Emission Of Nanocrystals Research Articles

Understanding the emission behaviour of 0D Cs4PbBr6 perovskite nanocrystals at room temperature

We report 0D Cs4PbBr6 perovskite nanocrystals emitting at room temperature, synthesized by hot injection technique. Effect of injection temperature (TR) on the emission of Cs4PbBr6 nanocrystals (NCs) has been studied. High-quality NCs are synthesized in the 100 °C–180 °C temperature range. Pure phase Cs4PbBr6 nanocrystals are formed at lower temperatures (TR = 100 °C), while at higher temperatures, CsPbBr3 impurity phase appears along with Cs4PbBr6. Cs4PbBr6 nanocrystals emit blue light with broad emission spectra in the 400–500 nm wavelength range, while a green emission from CsPbBr3 impurities at 520 nm wavelength is observed. The emission spectra from Cs4PbBr6 NCs shows multiple radiative centers in the 400–500 nm range, unaffected by the change in excitation wavelength. The emission of pure Cs4PbBr6 is attributed to charge transfer states of Pb2+ ions and surface states incorporated by presence of ligands on NC surface. Further, it is to be emphasized that the Cs4PbBr6 perovskite NCs are highly stable and maintain their emission even after two years of synthesis.

Spectator Exciton Effects in Nanocrystals III: Unveiling the Stimulated Emission Cross Section in Quantum Confined CsPbBr3 Nanocrystals.

Quantifying stimulated emission in semiconductor nanocrystals (NCs) remains challenging due to masking of its effects on pump-probe spectra by excited state absorption and ground state bleaching signals. The absence of this defining photophysical parameter in turn impedes assignment of band edge electronic structure in many of these important fluorophores. Here we employ a generally applicable 3-pulse ultrafast spectroscopic method coined the "Spectator Exciton" (SX) approach to measure stimulated-emission efficiency in quantum confined inorganic perovskite CsPbBr3 NCs, the band edge electronic structure of which is the subject of lively ongoing debate. Our results show that in 5-6 nm CsPbBr3 NCs, a single exciton bleaches more than half of the intense band edge absorption band, while the cross section for stimulated emission from the same state is nearly 6 times weaker. Discussion of these findings in light of several recent electronic structure models for this material proves them unable to simultaneously explain both measures, proving the importance of this new input to resolving this debate. Along with femtosecond time-resolved photoluminescence measurements on the same sample, SX results also verify that biexciton interaction energy is intensely attractive with a magnitude of ∼80 meV. In light of this observation, our previous suggestion that biexciton interaction is repulsive is reassigned to hot phonon induced slowdown of carrier relaxation leading to direct Auger recombination from an excited state. The mechanism behind the extreme slowing of carrier cooling after several stages of exciton recombination remains to be determined.

Regulating Planarized Intramolecular Charge Transfer for Efficient Single-Phase White-Light Emission in Undoped Metal-Organic Framework Nanocrystals.

The technology of combining multiple emission centers to exploit white-light-emitting (WLE) materials by taking advantage of porous metal-organic frameworks (MOFs) is mature, but preparing undoped WLE MOFs remains a challenge. Herein, a pressure-treated strategy is reported to achieve efficient white photoluminescence (PL) in undoped [Zn(Tdc)(py)]n nanocrystals (NCs) at ambient conditions, where the Commission International del'Eclairage coordinates and color temperature reach (0.31, 0.37) and 6560 K, respectively. The initial [Zn(Tdc)(py)]n NCs exhibit weak-blue PL consisting of localized excited (LE) and planarized intramolecular charge transfer (PLICT) states. After pressure treatment, the emission contributions of LE and PLICT states are balanced by increasing the planarization of subunits, thereby producing white PL. Meanwhile, the reduction of nonradiative decay triggered by the planarized structure results in 5-fold PL enhancement. Phosphor-converted light-emitting diodes based on pressure-treated samples show favorable white-light characteristics. The finding provides a new platform for the development of undoped WLE MOFs.

Size-Tunable Manganese-Doped Spheroidal CsPbCl3 Quantum Dots.

