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Exploration of the full potential of the perovskite nanocrystals (NCs) for different applications requires a thorough understanding of the pathways of recombination of the photogenerated charge carriers and associated dynamics. In this work, we have tracked the recombination routes of the charge carriers by probing photoluminescence (PL) intermittency of the immobilized and freely diffusing single CsPbBr 3 NCs employing a time-tagged-time-resolved method. The immobilized single CsPbBr 3 NCs show a complex PL time-trace, a careful analysis of which reveals that nonradiative band-edge recombination through trap states, trion recombination, and trapping of the hot carriers contribute to the blinking behavior of any given NC. A drastically suppressed PL blinking observed for the NCs treated with a tetrafluoroborate salt indicates elimination of most of the undesired recombination processes. A fluorescence correlation spectroscopy (FCS) study on the freely diffusing single NCs shows that enhanced PL and suppressed blinking of the treated particles are the outcome of an increase in per-particle brightness, not due to any increase in the number of particles undergoing "off"-"on" transition in the observation volume. The mechanistic details obtained from this study on the origin of blinking in CsPbBr 3 NCs provide deep insight into the radiative and nonradiative charge carrier recombination pathways in these important materials, and this knowledge is expected to be useful for better design and development of bright photoluminescent samples of this class for optoelectronic applications.

Colloidal halide perovskite nanocrystals are promising candidates for next-generation optoelectronics because of their facile synthesis and their outstanding and size-tunable properties. However, these materials suffer from rapid degradation, similarly to their bulk perovskite counterparts. Here, we survey the most recent strategies to boost perovskite nanocrystals stability, with a special focus on the intrinsic chemical- and compositional-factors at synthetic and post-synthetic stage. Finally, we review the most promising approaches to address the environmental extrinsic stability of perovskite nanocrystals (PNCs). Our final goal is to outline the most promising research directions to enhance PNCs' lifetime, bringing them a step closer to their commercialization.

The growing demand for perovskite nanocrystals (NCs) for various applications has stimulated the development of facile synthetic methods. Perovskite NCs have often been synthesized by either ligand-assisted reprecipitation (LARP) at room temperature or by hot-injection at high temperatures and inert atmosphere. However, the use of polar solvents in LARP affects their stability. Herein, we report on the spontaneous crystallization of perovskite NCs in nonpolar organic media at ambient conditions by simple mixing of precursor-ligand complexes without application of any external stimuli. The shape of the NCs can be controlled from nanocubes to nanoplatelets by varying the ratio of monovalent (e.g. formamidinium + (FA + ) and Cs + ) to divalent (Pb 2+ ) cation-ligand complexes. The precursor-ligand complexes are stable for months, and thus perovskite NCs can be readily prepared prior to use. Moreover, we show that this versatile synthetic process is scalable and generally applicable for perovskite NCs of different compositions., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Hybrid graphene-perovskite photodetectors embrace the excellent photoabsorption properties of perovskites and high carrier mobility of graphene in a single device. Here, we demonstrate the integration of halide-ion-exchanged CsPbBr x I 3- x nanocrystals (NCs) as a photoabsorber and graphene as a transport layer. The NCs conform to a cubic lattice structure and exhibit an optical band gap of 1.93 eV. The hybrid device attained a maximum responsivity of 1.13 × 10 4 A/W and specific detectivity of 1.17 × 10 11 Jones in low light intensity (∼80 μW/cm 2 ). Specifically, an ultrahigh photoconductive gain of 9.32 × 10 10 is attained because of fast hole transit time in the graphene transistor and long recombination lifetime in the perovskite NCs simultaneously. The phototransistor also shows good stability and can maintain ∼95% of the photocurrent under continuous illumination over 5 h and ∼82% under periodic illumination over 37 h. Our results also revealed that the common issue of ion separation and segregated halide domains in mixed halide perovskite NCs do not occur under low light intensities. The intensive degradation of CsPbBr x I 3- x NCs is only observed under stronger light excitation (≥55 mW/cm 2 ), reflecting as emission shifts. Our work establishes the use of fully inorganic perovskite NCs as highly stable photodetectors with high responsivity and low power light detection.

Semiconductor nanorods (NRs) offer the useful property of linearly polarized light emission. While this would be an attractive functionality for strongly emitting perovskite nanoparticles, to date, there has been limited success in demonstrating a direct chemical synthesis of cesium lead halide perovskite NRs. In this work, we realized the direct synthesis of CsPbBr 3 NRs with an average width of around 5 nm and average lengths of 10.8 and 23.2 nm, respectively, in two samples, which show a high photoluminescence quantum yield of 60-76% and reasonably high emission anisotropy of about 0.2 for longer rods. Both CsPbCl 3 and CsPbI 3 NRs with similar dimensions have then been derived from the CsPbBr 3 NRs by anion-exchange reactions. Remarkably, the synthesis of the NRs has been achieved in polar alcohols, a class of solvents not usually found to be beneficial in classical perovskite nanoparticle synthesis. This work not only offers the possibility to control the shape of chemically synthesized perovskite nanocrystals but also constitutes the hitherto less common strategy of synthesizing perovskite nanoparticles in polar rather than nonpolar or only weakly polar solvents.

