Hybrid Perovskite Nanocrystals Research Articles

Integrating Hybrid Perovskite Nanocrystals into Metal-Organic Framework as Efficient S-Scheme Heterojunction Photocatalyst for Synergistically Boosting Controlled Radical Photopolymerization under 980 nm NIR Light.

S-scheme heterojunction photocatalyst MAPbI3@PCN-222 with light absorption extending to the NIR region is constructed by embedding organic-inorganic hybrid perovskite (MAPbI3) into porphyrinic Zr-MOF (PCN-222). Both in situ X-ray photoelectron spectroscopy, ultraviolet photoelectron spectral characterization, and photocatalytic polymerization experiment prove the formation of S-scheme heterojunction. MAPbI3@PCN-222 with a low dosage (90 ppm) displays an impressive photocatalytic ability for 980 nm light-mediated photoinduced electron/energy-transfer-reversible addition-fragmentation chain-transfer (PET-RAFT) polymerization in air. The well-defined controllable-molecular weight polymers including block copolymers and ultrahigh-molecular weight polymers can be achieved with narrow distributions (Mw/Mn < 1.20) via rapid photopolymerization. The industrial application potential of the photocatalyst also has been proved by scale-up synthesis of polymers with low polydispersity under NIR light-induced photopolymerization in a large-volume reaction system (200 mL) with high monomer conversion up to 99%. The penetration photopolymerization through the 5 mm polytetrafluoroethylene plate and excellent photocontrollable behavior illustrate the existence of long-term photogenerated electron transfer of heterojunction and abundant free radicals in photopolymerization. The photocatalyst still retains high catalytic activity after 10 cycles of photopolymerization in air. It is revealed for the first time that the special PET-RAFT polymerization pathway is initiated by the aldehyde-bearing α-aminoalkyl radical derived from the oxidization of triethanolamine (TEOA) by the heterojunction photocatalyst. This research offers a new insight into understanding the NIR-light-activated PET-RAFT polymerization mechanism in the presence of TEOA.

Tunable Green-to-Blue Light Emitting Hybrid Perovskite Nanocrystals: Status Updates and Roadblocks

Tunable Green-to-Blue Light Emitting Hybrid Perovskite Nanocrystals: Status Updates and Roadblocks

FAPbBr3@PbBr(OH) phosphor with high stability for anti-counterfeiting application via water induction

Organic–inorganic hybrid perovskite nanocrystals have become a very widely used as semiconductor light-emitting materials. However, perovskite nanocrystals face stability challenges, which is a key factor hindering their application. In this paper, by introducing water into the synthesis of formamidinium lead bromide (FAPbBr3) perovskite, ultra-stable FAPbBr3@PbBr(OH) fluorescent material was prepared. The photoluminescence intensity of the material after the addition of water increased 2.9 times compared with that before the addition of water. The excellent green fluorescence emission was still maintained after four cycles of wash–dry treatment. Meanwhile, it also exhibits good ultraviolet and thermal stability. The above enhanced performance of FAPbBr3 nanocrystals is attributed the protection of PbBr(OH). In addition, the prepared material can be used in anti-counterfeit patterns. The anti-counterfeit patterns have good color rendering and the luminous color has a high dependence on temperature. Both of these features make it very valuable for various fluorescent anti-counterfeiting labels.

Enhanced Hygrothermal Stability of In-Situ-Grown MAPbBr3 Nanocrystals in Polymer with Suppressed Desorption of Ligands.

Currently, the intrinsic instability of organic-inorganic hybrid perovskite nanocrystals (PNCs) at high temperature and high humidity still stands as a big barrier to hinder their potential applications in optoelectronic devices. Herein, we report the controllable in-situ-grown PNCs in polyvinylidene fluoride (PVDF) polymer with profoundly enhanced hygrothermal stability. It is found that the introduced tetradecylphosphonic acid (TDPA) ligand enables significantly improved binding to the surface of PNCs via a strong covalently coordinated P-O-Pb bond, as evidenced by density functional theory calculations and X-ray photoelectron spectroscopy analyses. Accordingly, such enhanced binding could not only make efficient passivation of the surface defects of PNCs but also enable the remarkably suppressed desorption of the ligand from the PNCs under high-temperature environments. Consequently, the photoluminescence quantum yield (PL QY) of the as-fabricated MAPbBr3-PNCs@PVDF film exhibits almost no decay after exposure to air at 333 K over 1800 h. Once the temperatures are increased from 293 to 353 K, their PL intensity can be kept as 88.6% of the initial value, much higher than that without the TDPA ligand (i.e., 42.4%). Moreover, their PL QY can be maintained above 50% over 1560 h (65 days) under harsh working conditions of 333 K and 90% humidity. As a proof of concept, the as-assembled white light-emitting diodes display a large color gamut of 125% National Television System Committee standard, suggesting their promising applications in backlight devices.