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

Room temperature circularly polarized emission in perovskite nanocrystals through bichiral-molecule-induced lattice reconstruction

Room temperature circularly polarized emission in perovskite nanocrystals through bichiral-molecule-induced lattice reconstruction

Micro assembly strategies for enhancing solid-state emission of cellulose nanocrystals and application in photoluminescent inks

Crystalline cellulose exhibits photoluminescent properties, making it ideal for solid-state emission through properly assembling crystal arrays. However, assembling in water or other polar solvents poses structural integrity issues. To address this, a micro-assembly method is proposed. Cellulose nanocrystals (CNCs) are organized within a sub-micrometer-sized ZIF-8 metal-organic framework and coated with TiO2. Notably, the assembly within ZIF-8 improves the CNCs' emission quantum yield to 37.8 %. The bonding between ZIF-8 and CNCs relies on electrostatic interactions and hydrogen bonds, which are sensitive to polar solvents. Yet, the sturdy coordination bonds between TiO2 and ZIF-8 enhance resistance. Solvent-resistance tests confirm that TiO2 prevents CNC assembly breakdown, resulting in only an 8.0 % drop in photoluminescent intensity in an alkaline solution after 24 h, compared to 33 % without the coating. For anti-counterfeiting purposes, TiO2@ZIF-8@CNC is combined with a polymer matrix, allowing information to be revealed under specific wavelengths using screen-printed labels.

Selective Passivation of Surface toward Bright Yellow Defective Emission of CdS Quantum Dots.

CdE (E = S, Se) quantum dots (QDs) with a broad and large Stokes shift PL emission have emerged as potential materials for white-light LEDs. However, this surface-related emission of nanocrystals is currently limited by low quantum efficiency. Herein, a convenient noninjected one-pot method at a relatively low temperature to prepare CdS QDs was readily achieved. The CdS-368 QD displays intense broad yellow emission in both solution and the solid state at room temperature. The coligation of organic and inorganic ligands passivates the electron trap states at the QD surface and suppresses nonradiative recombination, which is responsible for the high stability of colloids in organic solvents and the distinct fluorescence quantum yield.

Resolving the Emission Transition Dipole Moments of Single Doubly Excited Seeded Nanorods via Heralded Defocused Imaging.

Semiconductor nanocrystal emission polarization is a crucial probe of nanocrystal physics and an essential factor for nanocrystal-based technologies. While the transition dipole moment for the lowest excited state to ground state transition is well characterized, the dipole moment of higher multiexcitonic transitions is inaccessible via most spectroscopy techniques. Here, we realize direct characterization of the doubly excited-state relaxation transition dipole by heralded defocused imaging. Defocused imaging maps the dipole emission pattern onto a fast single-photon avalanche diode detector array, allowing the postselection of photon pairs emitted from the biexciton-exciton emission cascade and resolving the differences in transition dipole moments. Type-I1/2 seeded nanorods exhibit higher anisotropy of the biexciton-to-exciton transition compared to the exciton-to-ground state transition. In contrast, type-II seeded nanorods display a reduction of biexciton emission anisotropy. These findings are rationalized in terms of an interplay between the transient dynamics of the refractive index and the excitonic fine structure.

Multicolor emission from lanthanide ions doped lead-free Cs3Sb2Cl9 perovskite nanocrystals

The toxicity of lead ions has become the severe challenge for the all-inorganic lead halide perovskite materials, although some works have reported the lead-free perovskite nanocrystals (NCs), the photoluminescence quantum yield (PLQY) of these materials is still unsatisfactory. Meanwhile, because the halogen ions can be easily exchanged, the controllable multicolor emission in perovskite NCs is difficult to realize in current reports. In this work, we introduced lanthanide ions into lead-free Cs3Sb2Cl9 perovskite NCs. Benefitting from the energy transfer between Cs3Sb2Cl9 perovskite NC host and lanthanide ions, the multicolor emission was realized. Based on controlling the doping concentration of Tb3+ and Eu3+ ions, the white light emission under UV excitation would be turned easily in the Tb3+/Eu3+ codoped NCs. In addition, efficient energy transfer from perovskite NCs to Tb3+ or Eu3+ ions is beneficial to improving the optical properties of lead-free perovskite NCs, resulting in maximum PLQYs of red, green and white light emission of 22.6%, 19.7% and 28.5%, respectively. Finally, a white light emitting device (WLED) was fabricated with a power efficiency of 18.5 lm/W, which presents the Commission Internationale de l’Eclairage (CIE) of (0.33, 0.35).