Lead halide perovskites have been extensively investigated in a host of optoelectronic devices, such as solar cells, light-emitting diodes, and photodetectors. The halogen vacancy defects arising from the halogen-poor growth environment are normally regarded as an unfavorable factor to restrict the device performance. Here, for the first time, we demonstrate the utilization of the vacancy defects in lead halide perovskite nanostructures for achieving high-performance nanofloating gate memories (NFGMs). CH 3 NH 3 PbBr 3 nanocrystals (NCs) were uniformly decorated on the CdS nanoribbon (NR) surface via a facile dip-coating process, forming a CdS NR/CH 3 NH 3 PbBr 3 NC core-shell structure. Significantly, owing to the existence of sufficient carrier trapping states in CH 3 NH 3 PbBr 3 NCs, the hybrid device possessed an ultralarge memory window up to 77.4 V, a long retention time of 12 000 s, a high current ON/OFF ratio of 7 × 10 7 , and a long-term air stability for 50 days. The memory window of the device is among the highest for the low-dimensional nanostructure-based NFGMs. Also, this strategy shows good universality and can be extended to other perovskite nanostructures for the construction of high-performance NFGMs. This work paves the way toward the fabrication of new-generation, high-capacity nonvolatile memories using lead halide perovskite nanostructures.

CsPbX 3 (X = I, Br, Cl) perovskite nanocrystals (NCs) have recently emerged as emitting materials for optoelectronic and display applications owing to their easily tunable emissions, high photoluminescence quantum yield (PLQY), and vivid color purity (full width at half maximum of approximately 20 nm). However, the lagging quantum yields of blue-emitting perovskite NCs have resulted in low efficiency compared to green or red perovskite light-emitting diodes (PeLEDs); moreover, the long insulating ligands (such as oleylamine and oleic acid) inhibit charge carrier injection. In this study, we demonstrated a facile ligand-mediated post-treatment (LMPT) method for high-quality perovskite NCs with changing optical properties to allow fine-tuning of the target emission wavelength. This method involves the use of a mixed halide ion-pair ligand, di-dodecyl dimethyl ammonium bromide, and chloride, which can induce a reconstruction through a self-anion exchange. Using the LMPT method, the PLQY of the surface-passivated blue-emitting NCs was dramatically enhanced to over 70% within the 485 nm blue emission region and 50% within the 467 nm deep-blue emission region. Through this treatment, we achieved highly efficient blue-PeLED maximum external quantum efficiencies of 0.44 and 0.86% within the 470 and 480 ± 2 nm electroluminescence emission regions, respectively.

Lead-halide perovskite APbX 3 (A = Cs or organic cation; X = Cl, Br, I) nanocrystals (NCs) are the subject of intense research due to their exceptional characteristics as both classical and quantum light sources. Many challenges often faced with this material class concern the long-term optical stability, a serious intrinsic issue connected with the labile and polar crystal structure of APbX 3 compounds. When conducting spectroscopy at a single particle level, due to the highly enhanced contaminants (e.g., water molecules, oxygen) over the NC ratio, deterioration of NC optical properties occurs within tens of seconds with typically used excitation power densities (1-100 W/cm 2 ) and in ambient conditions. Here, we demonstrate that choosing a suitable polymer matrix is of paramount importance for obtaining stable spectra from a single NC and for suppressing the dynamic photoluminescence blueshift. In particular, polystyrene (PS), the most hydrophobic among four tested polymers, leads to the best optical stability, one to two orders of magnitude higher than that obtained with poly(methyl methacrylate), a common polymeric encapsulant containing polar ester groups. Molecular mechanics simulations based on a force-field approximation corroborate the hypothesis that PS affords for a denser molecular packing at the NC surface. These findings underscore the often-neglected role of the sample preparation methodologies for the assessment of the optical properties of perovskite NCs at a single-particle level and guide the further design of robust single photon sources.

Moisture- or oxidation-induced degradation is a major challenge in the advancement of perovskites-based technology. The oxidation is caused by electron transfer from a photo-excited perovskite nanocrystal to oxygen and the formation of superoxide that disintegrates the perovskite structure. In air, the emission intensity of a methylammonium lead iodide (MAPbI 3 ) perovskite nanocrystal continuously decreases, whereas a nanocrystal in argon or a polymer shows exceptionally stable emission intensity. Surprisingly, in air, the emission intensity of a nanocrystal with long-lived OFF states completely recovers after the OFF state. This property, along with the rate of non-radiative relaxation that exceeds the rate of electron transfer suggest that the perovskite nanocrystals produce and react with superoxide in the excited neutral state, but not in the ionized state. In other words, the ultrafast non-radiative relaxation in the ionized state hinders electron transfer to oxygen and prevents oxidation of perovskites., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

