscopy was used to cross-correlate the size and composition of these QDs directly to the energy of the first two excitonic absorption transitions. This work therefore provides not only a method for monodisperse CsPb(Cl:Br)3 QDs but also a protocol to determine their size, concentration, and halide ratio, circumventing conventional expensive and time-consuming techniques.

Confined Excitons in Spherical-Like Halide Perovskite Quantum Dots.

Quantum dots (QDs) offer unique physical properties and novel application possibilities like single-photon emitters for quantum technologies. While strongly confined III-V and II-VI QDs have been studied extensively, their complex valence band structure often limits clear observations of individual transitions. In recently emerged lead-halide perovskites, band degeneracies are absent around the bandgap reducing the complexity of optical spectra. We show that for spherical-like CsPbBr3 QDs with diameters >6 nm, excitons confine with respect to their center-of-mass motion leading to well-pronounced resonances in their absorption spectra. Optical pumping of the lowest-confined exciton with femtosecond laser pulses not only bleaches all excitons but also reveals a series of distinct induced absorption resonances which we attribute to exciton-to-biexciton transitions and are red-shifted by the biexciton binding energy (∼40 meV). The temporal dynamics of the bleached excitons further support our exciton confinement model. Our study provides the first insight into confined excitons in CsPbBr3 QDs and gives a detailed understanding of their linear and nonlinear optical spectra.

Nanocrystals of Lead Chalcohalides: A Series of Kinetically Trapped Metastable Nanostructures.

We report the colloidal synthesis of a series of surfactant-stabilized lead chalcohalide nanocrystals. Our work is mainly focused on Pb4S3Br2, a chalcohalide phase unknown to date that does not belong to the ambient-pressure PbS-PbBr2 phase diagram. The Pb4S3Br2 nanocrystals herein feature a remarkably narrow size distribution (with a size dispersion as low as 5%), a good size tunability (from 7 to ∼30 nm), an indirect bandgap, photoconductivity (responsivity = 4 ± 1 mA/W), and stability for months in air. A crystal structure is proposed for this new material by combining the information from 3D electron diffraction and electron tomography of a single nanocrystal, X-ray powder diffraction, and density functional theory calculations. Such a structure is closely related to that of the recently discovered high-pressure chalcohalide Pb4S3I2 phase, and indeed we were able to extend our synthesis scheme to Pb4S3I2 colloidal nanocrystals, whose structure matches the one that has been published for the bulk. Finally, we could also prepare nanocrystals of Pb3S2Cl2, which proved to be a structural analogue of the recently reported bulk Pb3Se2Br2 phase. It is remarkable that one high-pressure structure (for Pb4S3I2) and two metastable structures that had not yet been reported (for Pb4S3Br2 and Pb3S2Cl2) can be prepared on the nanoscale by wet-chemical approaches. This highlights the important role of colloidal chemistry in the discovery of new materials and motivates further exploration into metal chalcohalide nanocrystals.

Genesis, challenges and opportunities for colloidal lead halide perovskite nanocrystals.

Lead halide perovskites (LHPs) in the form of nanometre-sized colloidal crystals, or nanocrystals (NCs), have attracted the attention of diverse materials scientists due to their unique optical versatility, high photoluminescence quantum yields and facile synthesis. LHP NCs have a 'soft' and predominantly ionic lattice, and their optical and electronic properties are highly tolerant to structural defects and surface states. Therefore, they cannot be approached with the same experimental mindset and theoretical framework as conventional semiconductor NCs. In this Review, we discuss LHP NCs historical and current research pursuits, challenges in applications, and the related present and future mitigation strategies explored.

Ultrafast THz Probe of Photoinduced Polarons in Lead-Halide Perovskites.

We study the nature of photoexcited charge carriers in CsPbBr_{3} nanocrystal thin films by ultrafast optical pump-THz probe spectroscopy. We observe a deviation from a pure Drude dispersion of the THz dielectric response that is ascribed to the polaronic nature of carriers; a transient blueshift of observed phonon frequencies is indicative of the coupling between photogenerated charges and stretching-bending modes of the deformed inorganic sublattice, as confirmed by DFT calculations.

Shape-Pure, Nearly Monodispersed CsPbBr3 Nanocubes Prepared Using Secondary Aliphatic Amines.