High Green Purity and Narrow Emission Ceramic‐Like Perovskite Nanocrystals Enabled by Solid‐Phase Reaction Process

AbstractHere, ceramic‐like CsPbBr3@SiO2 nanocrystals (NCs) with a high photoluminescence quantum yield of 98.7%, green purity of 90%, and narrow full width at half maximum of 22 nm are successfully achieved by a solid‐phase reaction process. The SiO2 shell covers the surface of the NCs, providing long‐term working and excellent thermal cycling stability. Ba2+ dopes the lattice of the perovskite structure under high‐temperature sintering at 700 °C, resulting in the red‐shift of the NCs emission due to the decrease of the bandgap caused by the lattice modulation with Ba2+. At the same time, the halogen vacancies are effectively passivated by a halogen‐rich environment of dopants (BaBr2). The Commission Internationale de l'Eclairage of the doped ceramic‐like NCs is (0.170, 0.760), which approaches the Rec.2020 standard. By means of this solid reaction process, red, green, and blue ceramic‐like perovskite NCs are prepared to achieve white light‐emitting diodes, covering 124% of the National Television Standards Committee.

Laser induced emission of NdAlO3 nanocrystals in vacuum, air, and liquid N2

The broadband laser induced white emission (LIWE) spectra of NdAlO3 nanocrystals in vacuum, air, and liquid N2 were explored. In particular, their dependence on excitation laser power was investigated. It was found that the LIWE spectra intensity increased exponentially the with laser power above the excitation threshold in all three cases. The process for NdAlO3 nanocrystals was discussed in terms of multiphoton ionization assisted by ejection of hot electrons. Two differences were observed depending on the conditions: the number of photons involved in the emission was higher in liquid N2 due to additional multiphoton ionization contribution of N2. Also, threshold value for LIWE showed an increasing behavior in air and liquid N2, discussed in terms of relative permittivity and thermal dissipation.

Aging Effects on the Exciton Relaxation and Diffusion Processes in CsPbBr3 Nanocrystals

AbstractFully inorganic perovskite nanocrystals (NCs) have been widely investigated due to their potential as very interesting active materials for several types of photonic and optoelectronic devices. Despite several experiments designed to investigate the basic emission properties of these NCs, a clear and complete understanding of their photophysics is still missing. In this work, temperature‐dependent steady state and time‐resolved photoluminescence (PL) measurements are used to investigate the nature of the emitting states, the origin of the excitation relaxation dynamics and the effects of aging upon long exposure to wet air for thin films of CsPbBr3 NCs prepared by coprecipitation. It is demonstrated that both free excitons and localized excitons contribute to the NC emission and that electron traps within the conduction band, ≈14 meV and ≈80 meV above the band edge, determine thermal emission quenching. Moreover, it is shown that the non‐exponential PL relaxation dynamics are due to short‐range energy migration within a disordered distribution of localized states between 10 and 100 K, with activation of a second, long‐range diffusion process at higher temperatures. It is also demonstrated that aging determines the variations in defect levels, exciton‐phonon coupling and exciton relaxation dynamics. The results substantially improve the current understanding of the basic photophysics of CsPbBr3 NC films and of the aging effects and are expected to provide a useful guide for future characterization of other similar materials.

Tb3+ and Bi3+ Co-Doping of Lead-Free Cs2NaInCl6 Double Perovskite Nanocrystals for Tailoring Optical Properties.

Lead halide perovskites have achieved remarkable success in various photovoltaic and optoelectronic applications, especially solar cells and light-emitting diodes (LEDs). Despite the significant advances of lead halide perovskites, lead toxicity and insufficient stability limit their commercialization. Lead-free double perovskites (DPs) are potential materials to address these issues because of their non-toxicity and high stability. By doping DP nanocrystals (NCs) with lanthanide ions (Ln3+), it is possible to make them more stable and impart their optical properties. In this work, a variable temperature hot injection method is used to synthesize lead-free Tb3+-doped Cs2NaInCl6 DP NCs, which exhibit a major narrow green photoluminescence (PL) peak at 544 nm derived from the transition of Tb3+ 5D4→7F5. With further Bi3+ co-doping, the Tb3+-Bi3+-co-doped Cs2NaInCl6 DP NCs are not only directly excited at 280 nm but are also excited at 310 nm and 342 nm. The latter have a higher PL intensity because partial Tb3+ ions are excited through more efficient energy transfer channels from the Bi3+ to the Tb3+ ions. The investigation of the underlying mechanism between the intrinsic emission of Cs2NaInCl6 NCs and the narrow green PL caused by lanthanide ion doping in this paper will facilitate the development of lead-free halide perovskite NCs.

Boosting the Self-Trapped Exciton Emission in Cs2NaYCl6 Double Perovskite Single Crystals and Nanocrystals.