Effect of Acidic Strength of Surface Ligands on the Carrier Relaxation Dynamics of Hybrid Perovskite Nanocrystals.

Perovskite nanocrystals (PeNCs) are known for their use in numerous optoelectronic applications. Surface ligands are critical for passivating surface defects to enhance the charge transport and photoluminescence quantum yields of the PeNCs. Herein, we investigated the dual functional abilities of bulky cyclic organic ammonium cations as surface-passivating agents and charge scavengers to overcome the lability and insulating nature of conventional long-chain type oleyl amine and oleic acid ligands. Here, red-emitting hybrid PeNCs of the composition CsxFA(1-x)PbBryI(3-y) are chosen as the standard (Std) sample, where cyclohexylammonium (CHA), phenylethylammonium (PEA) and (trifuluoromethyl)benzylamonium (TFB) cations were chosen as the bifunctional surface-passivating ligands. Photoluminescence decay dynamics showed that the chosen cyclic ligands could successfully eliminate the shallow defect-mediated decay process. Further, femtosecond transient absorption spectral (TAS) studies uncovered the rapidly decaying non-radiative pathways; i.e., charge extraction (trapping) by the surface ligands. The charge extraction rates of the bulky cyclic organic ammonium cations were shown to depend on their acid dissociation constant (pKa) values and actinic excitation energies. Excitation wavelength-dependent TAS studies indicate that the exciton trapping rate is slower than the carrier trapping rate of these surface ligands.

Energy and Charge Transfer Dynamics in Red-Emitting Hybrid Organo-Inorganic Mixed Halide Perovskite Nanocrystals.

We report time-resolved spectral properties of highly stable and efficient red-emitting hybrid perovskite nanocrystals with the composition FA0.5MA0.5PbBr0.5I2.5 (FAMA PeNC) synthesized by using the hot-addition method. The PL spectrum of the FAMA PeNC shows a broad asymmetric band covering 580 to 760 nm with a peak at 690 nm which can be deconvoluted into two bands corresponding to the MA and FA domains. The interactions between the MA and FA domains are shown to affect the relaxation dynamics of the PeNCs from the subpicosecond to tens of nanoseconds scale. Time-correlated single-photon counting (TCSPC), femtosecond PL optical gating (FOG), and femtosecond transient absorption spectral (TAS) techniques were employed to study the intercrystal energy transfer (photon recycling) and intracrystal charge transfer processes between the MA and the FA domains of the crystals. These two processes are shown to increase the radiative lifetimes for the PLQYs exceeding 80%, which may play a key role in enhancing the performance of PeNC-based solar cells.

Nanoimprinted 2D-Chiral Perovskite Nanocrystal Metasurfaces for Circularly Polarized Photoluminescence.

The versatile hybrid perovskite nanocrystals (NCs) are one of the most promising materials for optoelectronics by virtue of their tunable bandgaps and high photoluminescence (PL) quantum yields. However, their inherent crystalline chemical structure limits the chiroptical properties achievable with the material. The production of chiral perovskites has become an active field of research for its promising applications in optics, chemistry, or biology. Typically, chiral halide perovskites are obtained by the incorporation of different chiral moieties in the material. Unfortunately, these chemically modified perovskites have demonstrated moderate values of chiral PL so far. Here, a general and scalable approach is introduced to produce chiral PL from arbitrary nanoemitters assembled into 2D-chiral metasurfaces. The fabrication via nanoimprinting lithography employs elastomeric molds engraved with chiral motifs covering millimeter areas that are used to pattern two types of unmodified colloidal perovskite NC inks: green-emissive CsPbBr3 and red-emissive CsPbBr1 I2 . The perovskite 2D-metasurfaces exhibit remarkable PL dissymmetry factors (glum ) of 0.16 that can be further improved up to glum of 0.3 by adding a high-refractive-index coating on the metasurfaces. This scalable approach to produce chiral photoluminescent thin films paves the way for the seamless production of bright chiral light sources for upcoming optoelectronic applications.