All-inorganic perovskites nanostructures, such as CsPbCl 3 nanocrystals (NCs), are promising in many applications including light-emitting diodes, photovoltaics, and photodetectors. Despite the impressive performance that was demonstrated, a critical issue remains due to the instability of the perovskites in ambient. Herein, we report a method of passivating crystalline CsPbCl 3 NC surfaces with 3-mercaptopropionic acid (MPA), and superior ambient stability is achieved. The printing of these colloidal NCs on the channel of graphene field-effect transistors (GFETs) on solid Si/SiO 2 and flexible polyethylene terephthalate substrates was carried out to obtain CsPbCl 3 NCs/GFET heterojunction photodetectors for flexible and visible-blind ultraviolet detection at wavelength below 400 nm. Besides ambient stability, the additional benefits of passivating surface charge trapping by the defects on CsPbCl 3 NCs and facilitating high-efficiency charge transfer between the CsPbCl 3 NCs and graphene were provided by MPA. Extraordinary optoelectronic performance was obtained on the CsPbCl 3 NCs/graphene devices including a high ultraviolet responsivity exceeding 10 6 A/W, a high detectivity of 2 × 10 13 Jones, a fast photoresponse time of 0.3 s, and ambient stability with less than 10% degradation of photoresponse after 2400 h. This result demonstrates the crucial importance of the perovskite NC surface passivation not only to the performance but also to the stability of the perovskite optoelectronic devices.

Perovskite nanocrystals (PNCs) are emerging luminescent materials due to their fascinating physic-optical properties. However, their sensitive surface chemistry with organic polar solvents, oxygen, and moisture greatly hinders their developments towards practical applications. Herein we promote silica-passivated PNCs (SP-PNCs) by in situ hydrolyzing the surface ligands of (3-aminopropyl) triethoxysilane. The resultant SP-PNCs possesses a high quantum yield (QY) of 80 % and are precipitable by polar solvents, such as ethanol and acetone, without destroying their surface chemistry or losing QY, which offers an eco-friendly and efficient method for separation, purification, and phase transfer of PNCs. Moreover, we further promoted a swelling-deswelling encapsulation process to incorporate the as-made SP-PNCs into non-crosslinked polystyrene microspheres (PMs), which can largely increase the stability of the SP-PNCs against moisture for long-term storage., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Colloidal halide perovskite nanocrystals of CsPbCl 3 doped with Yb 3+ have demonstrated remarkably high sensitized photoluminescence quantum yields (PLQYs), approaching 200%, attributed to a picosecond quantum-cutting process in which one photon absorbed by the nanocrystal generates two photons emitted by the Yb 3+ dopants. This quantum-cutting process is thought to involve a charge-neutral defect cluster within the nanocrystal's internal volume. We demonstrate that Yb 3+ -doped CsPbCl 3 nanocrystals can be converted postsynthetically to Yb 3+ -doped CsPb(Cl 1- x Br x ) 3 nanocrystals without compromising the desired high PLQYs. Nanocrystal energy gaps can be tuned continuously from E g ≈ 3.06 eV (405 nm) in CsPbCl 3 down to E g ≈ 2.53 eV (∼490 nm) in CsPb(Cl 0.25 Br 0.75 ) 3 while retaining a constant PLQY above 100%. Reducing E g further causes a rapid drop in PLQY, interpreted as reflecting an energy threshold for quantum cutting at approximately twice the energy of the Yb 3+ 2 F 7/2 → 2 F 5/2 absorption threshold. These data demonstrate that very high quantum-cutting energy efficiencies can be achieved in Yb 3+ -doped CsPb(Cl 1- x Br x ) 3 nanocrystals, offering the possibility to circumvent thermalization losses in conventional solar technologies. The presence of water during anion exchange is found to have a deleterious effect on the Yb 3+ PLQYs but does not affect the nanocrystal shapes or morphologies, or even reduce the excitonic PLQYs of analogous undoped CsPb(Cl 1- x Br x ) 3 nanocrystals. These results provide valuable information relevant to the development and application of these unique materials for spectral-shifting solar energy conversion technologies.

A method is proposed to improve the photo/electroluminescence efficiency and stability of CsPbI 3 perovskite nanocrystals (NCs) by using SrCl 2 as a co-precursor. The SrCl 2 is chosen as the dopant to synthesize the CsPbI 3 NCs. Because the ion radius of Sr 2+ (1.18 Å) is slightly smaller than that of Pb 2+ (1.19 Å) ions, divalent Sr 2+ cations can partly replace the Pb 2+ ions in the lattice structure of perovskite NCs and cause a slight lattice contraction. At the same time, Cl - anions from SrCl 2 are able to efficiently passivate surface defect states of CsPbI 3 nanocrystals, thus converting nonradiative trap states to radiative states. The simultaneous Sr 2+ ion doping and surface Cl - ion passivation result in the enhanced photoluminescence quantum yield (up to 84%), elongated emission lifetime, and improved stability. Sr 2+ -doped CsPbI 3 NCs are employed to produce light-emitting devices with a high external quantum yield of 13.5%., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The front cover of the January 2017 issue of the journal "Angewandte Chemie International Edition" is presented.

