Lead-Free, Luminescent Perovskite Nanocrystals Obtained through Ambient Condition Synthesis.

Heterovalently substituting toxic lead is an increasingly popular design strategy to obtain environmentally sustainable variants of the exciting material class of halide perovskites. Perovskite nanocrystals (NCs) obtained through solution-based methods exhibit exceedingly high optical quality. Unfortunately, most of these synthesis routes still require reaction under inert gas and at very high temperatures. Herein a novel synthesis routine for lead-free double perovskite (LFDP) NCs is presented. An approach based upon the hot injection and ligand-assisted reprecipitation (LARP) methods to achieve a low-temperature and ambient atmosphere-based synthesis for manganese-doped Cs2 NaBiCl6 NCs is presented. Mn incorporation is critical for the otherwise non-emissive material, with a 9:1 Bi:Mn precursor ratio maximizing the bright orange photoluminescence (PL) and quantum yield (QY). Higher synthesis temperatures slightly increase the material's performance, yet NCs synthesized at room temperature are still emissive, highlighting the versatility of the synthetic approach. While the material's indirect bandgap limits its appeal for optoelectronics, this feature could benefit photocatalysis due to longer carrier lifetimes. Moreover, the developed synthesis is facile and can rapidly be adapted to other more viable material compositions and up-scaled to realize applications directly.

Rapid Data-Efficient Optimization of Perovskite Nanocrystal Syntheses through Machine Learning Algorithm Fusion.

With the demand for renewable energy and efficient devices rapidly increasing, a need arises to find and optimize novel (nano)materials. With sheer limitless possibilities for material combinations and synthetic procedures, obtaining novel, highly functional materials has been a tedious trial and error process. Recently, machine learning has emerged as a powerful tool to help optimize syntheses; however, most approaches require a substantial amount of input data, limiting their pertinence. Here, three well-known machine-learning models are merged with Bayesian optimization into one to optimize the synthesis of CsPbBr3 nanoplatelets with limited data demand. The algorithm can accurately predict the photoluminescence emission maxima of nanoplatelet dispersions using only the three precursor ratios as input parameters. This allows us to fabricate previously unobtainable seven and eight monolayer-thick nanoplatelets. Moreover, the algorithm dramatically improves the homogeneity of 2-6-monolayer-thick nanoplatelet dispersions, as evidenced by narrower and more symmetric photoluminescence spectra. Decisively, only 200 total syntheses are required to achieve this vast improvement, highlighting how rapidly material properties can be optimized. The algorithm is highly versatile and can incorporate additional synthetic parameters. Accordingly, it is readily applicable to other less-explored nanocrystal syntheses and can help rapidly identify and improve exciting compositions' quality.

Energy Transfer in Stability-Optimized Perovskite Nanocrystals.

Outstanding optoelectronic properties and a facile synthesis render halide perovskite nanocrystals (NCs) a promising material for nanostructure-based devices. However, the commercialization is hindered mainly by the lack of NC stability under ambient conditions and inefficient charge carrier injection. Here, we investigate solutions to both problems, employing methylammonium lead bromide (MAPbBr3) NCs encapsulated in diblock copolymer core-shell micelles of tunable size. We confirm that the shell does not prohibit energy transfer, as FRET efficiencies between these NCs and 2D CsPbBr3 nanoplatelets (NPLs) reach 73.6%. This value strongly correlates to the micelle size, with thicker shells displaying significantly reduced FRET efficiencies. Those high efficiencies come with a price, as the thinnest shells protect the encapsulated NCs less from environmentally induced degradation. Finding the sweet spot between efficiency and protection could lead to the realization of tailored energy funnels with enhanced carrier densities for high-power perovskite NC-based optoelectronic applications.

Thickness-Dependent Dark-Bright Exciton Splitting and Phonon Bottleneck in CsPbBr3-Based Nanoplatelets Revealed via Magneto-Optical Spectroscopy.

The optimized exploitation of perovskite nanocrystals and nanoplatelets as highly efficient light sources requires a detailed understanding of the energy spacing within the exciton manifold. Dark exciton states are particularly relevant because they represent a channel that reduces radiative efficiency. Here, we apply large in-plane magnetic fields to brighten optically inactive states of CsPbBr3-based nanoplatelets for the first time. This approach allows us to access the dark states and directly determine the dark-bright splitting, which reaches 22 meV for the thinnest nanoplatelets. The splitting is significantly less for thicker nanoplatelets due to reduced exciton confinement. Additionally, the form of the magneto-PL spectrum suggests that dark and bright state populations are nonthermalized, which is indicative of a phonon bottleneck in the exciton relaxation process.