Fully inorganic cesium lead halide perovskite (CsPbX3) nanocrystals (NCs) have been extensively studied due to their excellent optical properties, especially their high photoluminescence quantum yield (PLQY) and the ease with which the PL can be tuned across the visible spectrum. So far, most strategies for synthesizing CsPbX3 NCs are highly sensitive to the processing conditions and ligand combinations. For example, in the synthesis of nanocubes of different sizes, it is not uncommon to have samples that contain various other shapes, such as nanoplatelets and nanosheets. Here, we report a new colloidal synthesis method for preparing shape-pure and nearly monodispersed CsPbBr3 nanocubes using secondary amines. Regardless of the length of the alkyl chains, the oleic acid concentration, and the reaction temperature, only cube-shaped NCs were obtained. The shape purity and narrow size distribution of the nanocubes are evident from their sharp excitonic features and their ease of self-assembly in superlattices, reaching lateral dimensions of up to 50 µm. We attribute this excellent shape and phase purity to the inability of secondary amines to find the right steric conditions at the surface of the NCs, which consequently limits the formation of low-dimensional structures. Furthermore, no contamination from other phases was observed, not even from Cs4PbBr6, presumably due to the poor ability of secondary aliphatic amines to coordinate to PbBr2 and, hence, to provide a reaction environment that is depleted in Pb.

The Phosphine Oxide Route toward Lead Halide Perovskite Nanocrystals.

We report an amine-free synthesis of lead halide perovskite (LHP) nanocrystals, using trioctylphosphine oxide (TOPO) instead of aliphatic amines, in combination with a protic acid (e.g., oleic acid). The overall synthesis scheme bears many similarities to the chemistry behind the preparation of LHP thin films and single crystals, in terms of ligand coordination to the chemical precursors. The acidity of the environment and hence the extent of protonation of the TOPO molecules tune the reactivity of the PbX2 precursor, regulating the size of the nanocrystals. On the other hand, TOPO molecules are virtually absent from the surface of our nanocrystals, which are simply passivated by one type of ligand (e.g., Cs-oleate). Furthermore, our studies reveal that Cs-oleate is dynamically bound to the surface of the nanocrystals and that an optimal surface coverage is critical for achieving high photoluminescence quantum yield. Our scheme delivers NCs with a controlled size and shape: only cubes are formed, with no contamination with platelets, regardless of the reaction conditions that were tested. We attribute such a shape homogeneity to the absence of primary aliphatic amines in our reaction environment, since these are known to promote the formation of nanocrystals with sheet/platelet morphologies or layered phases under certain reaction conditions. The TOPO route is particularly appealing with regard to synthesizing LHP nanocrystals for large-scale manufacturing, as the yield in terms of material produced is close to the theoretical limit: i.e., almost all precursors employed in the synthesis are converted into nanocrystals.

Role of Nonradiative Defects and Environmental Oxygen on Exciton Recombination Processes in CsPbBr3 Perovskite Nanocrystals.

Lead halide perovskite nanocrystals (NCs) are emerging as optically active materials for solution-processed optoelectronic devices. Despite the technological relevance of tracing rational guidelines for optimizing their performances and stability beyond their intrinsic resilience to structural imperfections, no in-depth study of the role of selective carrier trapping and environmental conditions on their exciton dynamics has been reported to date. Here we conduct spectro-electrochemical (SEC) experiments, side-by-side to oxygen sensing measurements on CsPbBr3 NCs for the first time. We show that the application of EC potentials controls the emission intensity by altering the occupancy of defect states without degrading the NCs. Reductive potentials lead to strong (60%) emission quenching by trapping of photogenerated holes, whereas the concomitant suppression of electron trapping is nearly inconsequential to the emission efficiency. Consistently, oxidizing conditions result in minor (5%) brightening due to suppressed hole trapping, confirming that electron traps play a minor role in nonradiative decay. This behavior is rationalized through a model that links the occupancy of trap sites with the position of the NC Fermi level controlled by the EC potential. Photoluminescence measurements in controlled atmosphere reveal strong quenching by collisional interactions with O2, which is in contrast to the photobrightening effect observed in films and single crystals. This indicates that O2 acts as a scavenger of photoexcited electrons without mediation by structural defects and, together with the asymmetrical SEC response, suggests that electron-rich defects are likely less abundant in nanostructured perovskites than in the bulk, leading to an emission response dominated by direct interaction with the environment.

Nearly Monodisperse Insulator Cs4PbX6 (X = Cl, Br, I) Nanocrystals, Their Mixed Halide Compositions, and Their Transformation into CsPbX3 Nanocrystals.