Air stable highly luminescent 2D tin halide perovskite nanocrystals as photodetectors.

Hybrid and inorganic perovskite nanocrystals are a hot topic in materials chemistry due to their versatile optoelectronic properties. Herein, we report highly luminescent water stable lead-free orange emissive (OleylAm)2SnBr4 (OleylAm = oleylammonium cation) 2D tin halide perovskite nanocrystals in humid conditions in a solution-based process. The photoresponse study performed with the synthesized nanocrystals exhibits a responsivity of 4.9 mA W-1 at a 5 V operating voltage.

Bandgap narrowing and piezochromism of doped two-dimensional hybrid perovskite nanocrystals under pressure

We provide a facile pressure engineering to achieve the optical control of Mn doped 2D perovskite (PEA)2PbBr4 NCs. A successive bandgap narrowing and marked piezochromism which changes emission from orange to bluish violet were realized.

One-pot ultrasonicated synthesized lead-less hybrid perovskite nanocrystals: structural, morphological and optical analysis

In contemporary years, hybrid lead halide perovskites nanocrystals (HPNCs) have emerged as core materials for low-cost solution-processable photovoltaic, light-emitting devices as well as in other optoelectronic fields, such as high-efficiency perovskite fluorescent quantum dots (quantum dot, QD). Although the high efficiency makes them an attractive active material, reducing the Pb-toxicity and enhancing the stability while sustaining the efficiency of the HPNCs devices is important for their successful commercialization in future. Here, we report for the first time the fabrication of excellent quality Pb-less, MAPb1-x Sn x Br3 (x = 0 to 0.50) perovskite NCs by one-pot ultrasonication method. Interestingly, an outstanding photoluminescence quantum yield (PLQY) of 94% and better lifetime performance than 100% Pb-based HPNCs is obtained for Pb-less HPNCs. The successful incorporation of Sn MAPb1-x Sn x Br3 HPNCs is confirmed by energy-dispersive x-ray (EDX) and x-ray photoelectron spectroscopy (XPS) analysis. Although the particle size for Pb-less HPNCs was different, the change in morphology and structure was minimal as confirmed by transmission electron microscopy (TEM) analysis. The optical analysis indicated bandgap tuning, which is evident by the blue shift of the band edge in absorbance spectra and photoluminescence peak after incorporating Sn2+. To the best of our knowledge, this is the highest achieved PLQY for Sn-substituted hybrid Pb-based HPNCs. The synthesis by using one pot ultrasonication method might be helpful for large-scale HPNCs production and can pave the way for future research on less-toxic and stable alternatives to Pb-based HPNCs.

Experimental demonstration of weak chirality enhancement by hybrid perovskite nanocrystals using photonic spin Hall effect

Abstract Chiral perovskites have attracted considerable attention as excellent spin-emitting materials for applications in spintronics, quantum optics, and biological. Especially in drug development of biological, weak chirality molecules are frequently selected to reduce the side effects of toxics, and there is a common defect for accurately detecting the weak chirality with common methods at room temperature. In this study, formamidine lead bromide perovskite nanocrystals (FAPbBr3 NCs) were coated with chiral ligands, whose chirality was too weak to be observed in the visible region at room temperature. Thus, by characterizing the transverse shift of photonic spin Hall effect (SHE), the accurate discrimination of weak chirality in the visible region was achieved successfully. By measuring the shift value and light spot splitting of photonic SHE at the same concentration, NEA-coated FAPbBr3 NCs can effectively enhance the chirality of naphthalene ethylamine (NEA) ligands when under the mutually reinforcement of chiral molecular and inorganic parts. In addition, we furtherly clearly distinguished the tiny chiral distinction of NEA-coated FAPbBr3 NCs with different particle sizes, which revealed that the chirality decreases with the increase of particle size. These findings could provide effective solutions for the detection and application of weak chirality in hybrid perovskite nanocrystals in universal environment.