Electron-Hole Binding Governs Carrier Transport in Halide Perovskite Nanocrystal Thin Films.

Two-dimensional halide perovskite nanoplatelets (NPLs) have exceptional light-emitting properties, including wide spectral tunability, ultrafast radiative decays, high quantum yields (QY), and oriented emission. Due to the high binding energies of electron-hole pairs, excitons are generally considered the dominant species responsible for carrier transfer in NPL films. To realize efficient devices, it is imperative to understand how exciton transport progresses therein. We employ spatially and temporally resolved optical microscopy to map exciton diffusion in perovskite nanocrystal (NC) thin films between 15 °C and 55 °C. At room temperature (RT), we find the diffusion length to be inversely correlated to the thickness of the nanocrystals (NCs). With increasing temperatures, exciton diffusion declines for all NC films, but at different rates. This leads to specific temperature turnover points, at which thinner NPLs exhibit higher diffusion lengths. We attribute this anomalous diffusion behavior to the coexistence of excitons and free electron hole-pairs inside the individual NCs within our temperature range. The organic ligand shell surrounding the NCs prevents charge transfer. Accordingly, any time an electron-hole pair spends in the unbound state reduces the FRET-mediated inter-NC transfer rates and, consequently, the overall diffusion. These results clarify how exciton diffusion progresses in strongly confined halide perovskite NC films, emphasizing critical considerations for optoelectronic devices.

Dark and Bright Excitons in Halide Perovskite Nanoplatelets.

Semiconductor nanoplatelets (NPLs), with their large exciton binding energy, narrow photoluminescence (PL), and absence of dielectric screening for photons emitted normal to the NPL surface, could be expected to become the fastest luminophores amongst all colloidal nanostructures. However, super-fast emission is suppressed by a dark (optically passive) exciton ground state, substantially split from a higher-lying bright (optically active) state. Here, the exciton fine structure in 2-8 monolayer (ML) thick Csn - 1 Pbn Br3n + 1 NPLs is revealed by merging temperature-resolved PL spectra and time-resolved PL decay with an effective mass model taking quantum confinement and dielectric confinement anisotropy into account. This approach exposes a thickness-dependent bright-dark exciton splitting reaching 32.3 meV for the 2 ML NPLs. The model also reveals a 5-16 meV splitting of the bright exciton states with transition dipoles polarized parallel and perpendicular to the NPL surfaces, the order of which is reversed for the thinnest NPLs, as confirmed by TR-PL measurements. Accordingly, the individual bright states must be taken into account, while the dark exciton state strongly affects the optical properties of the thinnest NPLs even at room temperature. Significantly, the derived model can be generalized for any isotropically or anisotropically confined nanostructure.

How Exciton-Phonon Coupling Impacts Photoluminescence in Halide Perovskite Nanoplatelets.

Semiconductor nanocrystals are receiving increased interest as narrow-band emitters for display applications. Here, we investigate the underlying photoluminescence (PL) linewidth broadening mechanisms in thickness-tunable 2D halide perovskite (Csn-1PbnBr3n+1) nanoplatelets (NPLs). Temperature-dependent PL spectroscopy on NPL thin films reveals a blue-shift of the PL maximum for thicker NPLs, no shift for three monolayer (ML) thick NPLs, and a red-shift for the thinnest (2 ML) NPLs with increasing temperature. Emission linewidths also strongly depend on NPL thickness, with the thinnest NPLs showing the smallest temperature-induced broadening. We determine the combined interaction of exciton-phonon coupling and thermal lattice expansion to be responsible for both effects. Additionally, the 2 ML NPLs exhibit a significantly larger Fröhlich coupling constant and optical phonon energy, possibly due to an inversion in the exciton fine structure. These results illustrate that ultrathin halide perovskite NPLs could illuminate the next generation of displays, provided a slightly greater sample homogeneity and improved stability.

Thickness-Dependence of Exciton-Exciton Annihilation in Halide Perovskite Nanoplatelets.

Exciton-exciton annihilation (EEA) and Auger recombination are detrimental processes occurring in semiconductor optoelectronic devices at high carrier densities. Despite constituting one of the main obstacles for realizing lasing in semiconductor nanocrystals (NCs), the dependencies on NC size are not fully understood, especially for those with both weakly and strongly confined dimensions. Here, we use differential transmission spectroscopy to investigate the dependence of EEA on the physical dimensions of thickness-controlled 2D halide perovskite nanoplatelets (NPls). We find the EEA lifetimes to be extremely short on the order of 7-60 ps. Moreover, they are strongly determined by the NPl thickness with a power law dependence according to τ2 ∝ d5.3. Additional measurements show that the EEA lifetimes also increase for NPls with larger lateral dimensions. These results show that a precise control of the physical dimensions is critical for deciphering the fundamental laws governing the process especially in 1D and 2D NCs.