White light-emitting diodes (WLEDs) based on all-inorganic perovskite CsPbX 3 (X = Cl, Br, I) nanocrystals (NCs) have attracted extensive interests. However, the native ion exchange among halides makes them extremely difficult to realize the white emission. Herein, we demonstrate a novel strategy to obtain WLED phosphors based on the codoping of different metal ion pairs, such as Ce 3+ /Mn 2+ , Ce 3+ /Eu 3+ , Ce 3+ /Sm 3+ , Bi 3+ /Eu 3+ , and Bi 3+ /Sm 3+ into stable CsPbCl 3 and CsPbCl x Br 3- x NCs. Notably, by the typical anion exchange reaction, the highly efficient white emission of Ce 3+ /Mn 2+ -codoped all-inorganic CsPbCl 1.8 Br 1.2 perovskite NCs was achieved, with an optimal photoluminescence quantum yield of 75%, which is much higher than the present record of 49% for single perovskite phosphors. Moreover, the WLED with a luminous efficiency of 51 lm/W based on the 365 nm ultraviolet chip and CsPbCl 1.8 Br 1.2 :Ce 3+ /Mn 2+ nanophosphor was achieved. This work represents a novel device for perovskite-based phosphor-converted WLEDs.

Hybrid organic-inorganic and all-inorganic metal halide perovskite nanocrystals (PNCs) have aroused extensive attention from both academic and industrial researchers, considering their excellent performance in optoelectronic applications. Herein, we develop a facile and time-saving strategy to synthesize NH 2 CH═NH 2 PbBr 3 (NH 2 CH═NH + , FA) PNCs at room temperature. Benefiting from this facile method, high-quality FAPbBr 3 PNCs with photoluminescence quantum yield up to 76% and narrow full width at half-maxima of 20 nm can be produced on a large scale. Moreover, anion-exchange reactions run by using FAPbBr 3 as a template, producing various PNCs with different anion constituents. By manipulating the ratios of two different anions, a series PNCs with various bright photoluminescence ranging from 452 to 646 nm could be done. On account of superior and adjustable photoluminescence over the visible spectral region, FAPbBr 3 PNCs can be applied as a promising color-converting material in liquid-crystal display (LCD) backlight, white light-emitting diode (WLED), and inkjet printing pattern. As a proof of concept, FAPbBr 3 PNCs with green emission were integrated in WLED and LCD backlight, accomplishing a color rendering index of 87.5 and a wide color gamut of 116%, respectively.

In this paper, we reported the in situ fabrication of highly luminescent formamidinium lead bromide (FAPbBr 3 ) nanocrystal thin films by dropping toluene as an anti-solvent during the spin-coating with a perovskite precursor solution using 3,3-diphenylpropylamine bromide (DPPA-Br) as a ligand. The resulting films are uniform and composed of 5-20 nm FAPbBr 3 perovskite nanocrystals. By monitoring the solvent mixing of anti-solvent and precursor solution on the substrates, we illustrated the difference between the ligand-assisted reprecipitation (LARP) process and the nanocrystal-pinning (NCP) process. This understanding provides a guideline for film optimization, and the optimized films obtained through the in situ LARP process exhibit strong photoluminescence emission at 528 nm, with quantum yields up to 78% and an average photoluminescence lifetime of 12.7 ns. In addition, an exciton binding energy of 57.5 meV was derived from the temperature-dependent photoluminescence measurement. More importantly, we achieved highly efficient pure green perovskite based light-emitting diode (PeLEDs) devices with an average external quantum efficiency (EQE) of 7.3% (maximum EQE is 16.3%) and an average current efficiency (CE) of 29.5 cd A -1 (maximum CE is 66.3 cd A -1 ) by adapting a conventional device structure of ITO/PEDOT:PSS/TFB/perovskite film/TPBi/LiF/Al. It is expected that the in situ LARP process provides an effective methodology for the improvement of the performance of PeLEDs.

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 CsPbBr 3 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 PbBr 2 -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.

Creating CsPbBr 3 perovskite nanocrystals with bright blue emission is challenging because their optical properties depend sensitively on structure. Growing perovskites in mesoporous templates bypasses some of these purification issues because the size of the nanocrystal is governed by the dimensions of the pores. Mesoporous silica consisting of aligned channels with tunable diameter can be easily synthesized and used as a template. When the perovskite solution evaporates and retreats, some of the liquid remains trapped in the interconnecting pores by discontinuous dewetting. The precursor crystallizes, generating stable ca. 3.1 nm blue-emitting perovskite nanocrystals. The mesoporous template also serves as a protective barrier to preserve the optical properties of the CsPbBr 3 from atmospheric conditions. Compared to the bulk crystals and the powder composite, the strong blue-shift of the emission peak in the film is accompanied by a decrease in the longer lifetime component and an 8-fold increase in the external quantum efficiency., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