Halide double perovskites have aroused substantial research interest because of their unique optical properties and intriguing flexibility for various compositional adjustments. Herein, we report the synthesis and photophysics of rare-earth element yttrium (Y)-based double perovskite single crystals (SCs) and nanocrystals (NCs). The pristine Cs2NaYCl6 bulk SCs exhibit a weak sky-blue emission with a low photoluminescence quantum yield (PLQY) of 7.68% based on the self-trapped exciton (STE), while no PL emission was observed for NCs. Excitingly, the STE emission of SCs and NCs is greatly enhanced via Sb3+ doping. The optimized Cs2NaYCl6:Sb3+ SCs and NCs exhibit high PLQYs up to 82.5% and 51.8%, respectively. Theoretical calculations and charge-carrier dynamic studies demonstrate that the giant emission enhancement after Sb3+ doping is related with the enhancement of the sensitization of the emissive STE states, the passivating of the nonradiative carrier trapping processes, and the regulation of carrier-phonon coupling.

Doping-Mediated Size and Structure Tailoring of CaS Nanocrystals

Lanthanide-doped CaS crystals are extensively studied as light-emitting materials, but the investigation of CaS nanocrystals is largely lagging. This work reports a doping-induced modification of surface charge density and the local coordination environment in CaS:Ce nanocrystals, which offers precise control over the nanocrystal size (39–14 nm) and emission color (green to yellow). Our mechanistic investigations, corroborated by theoretical calculations, reveal a S-enriched nanocrystal surface that accommodates excess charges of the aliovalent lanthanide dopants. Owing to the altered surface structure, we identify a dark Ce state that selectively extinguishes light emission of the CaS:Ce nanocrystals. We demonstrate that the doping-induced surface effects can be offset by coating the CaS:Ce nanocrystals with an undoped CaS shell, giving rise to a shell-thickness-dependent emission. Our findings suggest that nanocrystals may respond differently to impurity dopants than the corresponding bulk crystals, thereby giving rise to extended control over materials properties for applications such as optical encryption.

Generation of Free Carriers in MoSe2 Monolayers Via Energy Transfer from CsPbBr3 Nanocrystals

AbstractTransition metal dichalcogenide (TMDCs) monolayers make an excellent component in optoelectronic devices such as photodetectors and phototransistors. Selenide‐based TMDCs, specifically molybdenum diselenide (MoSe2) monolayers with low defect densities, show much faster photoresponses compared to their sulfide counterpart. However, the typically low absorption of the atomically thin MoSe2 monolayer and high exciton binding energy limit the photogeneration of charge carriers. Yet, integration of light‐harvesting materials with TMDCs can produce increased photocurrents via energy transfer. In this article, it is demonstrated that the interaction of cesium lead bromide (CsPbBr3) nanocrystals with MoSe2 monolayers results into an energy transfer efficiency of over 86%, as ascertained from the quenching and decay dynamics of the CsPbBr3 nanocrystals emission. Notably, the increase in the MoSe2 monolayer emission in the heterostructure accounts only for 33% of the transferred energy. It is found that part of the excess energy generates directly free carriers in the MoSe2 monolayer, as a result of the transfer of energy into the exciton continuum. The efficiency of the heterostructure via enhanced photocurrents with respect to the single material unit is proven. These results demonstrate a viable route to overcome the high exciton binding energy typical for TMDCs, as such having an impact on optoelectronic processes that rely on efficient exciton dissociation.

Quantum Efficiency Enhancement of Lead-Halide Perovskite Nanocrystal LEDs by Organic Lithium Salt Treatment.

Surface-defect passivation is key to achieving a high photoluminescence quantum yield in lead halide perovskite nanocrystals. However, in perovskite light-emitting diodes, these surface ligands also have to enable balanced charge injection into the nanocrystals to yield high efficiency and operational lifetime. In this respect, alkaline halides have been reported to passivate surface trap states and increase the overall stability of perovskite light emitters. On the one side, the incorporation of alkaline ions into the lead halide perovskite crystal structure is considered to counterbalance cation vacancies, whereas on the other side, the excess halides are believed to stabilize the colloids. Here, we report an organic lithium salt, viz. LiTFSI, as a halide-free surface passivation on perovskite nanocrystals. We show that treatment with LiTFSI has multiple beneficial effects on lead halide perovskite nanocrystals and LEDs derived from them. We obtain a higher photoluminescence quantum yield and a longer exciton lifetime and a radiation pattern that is more favorable for light outcoupling. The ligand-induced dipoles on the nanocrystal surface shift their energy levels toward a lower hole-injection barrier. Overall, these effects add up to a 4- to 7-fold boost of the external quantum efficiency in proof-of-concept LED structures, depending on the color of the used lead halide perovskite nanocrystal emitters.

