Size Dependent Specific Heat Capacity of PbSe Nanocrystals.

Specific heat capacity is one of the most fundamental thermodynamic properties of materials. In this work, we measured the specific heat capacity of PbSe nanocrystals with diameters ranging from 5 to 23 nm, and its value increases significantly from 0.2 to 0.6 J g-1 °C-1. We propose a mass assignment model to describe the specific heat capacity of nanocrystals, which divides it into four parts: electron, inner, surface, and ligand. By eliminating the contribution of ligand and electron specific heat capacity, the specific heat capacity of the inorganic core is linearly proportional to its surface-to-volume ratio, showing the size dependence. Based on this linear relationship, surface specific heat capacity accounts for 40-60% of the specific heat capacity of nanocrystals with size decreasing. It can be attributed to the uncoordinated surface atoms, which is evidenced by the appearance of extra surface phonons in Raman spectra and ab initio molecular dynamics (AIMD) simulations.

Elucidating the Impact of Electron Accumulation in Quantum-Dot Light-Emitting Diodes.

Quantum-dot (QD) light-emitting diodes (QLEDs) are promising candidates for future display technology. An imbalance in the injection of electrons and holes into QLEDs leads to the accumulation of excess charges, predominantly electrons, in the QDs. The precise effects of these accumulated electrons have not yet been fully quantified. This study examines how electron accumulation affects QLED efficiency by operating multiple QLEDs at the same voltage and analyzing the correlation between device efficiency and the number of accumulated electrons, as measured by using electrically pumped transient absorption technology. We analyzed 186 QLED devices made with QDs of different colors and quantum yields. Our results show that when QLEDs utilize QDs with a quantum yield of 95%, electron accumulation indeed reduces device efficiency. However, in QLEDs using QDs with a quantum yield below 70%, a higher density of accumulated electrons enhances the device efficiency.

The Strain Effects and Interfacial Defects of Large ZnSe/ZnS Core/Shell Nanocrystals.

The shell growth of large ZnSe/ZnS nanocrystals( is of great importance in the pursuit of pure-blue emitters for display applications, however, suffers from the challenges of spectral blue-shifts and reduced photoluminescence quantum yields. In this work, the ZnS shell growth on different-sized ZnSe cores is investigated. By controlling the reactivity of Zn and S precursors, the ZnS shell growth can be tuned from defect-related strain-released to defect-free strained mode, corresponding to the blue- and red-shifts of resultant nanocrystals respectively. The shape of strain-released ZnSe/ZnS nanocrystals can be kept nearly spherical during the shell growth, while the shape of strained nanocrystals evolutes from spherical into island-like after the critical thickness. Furthermore, the strain between ZnSe core and ZnS shell can convert the band alignment from type-I into type-II core/shell structure, resulting in red-shifts and improved quantum yield. By correlating the strain effects with interfacial defects, a strain-released shell growth model is proposed to obtain large ZnSe/ZnS nanocrystals with isotropic shell morphology.

The warming-up effects of quantum-dot light emitting diodes: A reversible stability issue related to shell traps.

The aging phenomenon is commonly observed in quantum-dot light emitting diodes (QLEDs), involving complex chemical or physical processes. Resolving the underlying mechanism of these aging issues is crucial to deliver reliable electroluminescent devices in future display applications. Here, we report a reversible positive aging phenomenon that the device brightness and efficiency significantly improve after device operation, but recover to initial states after long-time storage or mild heat treatment, which can be termed as warming-up effects. Steady and transient equivalent circuit analysis suggest that the radiative recombination current dramatically increases but electron leakage from the quantum dots (QDs) to hole transport layer becomes more accessible during the warming-up process. Further analysis discloses that the notable enhancement of device efficiency can be ascribed to the filling of shell traps in gradient alloyed QDs. This work reveals a distinct positive aging phenomenon featured with reversibility, and further guidelines would be provided to achieve stable QLED devices in real display applications.

Machine Learning Assisted Stability Analysis of Blue Quantum Dot Light-Emitting Diodes.

The operational stability of the blue quantum dot light-emitting diode (QLED) has been one of the most important obstacles to initialize its industrialization. In this work, we demonstrate a machine learning assisted methodology to illustrate the operational stability of blue QLEDs by analyzing the measurements of over 200 samples (824 QLED devices) including current density-voltage-luminance (J-V-L), impedance spectra (IS), and operational lifetime (T95@1000 cd/m2). The methodology is able to predict the operational lifetime of the QLED with a Pearson correlation coefficient of 0.70 with a convolutional neural network (CNN) model. By applying a classification decision tree analysis of 26 extracted features of J-V-L and IS curves, we illustrate the key features in determining the operational stability. Furthermore, we simulated the device operation using an equivalent circuit model to discuss the device degradation related operational mechanisms.