Nonradiative Energy Transfer between Thickness-Controlled Halide Perovskite Nanoplatelets.

Despite showing great promise for optoelectronics, the commercialization of halide perovskite nanostructure-based devices is hampered by inefficient electrical excitation and strong exciton binding energies. While transport of excitons in an energy-tailored system via Förster resonance energy transfer (FRET) could be an efficient alternative, halide ion migration makes the realization of cascaded structures difficult. Here, we show how these could be obtained by exploiting the pronounced quantum confinement effect in two-dimensional CsPbBr3-based nanoplatelets (NPls). In thin films of NPls of two predetermined thicknesses, we observe an enhanced acceptor photoluminescence (PL) emission and a decreased donor PL lifetime. This indicates a FRET-mediated process, benefitted by the structural parameters of the NPls. We determine corresponding transfer rates up to k FRET = 0.99 ns-1 and efficiencies of nearly ηFRET = 70%. We also show FRET to occur between perovskite NPls of other thicknesses. Consequently, this strategy could lead to tailored energy cascade nanostructures for improved optoelectronic devices.

Fast Electron and Slow Hole Relaxation in InP-Based Colloidal Quantum Dots.

Colloidal InP-based quantum dots are a promising material for light-emitting applications as an environment friendly alternative to their Cd-containing counterparts. Especially for their use in optoelectronic devices, it is essential to understand how charge carriers relax to the emitting state after injection with excess energy and if all of them arrive at this desired state. Herein, we report time-resolved differential transmission measurements on colloidal InP/ZnS and InP/ZnSe core/shell quantum dots. By optically exciting and probing individual transitions, we are able to distinguish between electron and hole relaxation. This, in turn, allows us to determine how the initial excess energy of the charge carriers affects the relaxation processes. According to the electronic level scheme, one expects a strong phonon bottleneck for electrons, whereas holes should relax easier as their energy levels are more closely spaced. On the contrary, we find that electrons relax faster than holes. The fast electron relaxation occurs via an efficient Auger-like electron-hole scattering mechanism. On the other hand, a small wave function overlap between core and shell states slows the hole relaxation. Additionally, holes can be trapped at the core/shell interface, leading to either slow detrapping or nonradiative recombination. Overall, these results demonstrate that it is crucial to construct devices enabling the injection of charge carriers energetically close to their emitting states in order to maximize the radiative efficiency of the system.

Real-Time Electron and Hole Transport Dynamics in Halide Perovskite Nanowires.

For optoelectronic devices, high transport mobilities of electrons and holes are desirable, which, moreover, should be close to identical. Acousto-optoelectric spectroscopy is employed to probe the spatiotemporal dynamics of both electrons and holes inside CsPbI3 nanowires. These dynamics are induced without the need for electrical contacts simply by the piezoelectric field of a surface acoustic wave. Its radio frequency of fSAW = 324 MHz natively avoids spurious contributions from ion migration typically occurring in these materials. The observed dynamic modulation of the photoluminescence is faithfully reproduced by solving the drift and diffusion currents of electrons and holes induced by the surface acoustic wave. These calculations confirm that the mobilities of electrons and holes are equal and quantify them to be µe = µh = 3 ± 1 cm2 V-1 s-1. Additionally, carrier loss due to surface recombination is shown to be largely suppressed in CsPbI3 nanowires. Both findings mark significant advantages over traditional compound semiconductors, in particular, GaAs, for applications in future optoelectronic and photovoltaic devices. The demonstrated sublifetime modulation of the optical emission may find direct application in switchable perovskite light-emitting devices employing mature surface acoustic wave technology.

Polymer Nanoreactors Shield Perovskite Nanocrystals from Degradation.

Halide perovskite nanocrystals (NCs) have shown impressive advances, exhibiting optical properties that outpace conventional semiconductor NCs, such as near-unity quantum yields and ultrafast radiative decay rates. Nevertheless, the NCs suffer even more from stability problems at ambient conditions and due to moisture than their bulk counterparts. Herein, we report a strategy of employing polymer micelles as nanoreactors for the synthesis of methylammonium lead trihalide perovskite NCs. Encapsulated by this polymer shell, the NCs display strong stability against water degradation and halide ion migration. Thin films comprising these NCs exhibit a more than 15-fold increase in lifespan in comparison to unprotected NCs in ambient conditions and even survive over 75 days of complete immersion in water. Furthermore, the NCs, which exhibit quantum yields of up to 63% and tunability of the emission wavelength throughout the visible range, show no signs of halide ion exchange. Additionally, heterostructures of MAPI and MAPBr NC layers exhibit efficient Förster resonance energy transfer (FRET), revealing a strategy for optoelectronic integration.

