Highly Efficient and Stable White Light-Emitting Diodes Using Perovskite Quantum Dot Paper.
ABSTRACT: Perovskite quantum dots (PQDs) are a competitive candidate for next-generation display technologies as a result of their superior photoluminescence, narrow emission, high quantum yield, and color tunability. However, due to poor thermal resistance and instability under high energy radiation, most PQD-based white light-emitting diodes (LEDs) show only modest luminous efficiency of ?50 lm W-1 and a short lifetime of <100 h. In this study, by incorporating cellulose nanocrystals, a new type of QD film is fabricated: CH3NH3PbBr3 PQD paper that features 91% optical absorption, intense green light emission (518 nm), and excellent stability attributed to the complexation effect between the nanocellulose and PQDs. The PQD paper is combined with red K2SiF6:Mn4+ phosphor and blue GaN LED chips to fabricate a high-performance white LED demonstrating ultrahigh luminous efficiency (124 lm W-1), wide color gamut (123% of National Television System Committee), and long operation lifetime (240 h), which paves the way for advanced lighting technology.
Project description:Inorganic lead halide perovskite quantum dots (PQDs), especially red emission PQDs, are well-known to easily lose their luminescence emission with time, which shows from strong emission of fresh PQDs to no emission of aged PQDs. Here, we demonstrate that trioctylphosphine (TOP) can effectively and instantly recover the luminescence emission of aged red PQDs, making the "dead" PQDs "reborn". Furthermore, TOP also works to improve the emission intensity of freshly synthesized PQDs. In this process, TOP does not make any detectable structural changes to PQDs. Besides, TOP can effectively enhance the stability of PQDs against long-term storage, temperature, UV irradiation, and polar solvents. This unusual emission recovery and stability enhancement by TOP shall promote the understanding of particle surface conditions and the development of PQD devices.
Project description:Organic-inorganic halide perovskite nanocrystals or quantum dots (PQDs) are excellent candidates for optoelectronic applications, such as lasers, solar cells, light emitting diodes, and single photon sources. However, the potential applications of PQDs can expand once the photoluminescence, and in particular, the blinking behaviors of single PQDs are understood. Although the blinking of PQDs has been studied extensively recently, the underlying mechanism of the blinking behaviors is still under debate. In this study, we confirmed that type-A and type-B-HC (hot carrier) blinking, contributed to PQD blinking using their fluorescence lifetime intensity distribution (FLID). Type-B-HC blinking was experimentally confirmed for the first time for formamidinium based PQDs, and the simultaneous contributions of type-A and type-B blinking were clearly specified. Further, we related different FLID data to the ON/OFF time distribution as distinct features of different blinking types. We also emphasized that detection capability was crucial for correctly elucidating the blinking mechanism.
Project description:Organic-inorganic halide perovskite quantum dots (PQDs) constitute an attractive class of materials for many optoelectronic applications. However, their charge transport properties are inferior to materials like graphene. On the other hand, the charge generation efficiency of graphene is too low to be used in many optoelectronic applications. Here, we demonstrate the development of ultrathin phototransistors and photonic synapses using a graphene-PQD (G-PQD) superstructure prepared by growing PQDs directly from a graphene lattice. We show that the G-PQDs superstructure synchronizes efficient charge generation and transport on a single platform. G-PQD phototransistors exhibit excellent responsivity of 1.4 × 108 AW-1 and specific detectivity of 4.72 × 1015 Jones at 430 nm. Moreover, the light-assisted memory effect of these superstructures enables photonic synaptic behavior, where neuromorphic computing is demonstrated by facial recognition with the assistance of machine learning. We anticipate that the G-PQD superstructures will bolster new directions in the development of highly efficient optoelectronic devices.