Sum frequency generation vibrational spectra of perovskite nanocrystals at the single-nanocrystal and ensemble levels

Determination of molecular structures of organic-inorganic hybrid perovskite (OIHP) nanocrystals at the single-nanocrystal and ensemble levels is essential to understanding the mechanisms responsible for their size-dependent optoelectronic properties and the nanocrystal assembling process, but its detection is still a bit challenging. In this study, we demonstrate that femtosecond sum frequency generation (SFG) vibrational spectroscopy can provide a highly sensitive tool for probing the molecular structures of nanocrystals with a size comparable to the Bohr diameter (∼10 nm) at the single-nanocrystal level. The SFG signals are monitored using the spectral features of the phenyl group in (R-MBA)PbBr3 and (R-MBA)2PbI4 nanocrystals (MBA: methyl-benzyl-ammonium). It is found that the SFG spectra exhibit a strong resonant peak at 3067±3 cm−1 (ν2 mode) and a weak shoulder peak at 3045±4 cm−1 (ν7a mode) at the ensemble level, whereas a peak of the ν2 mode and a peak at 3025±3 cm−1 (ν20b mode) at the single-nanocrystal level. The nanocrystals at the single-nanocrystal level tend to lie down on the surface, but stand up as the ensemble number and the averaged sizes increase. This finding may provide valuable information on the structural origins for size-dependent photo-physical properties and photoluminescence blinking dynamics in nanocrystals.

Revisiting the nontemplate approach for the synthesis of highly green emissive hybrid perovskite nanocrystals: platelets or spheres?

The long-standing debate about the morphology of colloidal methylammonium lead bromide perovskites nanocrystals, manufactured by our nontemplate synthetic strategy reported in 2014, is now resolved; specifically, the highest green emissive single nanoplatelets (of up to 93%) with long-term chemical and photochemical stability have been obtained after suitable purification steps.

Anchoring of red perovskite nanocrystals on YAG:Ce phosphor for high color rendering index WLEDs

Widespread application of YAG:Ce-based white light-emitting diodes (WLEDs) is being challenged for their poor color rendering index (CRI) and high correlated color temperature (CCT) due to the lack of red emission. Organic-inorganic hybrid perovskite nanocrystals (MAPbX3 PNCs, X = Cl, Br, I or mixture of them), presenting high photoluminescence quantum yield, tunable emission color and simple fabrication process have been recognized as promising red-emitting component for warm WLEDs. However, additional protection process for PNCs always needed due to their poor stability, which complicates the fabrication procedures of WLEDs. Besides, nano-sized PNCs and micron YAG:Ce powder display different sinking behavior in silicone, which also hard to ensure the uniform distribution of the two components and subsequently stable optical characteristics of the device. Herein, a one-pot anchoring strategy is implemented to realize the enhanced thermal and photo-stabilities of in-situ generated red-emitting MAPbBr0.5I2.5 PNCs and simultaneously strong interaction between the PNCs and YAG:Ce to form PNCs@A-YAG composite, which greatly simplifies the processes, and also avoids the uneven distribution of phosphor and PNCs in silicone. Furthermore, the WLED, fabricated by PNCs@A-YAG and a commercial blue chip, exhibits high CRI of 92, low CCT of 4755 K, and super high saturated red color R9 of 95, which are of vital importance in achieving warm white light for indoor lighting applications. This work could promote the practical application of perovskite nanocrystals in the field of high color rendering index WLEDs.

Dimensionality Control of Inorganic and Hybrid Perovskite Nanocrystals by Reaction Temperature: From No-Confinement to 3D and 1D Quantum Confinement.