Thermally activated delayed fluorescence (TADF) organic molecules for efficient X-ray scintillation and imaging.

X-ray detection, which plays an important role in medical and industrial fields, usually relies on inorganic scintillators to convert X-rays to visible photons; although several high-quantum-yield fluorescent molecules have been tested as scintillators, they are generally less efficient. High-energy radiation can ionize molecules and create secondary electrons and ions. As a result, a high fraction of triplet states is generated, which act as scintillation loss channels. Here we found that X-ray-induced triplet excitons can be exploited for emission through very rapid, thermally activated up-conversion. We report scintillators based on three thermally activated delayed fluorescence molecules with different emission bands, which showed significantly higher efficiency than conventional anthracene-based scintillators. X-ray imaging with 16.6 line pairs mm-1 resolution was also demonstrated. These results highlight the importance of efficient and prompt harvesting of triplet excitons for efficient X-ray scintillation and radiation detection.

The fatigue effects in red emissive CdSe based QLED operated around turn-on voltage.

The operational stability is a current bottleneck facing the quantum dot light-emitting diodes (QLEDs). In particular, the device working around turn-on voltage suffers from unbalanced charge injection and heavy power loss. Here, we investigate the operational stability of red emissive CdSe QLEDs operated at different applied voltages. Compared to the rising luminance at higher voltages, the device luminance quickly decreases when loaded around the turn-on voltage, but recovers after unloading or slight heat treatment, which is termed fatigue effects of operational QLED. The electroluminescence and photoluminescence spectra before and after a period of operation at low voltages show that the abrupt decrease in device luminance derives from the reduction of quantum yield in quantum dots. Combined with transient photoluminescence and electroluminescence measurements, as well as equivalent circuit model analysis, the electron accumulation in quantum dots mainly accounts for the observed fatigue effects of a QLED during the operation around turn-on voltage. The underlying mechanisms at the low-voltage working regime will be very helpful for the industrialization of QLED.

Low-Threshold Blue Quasi-2D Perovskite Laser through Domain Distribution Control.

Quasi-2D perovskites, composed of self-organized quantum well structures, are emerging as gain materials for laser applications. Here we investigate the influence of domain distribution on the laser emission of CsPbCl1.5Br1.5-based quasi-2D perovskites. The use of 2,2-diphenylethylammonium bromide (DPEABr) as a ligand enables the formation of quasi-2D film with a large-n-dominated narrow domain distribution. Due to the reduced content of small-n domains, the incomplete energy transfer from small-n to large-n domains can be greatly addressed. Moreover, the photoinduced carriers can be concentrated on most of the large-n domains to reduce the local carrier density, thereby suppressing the Auger recombination. By controlling the domain distribution, we achieve blue amplified spontaneous emission and single-mode vertical-cavity surface-emitting lasing with low thresholds of 6.5 and 9.2 µJ cm-2, respectively. This work provides a guideline to design the domain distribution to realize low-threshold multicolor perovskite lasers.

Blinking Mechanisms and Intrinsic Quantum-Confined Stark Effect in Single Methylammonium Lead Bromide Perovskite Quantum Dots.

Lead halide perovskite quantum dots (QDs) are promising materials for next-generation photoelectric devices because of their low preparation costs and excellent optoelectronic properties. In this study, the blinking mechanisms and the intrinsic quantum-confined Stark effect (IQCSE) in single organic-inorganic hybrid CH3 NH3 PbBr3 perovskite QDs using single-dot photoluminescence (PL) spectroscopy is investigated. The PL quantum yield-recombination rates distribution map allows the identification of different PL blinking mechanisms and their respective contributions to the PL emission behavior. A strong correlation between the excitation power and the blinking mechanisms is reported. Most single QDs exhibit band-edge carrier blinking under a low excitation photon fluence. While under a high excitation photon fluence, different proportions of Auger-blinking emerge in their PL intensity trajectories. In particular, significant IQCSEs in the QDs that exhibit more pronounced Auger-blinking are observed. Based on these findings, an Auger-induced IQCSE model to explain the observed IQCSE phenomena is observed.

Inch-sized aligned polymer nanofiber films with embedded CH3NH3PbBr3 nanocrystals: electrospinning fabrication using a folded aluminum foil as the collector.