High temperature colloidal synthesis for obtaining thermal, colloidal and phase-stable CsPbI 3 nanocrystals with near-unity quantum yield is reported. While standard perovskite synthesis reactions were carried out at 160 °C (below 200 °C), increase of another ≈100 °C enabled the alkylammonium ions to passivate the surface firmly and prevented the nanocrystals from phase transformation. This did not require any inert atmosphere storage, use of heteroatoms, specially designed ligands, or the ice cooling protocol. Either at high temperature in reaction flask or in the crude mixture or purified dispersed solution; these nanocrystals were observed stable and retained the original emission. Different spectroscopic analyses were carried out and details of the surface binding of alkyl ammonium ligands in place of surface Cs in the crystal lattice were investigated. As CsPbI 3 is one of the most demanding optical materials, bringing stability by proper surface functionalization without use of secondary additives would indeed help in wide spreading of their applications., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Due to the sizable refractive index of lead halide perovskites, reflectivity off their interface with air exceeds 15%. This has prompted a number of investigations into the prominence of photoreflective contributions to pump-probe data in these materials, with conflicting results. Here we report experiments aimed at assessing this by comparing transient transmission from lead halide perovskite films and weakly quantum confined nanocrystals of cesium lead iodide (CsPbI 3 ) perovskite. By analyzing how complex refractive index changes impact the two experiments, results demonstrate that changes in absorption and not reflection dominate transient transmission measurements in thin films of these materials. None of the characteristic spectral signatures reported in such experiments are exclusively due to or even strongly affected by changes in sample reflectivity. This finding is upheld by another experiment where a methyl ammonium lead iodide (MAPbI 3 ) perovskite film was formed on high-index flint glass and probed after pump irradiation from either face of the sample. We conclude that interpretations of ultrafast pump-probe experiments on thin perovskite films in terms of photoinduced changes in absorption alone are qualitatively sound, requiring relatively minor adjustments to factor in photoreflective effects.

Recent advances in the ytterbium doping of CsPbX 3 (X = Cl or Cl/Br) nanocrystals have presented exciting new opportunities for their application as downconverters in solar-energy-conversion technologies. Here, we describe a hot-injection synthesis of Yb 3+ :CsPbCl 3 nanocrystals that reproducibly yields sensitized Yb 3+ 2 F 5/2 → 2 F 7/2 luminescence with near-infrared photoluminescence quantum yields (PLQYs) well over 100% and almost no excitonic luminescence. Near-infrared PLQYs of 170% have been measured. Through a combination of synthesis, variable-temperature photoluminescence spectroscopy, and transient-absorption and time-resolved photoluminescence spectroscopies, we show that the formation of shallow Yb 3+ -induced defects play a critical role in facilitating a picosecond nonradiative energy-transfer process that de-excites the photoexcited nanocrystal and simultaneously excites two Yb 3+ dopant ions, i.e., quantum cutting. Energy transfer is very efficient at all temperatures between 5 K and room temperature but only grows more efficient as the temperature is elevated in this range. Our results provide insights into the microscopic mechanism behind the extremely efficient sensitization of Yb 3+ luminescence in CsPbX 3 nanocrystals, with ramifications for future applications of high-efficiency spectral-conversion nanomaterials in solar technologies.

Replacing lead in halide perovskites is of great interest due to concerns about stability and toxicity. Recently, lead free double perovskites in which the unit cell is doubled and two divalent lead cations are substituted by a combination of mono- and trivalent cations have been synthesized as bulk single crystals and as thin films. Here, we study stability and optical properties of all-inorganic cesium silver(I) bismuth(III) chloride and bromide nanocrystals with the double perovskite crystal structure. The cube-shaped nanocrystals are monodisperse in size with typical side lengths of 8 to 15 nm. The absorption spectrum of the nanocrystals presents a sharp peak, which we assign to a direct bismuth s-p transition and not to a quantum confined excitonic transition. Using this spectroscopic handle combined with high-resolution transmission electron microscopy (TEM) based elemental analysis, we conduct stoichiometric studies at the single nanocrystal level as well as decomposition assays in solution and observe that Ag + diffusion and coalescence is one of the pathways by which this material degrades. Drying the nanocrystals leads to self-assembly into ordered nanocrystal solids, and these exhibit less degradation than nanocrystals in solution. Our results demonstrate that Cs 2 AgBiX 6 (X = Cl, Br) nanocrystals are a useful model system to study structure-function relationships in the search for stable nontoxic halide perovskites.