This work focuses on the systematic investigation of the shape, size, and composition‐controlled synthesis of perovskite nanocrystals (NCs) under inert gas‐free conditions and using pre‐synthesized precursor stock solutions. In the case of CsPbBr3 NCs, we find that the lowering of reaction temperature from ∼175 to 100 °C initially leads to a change of morphology from bulk‐like 3D nanocubes to 0D nanocubes with 3D‐quantum confinement, while at temperatures below 100 °C the reaction yields 2D nanoplatelets (NPls) with 1D‐quantum confinement. However, to our surprise, at higher temperatures (∼215 °C), the reaction yields CsPbBr3 hexapod NCs, which have been rarely reported. The synthesis is scalable, and their halide composition is tunable by simply using different combinations of precursor solutions. The versatility of the synthesis is demonstrated by applying it to relatively less explored shape‐controlled synthesis of FAPbBr3 NCs. Despite the synthesis carried out in the air, both the inorganic and hybrid perovskite NCs exhibit nearly‐narrow emission without applying any size‐selective separation, and it is precisely tunable by controlling the reaction temperature.

Dimensionality Control of Inorganic and Hybrid Perovskite Nanocrystals by Reaction Temperature: From No‐Confinement to 3D and 1D Quantum Confinement

AbstractThis work focuses on the systematic investigation of the shape, size, and composition‐controlled synthesis of perovskite nanocrystals (NCs) under inert gas‐free conditions and using pre‐synthesized precursor stock solutions. In the case of CsPbBr3 NCs, we find that the lowering of reaction temperature from ∼175 to 100 °C initially leads to a change of morphology from bulk‐like 3D nanocubes to 0D nanocubes with 3D‐quantum confinement, while at temperatures below 100 °C the reaction yields 2D nanoplatelets (NPls) with 1D‐quantum confinement. However, to our surprise, at higher temperatures (∼215 °C), the reaction yields CsPbBr3 hexapod NCs, which have been rarely reported. The synthesis is scalable, and their halide composition is tunable by simply using different combinations of precursor solutions. The versatility of the synthesis is demonstrated by applying it to relatively less explored shape‐controlled synthesis of FAPbBr3 NCs. Despite the synthesis carried out in the air, both the inorganic and hybrid perovskite NCs exhibit nearly‐narrow emission without applying any size‐selective separation, and it is precisely tunable by controlling the reaction temperature.

Highly Luminescent and Phase-Stable Red/NIR-Emitting All-Inorganic and Hybrid Perovskite Nanocrystals

Highly Luminescent and Phase-Stable Red/NIR-Emitting All-Inorganic and Hybrid Perovskite Nanocrystals

Properties of mesoporous hybrid perovskite nanocrystals and its application in light-emitting diodes

We fabricated mesoporous perovskite nanocrystal for the first time, and investigated its optical properties and application in light-emitting diodes (LEDs). The transformation of mesoporous structure can be ascribed to the decomposition of nanocrystals under dilution condition, which results in the blueshift of luminescence. The mesoporous nanocrystals under proper dilution may achieve improved perovskite LEDs, with maximum luminance and current efficiency of 23370 cd m−2 and 6.7 cd A−1, respectively. This work provide an avenue to the optical engineering of perovskite nanocrystals, and demonstrate that perovskite concentration is one of key factors for realizing efficient LEDs.

Quantum Confinement of Exfoliated Organic-Inorganic Hybrid Perovskite Nanocrystals

Quantum Confinement of Exfoliated Organic-Inorganic Hybrid Perovskite Nanocrystals

Tuning Facets and Controlling Monodispersity in Organic–Inorganic Hybrid Perovskite FAPbBr3 Nanocrystals

Lead halide hybrid perovskite nanocrystals are considered as one of the most efficient light-harvesting materials in current research. However, unlike all-inorganic perovskite nanocrystals, the quality optimization and synthetic progress for facet tuning of these hybrid nanocrystals have not moved forward at the same pace. To meet the current demand for high-quality, facet-tuned, and monodisperse nanocrystals, herein, surface A-site cations’ population-controlled facet tuning of FAPbBr3 nanocrystals is reported. Using specific alkylammonium ligands obtained from α-bromo ketones and comparing their concentration with FA+, cubic, dodecahedral, and quasi-spherical shapes of nanocrystals in cubic phase are obtained having monodispersity comparable to that of their best reports. In addition, upon changing of surface ligands, spontaneous formation of self-assembled blue-emitting platelets was also observed. Because of the importance of these materials, these findings will aid the fundamental understanding of formation of hybrid perovskite nanocrystals and also support accelerating their widespread applications.