Perovskite nanocrystal embedded polymer nanofibers with polarized emissions are interesting materials for down-shifting applications. By using a folded aluminum foil as a collector, we fabricated inch-size aligned polymer nanofiber films with embedded CH3NH3PbBr3 nanocrystals by adapting an electrospinning technique. It was found that the addition of an appropriate amount of cyanoethyl cellulose (CEC) makes the dispersion of MAPbBr3 in the nanofibers more uniform. Using a precursor solution with MAPbBr3 of 10% and CEC of 1 wt%, the resulting nanofiber films show strong polarized emission with quantum yields up to 51%. The emission dichroic ratio and emission polarization ratio can reach 5.21 and 0.43, respectively. These polarized emissive films can be potentially applied as down converters for liquid crystal display backlights and other polarization selective photonic devices.

Performance analysis of PQDCF-coated silicon image sensor using Monte-Carlo ray-trace simulation.

Perovskite quantum dots embedded composite film (PQDCF) exhibits strong photoluminescence emissions and is expected to be excellent down-shifting material for enhancing ultraviolet (UV) response of silicon devices. In this work, light conversion process is analyzed by combining the experiments with Monte-Carlo ray-trace simulation. Results show that external quantum efficiency (EQE) in the UV region was mainly determined by absorption loss and match of peak wavelength. Moreover, resolution was correlated with thickness and reabsorption. This conclusion provides a guideline for designing novel materials with enhanced UV sensitivity and an EQE of 28% is predicted. Our experimental results showed that the use of red emissive PQDCF achieved an EQE of 20%.

Polar Solvent Induced Lattice Distortion of Cubic CsPbI3 Nanocubes and Hierarchical Self-Assembly into Orthorhombic Single-Crystalline Nanowires.

Despite the recent surge of interest in inorganic lead halide perovskite nanocrystals, there are still significant gaps in their stability disturbance and the understanding of their destabilization, assembly, and growth processes. Here, we discover that polar solvent molecules can induce the lattice distortion of ligand-stabilized cubic CsPbI3, leading to the phase transition into orthorhombic phase, which is unfavorable for photovoltaic applications. Such lattice distortion triggers the dipole moment on CsPbI3 nanocubes, which subsequently initiates the hierarchical self-assembly of CsPbI3 nanocubes into single-crystalline nanowires. The systematic investigations and in situ monitoring on the kinetics of the self-assembly process disclose that the more amount or the stronger polarity of solvent can induce the more rapid self-assembly and phase transition. These results not only elucidate the destabilization mechanism of cubic CsPbI3 nanocrystals, but also open up opportunities to synthesize and store cubic CsPbI3 for their practical applications in photovoltaics and optoelectronics.

Large-area rainbow holographic diffraction gratings on a curved surface using transferred photopolymer films.

We report the fabrication of large-area holographic diffraction gratings on a curved surface from transferred photopolymer films by introducing a water-soluble interlayer. The holographic gratings on a curved surface have a diffraction efficiency of ∼63%, which is ∼80% of the recorded holographic film on a flat surface. By transferring a recorded holographic grating to a flat substrate, we obtained rainbow holographic gratings under white light illumination. This can be explained by the deformation of the holographic gratings. Our result provides a low-cost method for fabricating diffraction optical elements on a curved surface for optical systems.

Aqueous Synthesis of Methylammonium Lead Halide Perovskite Nanocrystals.

Methylammonium lead halide perovskite nanocrystals offer attractive optoelectronic properties but suffer from fast degradation in the presence of water. In contradiction to this observation, we demonstrate the possibility of a direct aqueous synthesis of CH3 NH3 PbX3 (X=Br or Cl/Br) nanocrystals through the reaction between the lead halide complex and methylamine when the pH is maintained in the range of 0-5. Under these synthetic conditions, the positively charged surface of the perovskite nanocrystals and the proper ionic balance help to prevent their decomposition in water. Additional surface capping with organic amine ligands further improves the photoluminescence quantum yield of the perovskite nanocrystals to values close to 40 %, ensures their stability under ambient conditions for several months, and their photoluminescence performance under continuous 0.1 W mm-2 405 nm light irradiation for over 250 hours.

Tetraphenylethylene derivative capped CH3NH3PbBr3 nanocrystals: AIE-activated assembly into superstructures.