Project description:Red-emitting Mn4+-doped fluorides are a promising class of materials to improve the color rendering and luminous efficacy of white light-emitting diodes (w-LEDs). For w-LEDs, the luminescence quenching temperature is very important, but surprisingly no systematic research has been conducted to understand the mechanism for thermal quenching in Mn4+-doped fluorides. Furthermore, concentration quenching of the Mn4+ luminescence can be an issue but detailed investigations are lacking. In this work, we study thermal quenching and concentration quenching in Mn4+-doped fluorides by measuring luminescence spectra and decay curves of K2TiF6:Mn4+ between 4 and 600 K and for Mn4+ concentrations from 0.01% to 15.7%. Temperature-dependent measurements on K2TiF6:Mn4+ and other Mn4+-doped phosphors show that quenching occurs through thermally activated crossover between the 4T2 excited state and 4A2 ground state. The quenching temperature can be optimized by designing host lattices in which Mn4+ has a high 4T2 state energy. Concentration-dependent studies reveal that concentration quenching effects are limited in K2TiF6:Mn4+ up to 5% Mn4+. This is important, as high Mn4+ concentrations are required for sufficient absorption of blue LED light in the parity-forbidden Mn4+ d-d transitions. At even higher Mn4+ concentrations (>10%), the quantum efficiency decreases, mostly due to direct energy transfer to quenching sites (defects and impurity ions). Optimization of the synthesis to reduce quenchers is crucial for developing more efficient highly absorbing Mn4+ phosphors. The present systematic study provides detailed insights into temperature and concentration quenching of Mn4+ emission and can be used to realize superior narrow-band red Mn4+ phosphors for w-LEDs.
Project description:High-quality inorganic cesium lead halide perovskite quantum dot (CsPbBr<sub>3</sub> PQD) thin films were successfully deposited directly from a powdered source and used as an active laser medium following the examination of their distinctive surface and structural properties. To determine the suitability of the CsPbBr<sub>3</sub> PQDs as an active laser medium, amplified spontaneous emission (ASE) and optical gain properties were investigated under picosecond pulse excitation using the variable stripe length (VSL) method. The thin film of CsPbBr<sub>3</sub> PQDs has exhibited a sufficient value of the optical absorption coefficient of ?0.86 × 10<sup>5</sup> cm<sup>-1</sup> near the band edge and a direct band gap energy <i>E</i> <sub>g</sub> ?2.38 eV. The samples showed enhanced emission, and ASE was successfully recorded at a low threshold. The light emitted from the edge was observed near 2.40 and 2.33 eV for the stimulated emission (SE) and ASE regimes, respectively. The nonradiative decay contributes excitons dominant over biexcitons in the sample edge emission above the ASE threshold, making it practical for CsPbBr<sub>3</sub> PQDs to be used as optical gain media without undergoing repeated SE processes above the threshold over long periods. A high value of the optical gain coefficient was recorded at 346 cm<sup>-1</sup>.
Project description:Magic clusters have attracted significant interest to explore the dynamics of quantum dot (QD) nucleation and growth. At the same time, CdSe magic-sized QDs reveal broadband emission in the visible wavelength region, which advantageously offer simple integration of a single-type of nanomaterial and high color rendering ability for white light-emitting diodes (LEDs). Here, we optimized the quantum yield of magic-sized CdSe QDs up to 22% via controlling the synthesis parameters without any shelling or post-treatment process and integrated them in liquid-state on blue LED to prevent the efficiency drop due to host-material effect. The fabricated white LEDs showed color-rendering index and luminous efficiency up to 89 and 11.7?lm/W, respectively.
Project description:Metastable multiexcitonic states (MESs) of semiconductor quantum dots can be involved in multielectron transfer reactions, which opens new perspectives in nanomaterials-based optoelectronic applications. Herein, we demonstrate the generation of a MES in CsPbBr3 perovskite quantum dots (PQDs) and its dissociation dynamics through multiple electron transfers to molecular electron acceptors, anthraquinones (AQs), bound to the PQD surface by a carboxylic anchor. As many as 14 excitons are produced at an excitation density of roughly 220 ?J cm-2 without detectable PQD degradation. Addition of AQ results in the formation of PQD-AQ hybrids with excess of AQs (PQD:AQ ? 1:20), which opens the possibility of multielectron transfer acts from MES to AQs. We found that the electron transfer saturates after roughly five transfer acts and that the first electron transfer (ET) time constant is as short as 1 ps. However, each ET increases the Coulomb potential barrier for the next ET, which decreases the rate of ET, resulting in a saturation after five ETs.