Effect of silica encapsulation on the stability and photoluminescence emission of FAPbI3 nanocrystals for white-light-emitting perovskite diodes

The α-FAPbI 3 perovskite nanocrystals exhibit interesting optical properties, which make them attractive for versatile optoelectronic applications; however, the spontaneous phase transformation to the non-perovskite phase (δ-FAPbI 3 ) in humid conditions requires a new strategy to improve the phase stability of the material. We employed 3-Aminopropyl triethoxysilane (APTES)-assisted reprecipitation and sol-gel methods at ambient temperature to prepare stable α-FAPbI 3 nanocrystals embedded in a silica matrix. Transmission electron microscopy (TEM) and X-ray diffraction analysis determined that ultrafine perovskite nanocrystals (11.5 ± 3 nm) were uniformly distributed in a silica matrix. Investigations of the optical properties of the synthesized materials revealed that about 94% of the photoluminescence (PL) emission of silica-encapsulated FAPbI 3 nanocrystals was preserved under humid conditions (60%) after at least a month, while the PL emission of untreated FAPbI 3 was significantly decayed after few days. The thermal analysis also determined that the thermal stability of FAPbI 3 nanocrystals was improved by silica encapsulation. The red-emitting silica-encapsulated FAPbI 3 nanocrystals with a wavelength of 720 nm were used to fabricate white light-emitting diodes (LEDs) in a vertical structure consisting of a blue-chip, PMMA/CsPbBr 3 QDs, and PMMA/FAPbI 3 -SiO 2 QDs. Stable perovskite-based white LEDs with a color gamut of 144% NTSC were fabricated, which was better than many phosphor-based and perovskite-based LEDs. The synthesized composite perovskite nanocrystals could be used for next-generation optoelectronic devices. • Synthesis of silica-encapsulated FAPbI 3 quantum dots at ambient temperature by a combined LARP and sol-gel process. • Minor PL intensity loss in the humidified atmosphere after few months. • WLEDs with a high color gamut of 144% NTSC. • A pure red LED with coordination (0.729, 0.270).

Blue-emitting 0D Cs3ZnX5 (X = Cl, Br) perovskite nanocrystals based on self-trapped excitons

All-inorganic Pb-free halide perovskites have recently received extensive attention due to their unique structures and optoelectronic properties. However, the realization of pure-blue emitting perovskite nanocrystals (NCs) with satisfactory stability and rational interpretation for their corresponding self-trapped excitons (STEs) emissions remains an arduous task. Herein, a modified hot-injection method is proposed to prepare a new family of zero-dimensional (0D) Cs3ZnX5 (X = Cl, Br) perovskite NCs with pure-blue and sky-blue photoluminescence (PL) emissions. Benefitting from the 0D tetragonal-phase structure, the Cs3ZnX5 NCs possess outstanding long-term stability in ambient air conditions. We employ the experimental results and first-principles calculations to confirm that the blue STEs emission of Cs3ZnX5 NCs is dominated by the halide vacancies (VX) in [ZnX4]2- tetrahedra. Our findings not only provide a simple and valid method to control the synthesis of blue-emitting 0D Zn-based perovskite NCs, but also clarify their underlying PL mechanism.

Unraveling the Phase Transition and Luminescence Tuning of Pb-Free Cs-Cu-I Perovskites Enabled by Reaction Temperature and Polar Solvent.

Ternary Pb-free Cs-Cu-I perovskites have attracted widespread attention because of their excellent optical properties and environmentally friendly advantages. Herein, two different Pb-free ternary Cs3Cu2I5 nanocrystals (NCs) and CsCu2I3 microrods (MRs) were synthesized via a heating method. The phase and morphology transition from blue emission of Cs3Cu2I5 NCs to yellow emission of CsCu2I3 MRs could be tuned effectively by manipulating the reaction temperature, decreasing the maximum photoluminescence quantum yields (PLQYs) from 82.7% to ∼10%. More interestingly, the Cs3Cu2I5 NCs could self-assemble into stacking chains, which exhibited a strong dependence on the polarity of solvents. In addition, it was demonstrated that the rapid phase transition and luminescence tuning between Cs3Cu2I5 and CsCu2I3 films took only a few seconds by direct heating or exposure to the polar solvent. This work may deepen the understanding of the phase transition process in Cu-based perovskites and provide a fluorescence material with a short switching time for anticounterfeiting applications.