We developed a microwave-assisted slowed-down synthesis of CsPbBr 3 perovskite nanocrystals, which retards the reaction and allows us to gather useful insights into the formation mechanism of these nanoparticles, by examining the intermediate stages of their growth. The trends in the decay of the emission intensity of CsPbBr 3 nanocrystals under light exposure are well correlated with their stability against decomposition in TEM under electron beam. The results show the change of the crystal structure of CsPbBr 3 nanocrystals from a deficient and easier to be destroyed lattice to a well crystallized one. Conversely the shift in the ease of degradation sheds light on the formation mechanism, indicating first the formation of a bromoplumbate ionic scaffold, with Cs-ion infilling lagging a little behind. Increasing the cation to halide ratio towards the stoichiometric level may account for the improved radiative recombination rates observed in the longer reaction time materials., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The unification of tunable band edge (BE) emission and strong Mn 2+ doping luminescence in all-inorganic cesium lead halide perovskite nanocrystals (NCs) CsPbX 3 (X = Cl and Br) is of fundamental importance in fine tuning their optical properties. Herein, we demonstrate that benefiting from the differentiation of the cation/anion exchange rate, ZnBr 2 and preformed CsPb 1- x Cl 3 : xMn 2+ NCs can be used to obtain high Br - content Cs(Pb 1- x- z Zn z )(Cl y Br 1- y ) 3 : xMn 2+ perovskite NCs with strong Mn 2+ emission, and the Mn 2+ substitution ratio can reach about 22%. More specifically, the fast anion exchange could be realized by the soluble halide precursors, leading to anion exchange within a few seconds as observed from the strong BE emission evolution, whereas the cation exchange instead generally required at least a few hours; moreover, their exchange mechanism and dynamics process have been evaluated. The Mn 2+ emission intensity could be further varied by controlling the replacement of Mn 2+ by Zn 2+ with prolonged ion exchange reaction time. White light emission of the doped perovskite NCs via this cation/anion synergistic exchange strategy has been realized, which was also successfully demonstrated in a prototype white light-emitting diode (LED) device based on a commercially available 365 nm LED chip.

Lead-halide perovskites are well known to decompose rapidly when exposed to polar solvents, such as water. Contrary to this common-place observation, we have found that through introducing a suitable minor amount of water into the reaction mixture, we can synthesize stable CsPbBr 3 nanocrystals. The size and the crystallinity, and as a result the band gap tunability of the strongly emitting CsPbBr 3 nanocrystals correlate with the water content. Suitable amounts of water change the crystallization environment, inducing the formation of differently shaped perovskites, namely spherical NCs, rectangular nanoplatelets, or nanowires. Bright CsPbBr 3 nanocrystals with the photoluminescence quantum yield reaching 90 % were employed for fabrication of inverted hybrid inorganic/organic light-emitting devices, with the peak luminance of 4428 cd m -2 and external quantum yield of 1.7 %., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Perovskite nanocrystals are attracting great interest due to their excellent photonic properties. Here, through a supramolecular self-assembly approach, the perovskite nanocrystals (NCs) with a novel circularly polarized luminescence (CPL) are successfully endowed. It is found that the achiral perovskite NCs can coassemble with chiral gelator in nonpolar solvents, in which the gelator molecules modify the surface of the perovskite NCs. Through such cogelation, the molecular chirality can transfer to the NCs resulting in CPL signals with a dissymmetric factor (g lum ) up to 10 -3 . Furthermore, depending on the molecular chirality of the gelator, the CPL sense can be selected and the mirror-imaged CPL is obtained. Such gels can be further embedded into the polymer film to facilitate flexible CPL devices. It is envisaged that this approach will afford a new insight into the designing of the functional chiroptical materials., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

All inorganic perovskite nanocrystals (NCs) of CsPbX 3 (X = Cl, Br, I, or their mixture) are regarded as promising candidates for high-performance light-emitting diode (LED) owing to their high photoluminescence (PL) quantum yield (QY) and easy synthetic process. However, CsPbX 3 NCs synthesized by the existing methods, where oleic acid (OA) and oleylamine (OLA) are generally used as surface-chelating ligands, suffer from poor stability due to the ligand loss, which drastically deteriorates their PL QY, as well as dispersibility in solvents. Herein, the OA/OLA ligands are replaced with octylphosphonic acid (OPA), which dramatically enhances the CsPbX 3 stability. Owing to a strong interaction between OPA and lead atoms, the OPA-capped CsPbX 3 (OPA-CsPbX 3 ) NCs not only preserve their high PL QY (>90%) but also achieve a high-quality dispersion in solvents after multiple purification processes. Moreover, the organic residue in purified OPA-CsPbBr 3 is only ∼4.6%, which is much lower than ∼29.7% in OA/OLA-CsPbBr 3 . Thereby, a uniform and compact OPA-CsPbBr 3 film is obtained for LED application. A green LED with a current efficiency of 18.13 cd A -1 , corresponding to an external quantum efficiency of 6.5%, is obtained. Our research provides a path to prepare high-quality perovskite NCs for high-performance optoelectronic devices.

In this "nano idea" paper, three concepts for the preparation of methylammonium lead halide perovskite particles are proposed, discussed, and tested. The first idea is based on the wet chemistry preparation of the perovskite particles, through the addition of the perovskite precursor solution to an anti-solvent to facilitate the precipitation of the perovskite particles in the solution. The second idea is based on the milling of a blend of the perovskite precursors in the dry form, in order to allow for the conversion of the precursors to the perovskite particles. The third idea is based on the atomization of the perovskite solution by a spray nozzle, introducing the spray droplets into a hot wall reactor, so as to prepare perovskite particles, using the droplet-to-particle spray approach (spray pyrolysis). Preliminary results show that the spray technology is the most successful method for the preparation of impurity-free perovskite particles and perovskite paste to deposit perovskite thin films. As a proof of concept, a perovskite solar cell with the paste prepared by the sprayed perovskite powder was successfully fabricated.