Project description:Mn4+ activated LaMgAl11O19 (LMA/Mn4+) with red emitting phosphor was obtained by sintering under air conditioning. The X-ray diffraction pattern Rietveld refinement results reveal that three six-fold coordinated Al sites are substituted by Mn4+ ions. Furthermore, the chemical valence state of manganese in the LMA host was further confirmed through X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR). Photoluminescence emission (PL) and excitation (PLE) spectra of LMA/Mn4+ as well as the lifetime were measured, and the 663 nm emission is ascribed to the ²Eg??A2g from the 3d³ electrons in the [MnO?]8- octahedral complex. The emission spectrum matches well with the absorption of phytochrome. Temperature-dependent PL spectra show that the color changes of the phosphor at 420 K are 0.0110 for ?x and -0.0109 for ?y. Moreover, doping Zn2+ and Mg2+ ions in the host enhances the emission intensity of Mn4+ ions. These results highlight the potential of LMA/Mn4+ phosphor for a light-emitting diode (LED) plant lamp.
Project description:Nanoscale phosphorene quantum dots (PQDs) with few-layer structures were fabricated by pulsed laser ablation of a bulk black phosphorus target in diethyl ether. An intense and stable photoluminescence (PL) emission of the PQDs in the blue-violet wavelength region is clearly observed for the first time, which is attributed to electronic transitions from the lowest unoccupied molecular orbital (LUMO) to the highest occupied molecular orbital (HOMO) and occupied molecular orbitals below the HOMO (H-1, H-2), respectively. Surprisingly, the PL emission peak positions of the PQDs are not red-shifted with progressively longer excitation wavelengths, which is in contrast to the cases of graphene and molybdenum disulphide quantum dots. This excitation wavelength-independence is derived from the saturated passivation on the periphery and surfaces of the PQDs by large numbers of electron-donating functional groups which cause the electron density on the PQDs to be dramatically increased and the band gap to be insensitive to the quantum size effect in the PQDs. This work suggests that PQDs with intense, stable and excitation wavelength-independent PL emission in the blue-violet region have a potential application as semiconductor-based blue-violet light irradiation sources.
Project description:Here, we report efficient composition-tunable Cu-doped ZnInS/ZnS (core and core/shell) colloidal nanocrystals (CNCs) synthesized by using a colloidal non-injection method. The initial precursors for the synthesis were used in oleate form rather than in powder form, resulting in a nearly defect-free photoluminescence (PL) emission. The change in Zn/In ratio tunes the percentage incorporation of Cu in CNCs. These highly monodisperse Cu-doped ZnInS CNCs having variable Zn/In ratios possess peak emission wavelength tunable from 550 to 650 nm in the visible spectrum. The quantum yield (QY) of these synthesized Cd-free CNCs increases from 6.0 to 65.0% after coating with a ZnS shell. The CNCs possessing emission from a mixed contribution of deep trap and dopant states to only dominant dopant-related Stokes-shifted emission are realized by a careful control of stoichiometric ratio of different reactant precursors during synthesis. The origin of this shift in emission was understood by using steady state and time-resolved fluorescence (TRF) spectroscopy studies. As a proof-of-concept demonstration, these blue excitable Cu-doped ZnInS/ZnS CNCs have been integrated with commercial blue LEDs to generate white-light emission (WLE). The suitable combination of these highly efficient doped CNCs results led to a Commission Internationale de l'Enclairage (CIE) color coordinates of (0.33, 0.31) at a color coordinate temperature (CCT) of 3694 K, with a luminous efficacy of optical radiation (LER) of 170 lm/Wopt and a color rendering index (CRI) of 88.