We have developed a colloidal synthesis of nearly monodisperse nanocrystals of pure Cs4PbX6 (X = Cl, Br, I) and their mixed halide compositions with sizes ranging from 9 to 37 nm. The optical absorption spectra of these nanocrystals display a sharp, high energy peak due to transitions between states localized in individual PbX64- octahedra. These spectral features are insensitive to the size of the particles and in agreement with the features of the corresponding bulk materials. Samples with mixed halide composition exhibit absorption bands that are intermediate in spectral position between those of the pure halide compounds. Furthermore, the absorption bands of intermediate compositions broaden due to the different possible combinations of halide coordination around the Pb2+ ions. Both observations are supportive of the fact that the [PbX6]4- octahedra are electronically decoupled in these systems. Because of the large band gap of Cs4PbX6 (>3.2 eV), no excitonic emission in the visible range was observed. The Cs4PbBr6 nanocrystals can be converted into green fluorescent CsPbBr3 nanocrystals by their reaction with an excess of PbBr2 with preservation of size and size distributions. The insertion of PbX2 into Cs4PbX6 provides a means of accessing CsPbX3 nanocrystals in a wide variety of sizes, shapes, and compositions, an important aspect for the development of precisely tuned perovskite nanocrystal inks.

Nonlinear Carrier Interactions in Lead Halide Perovskites and the Role of Defects.

The simple solution processability at room temperature exposes lead halide perovskite semiconductors to a non-negligible level of unintentional structural and chemical defects. Ascertained that their primary optoelectronic properties meet the requirement for high efficiency optoelectronic technologies, a lack of knowledge about the nature of defects and their role in the device operation currently is a major challenge for their market-scale application due to the issues with stability and reliability. Here, we use excitation correlation photoluminescence (ECPL) spectroscopy to investigate the recombination dynamics of the photogenerated carriers in lead bromide perovskites and quantitatively describe the carrier trapping dynamics within a generalization of the Shockley-Read-Hall formalism. The superior sensitivity of our spectroscopic tool to the many-body interactions enables us to identify the energetics of the defects. In fact, in the case of polycrystalline films, depending on the synthetic route, we demonstrate the presence of both deep and shallow carrier traps. The shallow defects, which are situated at about 20 meV below the conduction band, dope the semiconductor, leading to a substantial enhancement of the photoluminescence quantum yield despite carrier trapping. At excitation densities relevant for lasing, we observe breakdown of the rate-equation model, indicating a buildup of a highly correlated regime of the photocarrier population that suppresses the nonradiative Auger recombination. Furthermore, we demonstrate that colloidal nanocrystals represent virtually defect-free systems, suffering from nonradiative quenching only due to subpicosecond Auger-like interactions at high excitation density. By correlating the fabrication conditions to the nonradiative loss channels, this work provides guidelines for material engineering towards superior optoelectronic devices.

Solution Synthesis Approach to Colloidal Cesium Lead Halide Perovskite Nanoplatelets with Monolayer-Level Thickness Control.

We report a colloidal synthesis approach to CsPbBr3 nanoplatelets (NPLs). The nucleation and growth of the platelets, which takes place at room temperature, is triggered by the injection of acetone in a mixture of precursors that would remain unreactive otherwise. The low growth temperature enables the control of the plate thickness, which can be precisely tuned from 3 to 5 monolayers. The strong two-dimensional confinement of the carriers at such small vertical sizes is responsible for a narrow PL, strong excitonic absorption, and a blue shift of the optical band gap by more than 0.47 eV compared to that of bulk CsPbBr3. We also show that the composition of the NPLs can be varied all the way to CsPbBr3 or CsPbI3 by anion exchange, with preservation of the size and shape of the starting particles. The blue fluorescent CsPbCl3 NPLs represent a new member of the scarcely populated group of blue-emitting colloidal nanocrystals. The exciton dynamics were found to be independent of the extent of 2D confinement in these platelets, and this was supported by band structure calculations.

Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions.

We demonstrate that, via controlled anion exchange reactions using a range of different halide precursors, we can finely tune the chemical composition and the optical properties of presynthesized colloidal cesium lead halide perovskite nanocrystals (NCs), from green emitting CsPbBr3 to bright emitters in any other region of the visible spectrum, and back, by displacement of Cl(-) or I(-) ions and reinsertion of Br(-) ions. This approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs. We also show that anion exchange is a dynamic process that takes place in solution between NCs. Therefore, by mixing solutions containing perovskite NCs emitting in different spectral ranges (due to different halide compositions) their mutual fast exchange dynamics leads to homogenization in their composition, resulting in NCs emitting in a narrow spectral region that is intermediate between those of the parent nanoparticles.