High pressure (HP) can drive the direct sintering of nanoparticle assemblies for Ag/Au, CdSe/PbS nanocrystals (NCs). Instead of direct sintering for the conventional nanocrystals, this study experimentally observes for the first time high-pressure-induced comminution and recrystallization of organic-inorganic hybrid perovskite nanocrystals into highly luminescent nanoplates with a shorter carrier lifetime. Such novel pressure response is attributed to the unique structural nature of hybrid perovskites under high pressure: during the drastic cubic-orthorhombic structural transformation at ≈2 GPa, (301) the crystal plane fully occupied by organic molecules possesses a higher surface energy, triggering the comminution of nanocrystals into nanoslices along such crystal plane. Beyond bulk perovskites, in which pressure-induced modifications on crystal structures and functional properties will disappear after pressure release, the pressure-formed variants, i.e., large (≈100 nm) and thin (<10 nm) perovskite nanoplates, are retained and these exhibit simultaneous photoluminescence emission enhancing (a 15-fold enhancement in the photoluminescence) and carrier lifetime shortening (from ≈18.3 ± 0.8 to ≈7.6 ± 0.5 ns) after releasing of pressure from 11 GPa. This pressure-induced comminution of hybrid perovskite NCs and a subsequent amorphization-recrystallization treatment offer the possibilities of engineering the advanced hybrid perovskites with specific properties., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

CsPbX 3 (X = Cl, Br, I) nanocrystals (NCs) are competitive emitting materials for illumination and display because of their outstanding photophysical properties. However, the conventional synthetic approaches suffer from low yields, complex procedures, and toxic chemicals. In this work, we demonstrate a one-step microwave-assisted approach to prepare CsPbX 3 NCs. The homogeneous heating and rapid temperature increment of microwave preparation facilitate the growth of CsPbX 3 NCs, producing the NCs with high photoluminescence quantum yields up to 90%, narrow emission full-width at half-maximum, and emission color tunable from blue to red. By optimizing the preparation conditions of the microwave-assisted approach, CsPbX 3 NCs with cation- and halide anion-controlled emission properties, tunable reaction rate, and enhanced stability are prepared. Light-emitting diode (LED) prototypes are further fabricated by employing the as-prepared CsPbX 3 NCs as the color conversion materials on commercially available 365 nm GaN LED chips.

Despite the exceptional optoelectronic characteristics of the emergent perovskite nanocrystals, the ionic nature greatly limits their stability, and thus restricts their potential applications. Here we have adapted a self-assembly strategy to access a rarely reported nanorod suprastructure that provide excellent encapsulation of perovskite nanocrystals by polymer-grafted graphene oxide layers. Polyacrylic acid-grafted graphene oxide (GO-g-PAA) was used as a surface ligand during the synthesis of the CsPbX 3 perovskite nanocrystals (NCs), yielding particles (5-12 nm) with tunable halide compositions that were homogeneously embedded in the GO-g-PAA matrix. The resulting NC-GO-g-PAA exhibits a higher photoluminescence quantum yield than previously reported encapsulated NCs while maintaining an easily tunable bandgap, allowing for emission spanning the visible spectrum. The NC-GO-g-PAA hybrid further self-assembles into well-defined nanorods upon solvent treatment. The resulting nanorod morphology imparts extraordinary chemical stability toward protic solvents such as methanol and water and much enhanced thermal stability. The introduction of barrier layers by embedding the perovskite NCs in the GO-g-PAA matrix, together with its unique assembly into nanorods, provides a novel strategy to afford robust perovskite emissive materials with environmental stability that may meet or exceed the requirement for optoelectronic applications.

Cesium lead halide (CsPbX 3 , X = Cl, Br, I) perovskite nanocrystals (PNCs) have recently become a promising material for optoelectronic applications due to their high emission quantum yields and facile band gap tunability via both halide composition and size. The spectroscopy of single PNCs enhances our understanding of the effect of confinement on excitations in PNCs in the absence of obfuscating ensemble averaging and can also inform synthetic efforts. However, single PNC studies have been hampered by poor PNC photostability under confocal excitation, precluding interrogation of all but the most stable PNCs, and leading to a lack of understanding of PNCs in the regime of high confinement. Here, we report the first comprehensive spectroscopic investigation of single PNC properties using solution-phase photon-correlation methods, including both highly confined and blue-emitting PNCs, previously inaccessible to single NC techniques. With minimally perturbative solution-phase photon-correlation Fourier spectroscopy (s-PCFS), we establish that the ensemble emission linewidth of PNCs of all sizes and compositions is predominantly determined by the intrinsic single PNC linewidth (homogeneous broadening). The single PNC linewidth, in turn, dramatically increases with increasing confinement, consistent with what has been found for II-VI semiconductor nanocrystals. With solution-phase photon antibunching measurements, we survey the biexciton-to-exciton quantum yield ratio (BX/X QY) in the absence of user-selection bias or photodegradation. Remarkably, the BX/X QY ratio depends both on the PNC size and halide composition, with values between ∼2% for highly confined bromide PNCs and ∼50% for intermediately confined iodide PNCs. Our results suggest a wide range of underlying Auger rates, likely due to transitory charge carrier separation in PNCs with relaxed confinement.