Identifying and Reducing Interfacial Losses to Enhance Color-Pure Electroluminescence in Blue-Emitting Perovskite Nanoplatelet Light-Emitting Diodes.

Perovskite nanoplatelets (NPls) hold promise for light-emitting applications, having achieved photoluminescence quantum efficiencies approaching unity in the blue wavelength range, where other metal-halide perovskites have typically been ineffective. However, the external quantum efficiencies (EQEs) of blue-emitting NPl light-emitting diodes (LEDs) have reached only 0.12%. In this work, we show that NPl LEDs are primarily limited by a poor electronic interface between the emitter and hole injector. We show that the NPls have remarkably deep ionization potentials (≥6.5 eV), leading to large barriers for hole injection, as well as substantial nonradiative decay at the NPl/hole-injector interface. We find that an effective way to reduce these nonradiative losses is by using poly(triarylamine) interlayers, which lead to an increase in the  EQE of the blue (464 nm emission wavelength) and sky-blue (489 nm emission wavelength) LEDs to 0.3% and 0.55%, respectively. Our work also identifies the key challenges for further efficiency increases.

Ru(TAP)32+ uses multivalent binding to accelerate and constrain photo-adduct formation on DNA.

Ru(ii)-complexes with polyazaaromatic ligands can undergo direct electron transfer with guanine nucleobases on blue light excitation that results in DNA lesions with phototherapeutic potential. Here we use single molecule approaches to demonstrate DNA binding mode heterogeneity and evaluate how multivalent binding governs the photochemistry of [Ru(TAP)3]2+ (TAP = 1,4,5,8-tetraazaphenanthrene).

Metal Halide Perovskite Nanocrystals: Synthesis, Post-Synthesis Modifications, and Their Optical Properties.

Metal halide perovskites represent a flourishing area of research, which is driven by both their potential application in photovoltaics and optoelectronics and by the fundamental science behind their unique optoelectronic properties. The emergence of new colloidal methods for the synthesis of halide perovskite nanocrystals, as well as the interesting characteristics of this new type of material, has attracted the attention of many researchers. This review aims to provide an up-to-date survey of this fast-moving field and will mainly focus on the different colloidal synthesis approaches that have been developed. We will examine the chemistry and the capability of different colloidal synthetic routes with regard to controlling the shape, size, and optical properties of the resulting nanocrystals. We will also provide an up-to-date overview of their postsynthesis transformations, and summarize the various solution processes that are aimed at fabricating halide perovskite-based nanocomposites. Furthermore, we will review the fundamental optical properties of halide perovskite nanocrystals by focusing on their linear optical properties, on the effects of quantum confinement, and on the current knowledge of their exciton binding energies. We will also discuss the emergence of nonlinear phenomena such as multiphoton absorption, biexcitons, and carrier multiplication. Finally, we will discuss open questions and possible future directions.

Accelerated Carrier Relaxation through Reduced Coulomb Screening in Two-Dimensional Halide Perovskite Nanoplatelets.

For high-speed optoelectronic applications relying on fast relaxation or energy-transfer mechanisms, understanding of carrier relaxation and recombination dynamics is critical. Here, we compare the differences in photoexcited carrier dynamics in two-dimensional (2D) and quasi-three-dimensional (quasi-3D) colloidal methylammonium lead iodide perovskite nanoplatelets via differential transmission spectroscopy. We find that the cooling of excited electron-hole pairs by phonon emission progresses much faster and is intensity-independent in the 2D case. This is due to the low dielectric surrounding of the thin perovskite layers, for which the Fröhlich interaction is screened less efficiently leading to higher and less density-dependent carrier-phonon scattering rates. In addition, rapid dissipation of heat into the surrounding occurs due to the high surface-to-volume ratio. Furthermore, we observe a subpicosecond dissociation of resonantly excited 1s excitons in the quasi-3D case, an effect which is suppressed in the 2D nanoplatelets due to their large exciton binding energies. The results highlight the importance of the surrounding environment of the inorganic nanoplatelets on their relaxation dynamics. Moreover, this 2D material with relaxation times in the subpicosecond regime shows great potential for realizing devices such as photodetectors or all-optical switches operating at THz frequencies.