Self-assembly of colloidal hexagonal bipyramid- and bifrustum-shaped ZnS nanocrystals into two-dimensional superstructures.

We present a combined experimental, theoretical, and simulation study on the self-assembly of colloidal hexagonal bipyramid- and hexagonal bifrustum-shaped ZnS nanocrystals (NCs) into two-dimensional superlattices. The simulated NC superstructures are in good agreement with the experimental ones. This shows that the self-assembly process is primarily driven by minimization of the interfacial free-energies and maximization of the packing density. Our study shows that a small truncation of the hexagonal bipyramids is sufficient to change the symmetry of the resulting superlattice from hexagonal to tetragonal, highlighting the crucial importance of precise shape control in the fabrication of functional metamaterials by self-assembly of colloidal NCs.

Size-Tunable Manganese-Doped Spheroidal CsPbCl3 Quantum Dots.

Manganese doping has been demonstrated as a versatile tool to tune the emission of CsPbCl3 nanocrystals (NCs). Although this has been demonstrated in nanocubes and nanoplatelets, strategies for doping Mn2+ in size-tunable, excitonic CsPbCl3 quantum dots (QDs) remain absent. In this work, we demonstrate the synthesis of size-tunable spheroidal CsPbCl3:Mn2+ QDs, which can be obtained by a water-hexane interfacial combined anion and cation exchange strategy starting from CsPbBr3 QDs. Interestingly, the QDs exhibit a fast 0.2 ms Mn2+ photoluminescence (PL) lifetime and an energy transfer (ET) time of approximately 100 ps from the excitonic state of the QD to the atomic state of the Mn2+ ion. The size dependence observation of the manganese PL efficiency and the slow ET rate suggest that Mn2+ mainly gets incorporated at the QD's surface, highlighting the importance of strategies chosen for the incorporation of Mn2+ into perovskite QDs.

A Bound Exciton Resonance Modulated by Bulk and Localized Coherent Phonons in Double Perovskites.

Optically excited electronic excitations are coupled to the soft and polar halide perovskite lattice, generating coherent phonons after subpicosecond interband laser-excitation. In Ag-based halide double perovskites, Ag-vacancies can bind free excitons, resulting in a pronounced bound exciton resonance. Here, we report the detection of three modulation frequencies corresponding to coherent phonons in Ag-based double perovskite nanocrystals at distinct spectral positions at the bound exciton resonance. Two of them are found in oscillatory spectral shifts of the bound exciton resonance and are identified as Cs- and Br-related bulk phonons. Surprisingly, a third frequency is observed as an intensity modulation. We argue that this amplitude oscillation is a consequence of an optically generated vibronic wave packet localized at a Ag-vacancy. Consequently, the localized coherent phonon modulates the giant oscillator strength of the bound exciton. This optically induced and spatially localized lattice shaking could potentially be useful for initiating photochemical reactions with atomic precision.

Controlling the nucleation and growth kinetics of lead halide perovskite quantum dots.

Colloidal lead halide perovskite nanocrystals are of interest as photoluminescent quantum dots (QDs) whose properties depend on the size and shape. They are normally synthesized on subsecond time scales through hard-to-control ionic metathesis reactions. We report a room-temperature synthesis of monodisperse, isolable, spheroidal APbBr3 QDs ("A" indicates cesium, formamidinium, and methylammonium) that are size tunable from 3 to >13 nanometers. The kinetics of both nucleation and growth are temporally separated and substantially slowed down by the intricate equilibrium between the precursor (PbBr2) and the A[PbBr3] solute, with the latter serving as a monomer. QDs of all these compositions exhibit up to four excitonic transitions in their linear absorption spectra, and we demonstrate that the size-dependent confinement energy for all transitions is independent of the A-site cation.

Exploiting the Lability of Metal Halide Perovskites for Doping Semiconductor Nanocomposites.

Cesium lead halides have intrinsically unstable crystal lattices and easily transform within perovskite and nonperovskite structures. In this work, we explore the conversion of the perovskite CsPbBr3 into Cs4PbBr6 in the presence of PbS at 450 °C to produce doped nanocrystal-based composites with embedded Cs4PbBr6 nanoprecipitates. We show that PbBr2 is extracted from CsPbBr3 and diffuses into the PbS lattice with a consequent increase in the concentration of free charge carriers. This new doping strategy enables the adjustment of the density of charge carriers between 1019 and 1020 cm-3, and it may serve as a general strategy for doping other nanocrystal-based semiconductors.