The surfaces of semiconductor nanocrystals have been known to be a very important factor in determining their optical properties. The introduction of functionalized ligands can further enhance the interactions between nanocrystals, which is beneficial for the assembly of nanocrystals. In a previous report, we developed a ligand-assisted reprecipitation method to fabricate organometal halide perovskite nanocrystals capped with octylamine and oleic acid. Here, a TPE derivative 3-(4-(1,2,2-triphenylvinyl)phenoxy)propan-1-amine, which shows a typical aggregation induced emission feature, is applied to replace octylamine to fabricate CH3NH3PbBr3 nanocrystals. The obtained CH3NH3PbBr3 nanocrystals were nanocubes (average diameter ∼ 11.1 nm) and are likely to assemble into ordered superstructures. By adjusting the chain length of the TPE derivative, we found that the assembly of the CH3NH3PbBr3 nanocrystals was correlated with the interactions between the TPE groups. This provides a new platform to investigate the ligand effects in nanocrystal solids and may potentially achieve enhanced optical and electrical properties.

Top-Down Fabrication of Stable Methylammonium Lead Halide Perovskite Nanocrystals by Employing a Mixture of Ligands as Coordinating Solvents.

A top-down method is demonstrated for the fabrication of CH3 NH3 PbBr3 and CH3 NH3 PbI3 perovskite nanocrystals, employing a mixture of ligands oleic acid and oleylamine as coordinating solvents. This approach avoids the use of any polar solvents, skips multiple reaction steps by employing a simple ultrasonic treatment of the perovskite precursors, and yields rather monodisperse blue-, green-, and red-emitting methylammonium lead halide nanocrystals with a high photoluminescence quantum yield (up to 72 % for the green-emitting nanocrystals) and remarkably improved stability. After discussing all relevant reaction parameters, the green-emitting CH3 NH3 PbBr3 nanocrystals are employed as a component of down-conversion white-light-emitting devices.

Colloidal Synthesis of CH3 NH3 PbBr3 Nanoplatelets with Polarized Emission through Self-Organization.

We report a combined experimental and theoretical study of the synthesis of CH3 NH3 PbBr3 nanoplatelets through self-organization. Shape transformation from spherical nanodots to square or rectangular nanoplatelets can be achieved by keeping the preformed colloidal nanocrystals at a high concentration (3.5 mg mL-1 ) for 3 days, or combining the synthesis of nanodots with self-organization. The average thickness of the resulting CH3 NH3 PbBr3 nanoplatelets is similar to the size of the original nanoparticles, and we also noticed several nanoplatelets with circular or square holes, suggesting that the shape transformation experienced a self-organization process through dipole-dipole interactions along with a realignment of dipolar vectors. Additionally, the CH3 NH3 PbBr3 nanoplatelets exhibit excellent polarized emissions for stretched CH3 NH3 PbBr3 nanoplatelets embedded in a polymer composite film, showing advantageous photoluminescence properties for display backlights.

Tumor-Targeted Multimodal Optical Imaging with Versatile Cadmium-Free Quantum Dots.

The rapid development of fluorescence imaging technologies requires concurrent improvements in the performance of fluorescent probes. Quantum dots have been extensively used as an imaging probe in various research areas because of their inherent advantages based on unique optical and electronic properties. However, their clinical translation has been limited by the potential toxicity especially from cadmium. Here, a versatile bioimaging probe is developed by using highly luminescent cadmium-free CuInSe2/ZnS core/shell quantum dots conjugated with CGKRK (Cys-Gly-Lys-Arg-Lys) tumor-targeting peptides. This probe exhibits excellent photostability, reasonably long circulation time, minimal toxicity, and strong tumor-specific homing property. The most important feature of this probe is that it shows distinctive versatility in tumor-targeted multimodal imaging including near-infrared, time-gated, and two-photon imaging in different tumor models. In a glioblastoma mouse model, the targeted probe clearly denotes tumor boundaries and positively labels a population of diffusely infiltrating tumor cells, suggesting its utility in precise tumor detection during surgery. This work lays a foundation for potential clinical translation of the probe.

Electrically controllable plasmonic enhanced coherent random lasing from dye-doped nematic liquid crystals containing Au nanoparticles.

An electrically controllable plasmonic enhanced coherent random lasing from the dye-doped nematic liquid crystal containing Au nanoparticles is demonstrated. To achieve the optimal control of the RL properties, the polarization of the pump light should be parallel to the rubbing direction of the cells. The lasing output intensity is direction-dependent and the substantial output distributes in an angle range of 0°~30° deviating from the direction of the pump stripe. The coherent feedback associated with the coherent random lasing mainly originates from the cooperative effect of the enhanced localized electric field in the vicinity of Au nanoparticles and the multiple scattering caused by the fluctuations of the liquid crystal director and local dielectric tensor.