Boosting Tunable Blue Luminescence of Halide Perovskite Nanoplatelets through Postsynthetic Surface Trap Repair.

The easily tunable emission of halide perovskite nanocrystals throughout the visible spectrum makes them an extremely promising material for light-emitting applications. Whereas high quantum yields and long-term colloidal stability have already been achieved for nanocrystals emitting in the red and green spectral range, the blue region currently lags behind with low quantum yields, broad emission profiles, and insufficient colloidal stability. In this work, we present a facile synthetic approach for obtaining two-dimensional CsPbBr3 nanoplatelets with monolayer-precise control over their thickness, resulting in sharp photoluminescence and electroluminescence peaks with a tunable emission wavelength between 432 and 497 nm due to quantum confinement. Subsequent addition of a PbBr2-ligand solution repairs surface defects likely stemming from bromide and lead vacancies in a subensemble of weakly emissive nanoplatelets. The overall photoluminescence quantum yield of the blue-emissive colloidal dispersions is consequently enhanced up to a value of 73 ± 2%. Transient optical spectroscopy measurements focusing on the excitonic resonances further confirm the proposed repair process. Additionally, the high stability of these nanoplatelets in films and to prolonged ultraviolet light exposure is shown.

Spontaneous Self-Assembly of Perovskite Nanocrystals into Electronically Coupled Supercrystals: Toward Filling the Green Gap.

Self-assembly of nanoscale building blocks into ordered nanoarchitectures has emerged as a simple and powerful approach for tailoring the nanoscale properties and the opportunities of using these properties for the development of novel optoelectronic nanodevices. Here, the one-pot synthesis of CsPbBr3 perovskite supercrystals (SCs) in a colloidal dispersion by ultrasonication is reported. The growth of the SCs occurs through the spontaneous self-assembly of individual nanocrystals (NCs), which form in highly concentrated solutions of precursor powders. The SCs retain the high photoluminescence (PL) efficiency of their NC subunits, however also exhibit a redshifted emission wavelength compared to that of the individual nanocubes due to interparticle electronic coupling. This redshift makes the SCs pure green emitters with PL maxima at ≈530-535 nm, while the individual nanocubes emit a cyan-green color (≈512 nm). The SCs can be used as an emissive layer in the fabrication of pure green light-emitting devices on rigid or flexible substrates. Moreover, the PL emission color is tunable across the visible range by employing a well-established halide ion exchange reaction on the obtained CsPbBr3 SCs. These results highlight the promise of perovskite SCs for light emitting applications, while providing insight into their collective optical properties.

Resonantly enhanced multiple exciton generation through below-band-gap multi-photon absorption in perovskite nanocrystals.

Multi-photon absorption and multiple exciton generation represent two separate strategies for enhancing the conversion efficiency of light into usable electric power. Targeting below-band-gap and above-band-gap energies, respectively, to date these processes have only been demonstrated independently. Here we report the combined interaction of both nonlinear processes in CsPbBr3 perovskite nanocrystals. We demonstrate nonlinear absorption over a wide range of below-band-gap excitation energies (0.5-0.8 Eg). Interestingly, we discover high-order absorption processes, deviating from the typical two-photon absorption, at specific energetic positions. These energies are associated with a strong enhancement of the photoluminescence intensity by up to 105. The analysis of the corresponding energy levels reveals that the observed phenomena can be ascribed to the resonant creation of multiple excitons via the absorption of multiple below-band-gap photons. This effect may open new pathways for the efficient conversion of optical energy, potentially also in other semiconducting materials.

Tracking the Source of Carbon Dot Photoluminescence: Aromatic Domains versus Molecular Fluorophores.

Carbon dots (CDs) are an intriguing fluorescent material; however, due to a plethora of synthesis techniques and precursor materials, there is still significant debate on their structure and the origin of their optical properties. The two most prevalent mechanisms to explain them are based on polycyclic aromatic hydrocarbon domains and small molecular fluorophores, for instance, citrazinic acid. Yet, how these form and whether they can exist simultaneously is still under study. To address this, we vary the hydrothermal synthesis time of CDs obtained from citric acid and ethylenediamine and show that in the initial phase molecular fluorophores, likely 2-pyridone derivatives, account for the blue luminescence of the dots. However, over time, while the overall size of the CDs does not change, aromatic domains form and grow, resulting in a second, faster decay channel at similar wavelengths and also creating additional lower energetic states. Electrophoresis provides further evidence that the ensemble of CDs consists of several subsets with different internal structure and surface charge. The understanding of the formation mechanism enables a control of the chemical origin of these emitters and the ensuing optical properties of the CDs through synthetic means.