Bright and stable blue emitters with narrow full-width at half-maxima are particularly desirable for applications in television displays and related technologies. Here, this study shows that doping aluminum (Al 3+ ) ion into CsPbBr 3 nanocrystals (NCs) using AlBr 3 can afford lead-halide perovskites NCs with stable blue photoluminescence. First, theoretical and experimental analyses reveal that the extended band gap and quantum confinement effect of elongated shape give rise to the desirable blueshifted emission. Second, the aluminum ion incorporation path is rationalized qualitatively by invoking fundamental considerations about binding relations in AlBr 3 and its dimer. Finally, the absence of anion-exchange effect is corroborated when green CsPbBr 3 and blue Al:CsPbBr 3 NCs are mixed. Combinations of the above two NCs with red-emitting CdSe@ZnS NCs result in UV-pumped white light-emitting diodes (LED) with an National Television System Committee (NTSC) value of 116% and ITU-R Recommendation B.T. 2020 (Rec. 2020) of 87%. The color coordinates of the white LED are optimized at (0.32, 0.34) in CIE 1931. The results suggest that low-cost, earth-abundant, solution-processable Al-doped perovskite NCs can be promising candidate materials for blue down-conversion layer in backlit displays.

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 CsPbBr 3 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 O 2 , which is in contrast to the photobrightening effect observed in films and single crystals. This indicates that O 2 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.

In the past few years, hybrid organic-inorganic and all-inorganic metal halide perovskite nanocrystals have become one of the most interesting materials for optoelectronic applications. Here, we report a facile and rapid room temperature synthesis of 15-25 nm formamidinium CH(NH 2 ) 2 PbX 3 (X = Cl, Br, I, or mixed Cl/Br and Br/I) colloidal nanocrystals by ligand-assisted reprecipitation (LARP). The cubic and platelet-like nanocrystals with their emission in the range of 415-740 nm, full width at half-maximum (fwhm) of 20-44 nm, and radiative lifetimes of 5-166 ns enable band gap tuning by halide composition as well as by their thickness tailoring; they have a high photoluminescence quantum yield (up to 85%), colloidal and thermodynamic stability. Combined with surface modification that prevents degradation by water, this nanocrystalline material is an ideal candidate for optoelectronic devices and applications. In addition, optoelectronic measurements verify that the photodetector based on FAPbI 3 nanocrystals paves the way for perovskite quantum dot photovoltaics.

Colloidal perovskite nanocrystals support bright, narrow PL tunable over the visible spectrum. However, bandgap tuning of these materials remains limited to laboratory-scale syntheses. In this work, we present a polar-solvent-free ligand-mediated transport synthesis of high-quality organic-inorganic perovskite nanocrystals under ambient conditions with photoluminescence quantum yields up to 97%. Our synthesis employs a ligand-mediated transport mechanism that circumvents the need for exquisite external control (e.g., temperature control, inert-gas protection, dropwise addition of reagents) required by other methods due to extremely fast reaction kinetics. In the ligand-mediated transport mechanism, multiple equilibria cooperatively dictate reaction rates and enable precise control over NC size. These small nanocrystals exhibit high photoluminescence quantum yields due to quantum confinement. Nanosecond transient absorption spectroscopy experiments reveal a fluence-independent PL decay originating from exciton recombination. Two-dimensional electronic spectroscopy resolves multiple spectral features reflecting the electronic structure of the nanocrystals. The resolved features exhibit size-dependent spectral positions, further indicating the synthesized nanocrystals are quantum-confined.

Colloidally stable suspensions of lead halide perovskite nanocrystals are prepared from high-quality lead halide nanocrystal seeds. Perovskite nanocrystals with different layered crystal structures are reported. These systems are well suited for investigations of the intrinsic photophysics and spectroscopy of organic-inorganic metal halide perovskites., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Electroluminescence in light-emitting devices relies on the encounter and radiative recombination of electrons and holes in the emissive layer. In organometal halide perovskite light-emitting diodes, poor film formation creates electrical shunting paths, where injected charge carriers bypass the perovskite emitter, leading to a loss in electroluminescence yield. Here, we report a solution-processing method to block electrical shunts and thereby enhance electroluminescence quantum efficiency in perovskite devices. In this method, a blend of perovskite and a polyimide precursor dielectric (PIP) is solution-deposited to form perovskite nanocrystals in a thin-film matrix of PIP. The PIP forms a pinhole-free charge-blocking layer, while still allowing the embedded perovskite crystals to form electrical contact with the electron- and hole-injection layers. This modified structure reduces nonradiative current losses and improves quantum efficiency by 2 orders of magnitude, giving an external quantum efficiency of 1.2%. This simple technique provides an alternative route to circumvent film formation problems in perovskite optoelectronics and offers the possibility of flexible and high-performance light-emitting displays.