Photoluminescence blinking—random switching between states of high (ON) and low (OFF) emissivities—is a universal property of molecular emitters found in dyes, polymers, biological molecules and artificial nanostructures such as nanocrystal quantum dots, carbon nanotubes and nanowires. For the past 15 years, colloidal nanocrystals have been used as a model system to study this phenomenon. The occurrence of OFF periods in nanocrystal emission has been commonly attributed to the presence of an additional charge, which leads to photoluminescence quenching by non-radiative recombination (the Auger mechanism). However, this ‘charging’ model was recently challenged in several reports. Here we report time-resolved photoluminescence studies of individual nanocrystal quantum dots performed while electrochemically controlling the degree of their charging, with the goal of clarifying the role of charging in blinking. We find that two distinct types of blinking are possible: conventional (A-type) blinking due to charging and discharging of the nanocrystal core, in which lower photoluminescence intensities correlate with shorter photoluminescence lifetimes; and a second sort (B-type), in which large changes in the emission intensity are not accompanied by significant changes in emission dynamics. We attribute B-type blinking to charge fluctuations in the electron-accepting surface sites. When unoccupied, these sites intercept ‘hot’ electrons before they relax into emitting core states. Both blinking mechanisms can be electrochemically controlled and completely suppressed by application of an appropriate potential.

https://absimage.aps.org/image/MAR12/MWS_MAR12-2011-002227.pdf

Two types of luminescence blinking revealed by spectroelectrochemistry of single quantum dots

Quantum dots are a unique class of emitters with size-tunable emission wavelengths, saturated emission colors, near-unity luminance efficiency, inherent photo- and thermal- stability and excellent solution processability. Quantum dots have been used as down-converters for back-lighting in liquid-crystal displays to improve color gamut, leading to the booming of quantum-dot televisions in consumer market. In the past few years, efficiency and lifetime of electroluminescence devices based on quantum dots achieved tremendous progress. These encouraging facts foreshadow the commercialization of quantum-dot light-emitting diodes (QLEDs), which promises an unprecedented generation of cost-effective, large-area, energy-saving, wide-color-gamut, ultra-thin and flexible displays. Here we provide a Progress Report, covering interdisciplinary aspects including material chemistry of quantum dots and charge-transporting layers, optimization and mechanism studies of prototype devices and processing techniques to produce large-area and high-resolution red-green-blue pixel arrays. We also identify a few key challenges facing the development of active-matrix QLED displays.

Quantum-Dot Light-Emitting Diodes for Large-Area Displays: Towards the Dawn of Commercialization.

Metal-halide perovskites have rapidly emerged as one of the most promising materials of the 21st century, with many exciting properties and great potential for a broad range of applications, from photovoltaics to optoelectronics and photocatalysis. The ease with which metal-halide perovskites can be synthesized in the form of brightly luminescent colloidal nanocrystals, as well as their tunable and intriguing optical and electronic properties, has attracted researchers from different disciplines of science and technology. In the last few years, there has been a significant progress in the shape-controlled synthesis of perovskite nanocrystals and understanding of their properties and applications. In this comprehensive review, researchers having expertise in different fields (chemistry, physics, and device engineering) of metal-halide perovskite nanocrystals have joined together to provide a state of the art overview and future prospects of metal-halide perovskite nanocrystal research.

State of the Art and Prospects for Halide Perovskite Nanocrystals.

Transition-metal activated phosphors are an important family of luminescent materials that can produce white light with an outstanding color rendering index and correlated color temperature for use in light-emitting diodes. In recent years, work in this quite “hot” research field has focused on the development of Mn2+ and Mn4+ activated red phosphors. In this review article, we provide an overview of recent studies on Mn2+ and Mn4+ doped phosphors, including detailed synthesis routes (solid-state reaction and wet-chemical synthesis) and description of luminescence mechanisms and phosphors’ behaviors; discuss their promising applications in white light-emitting diodes; and present an extensive list of references to representative works in this field.

Mn2+ and Mn4+ red phosphors: synthesis, luminescence and applications in WLEDs. A review

Hybrid lead halide perovskites exhibit carrier properties that resemble those of pristine nonpolar semiconductors despite static and dynamic disorder, but how carriers are protected from efficient scattering with charged defects and optical phonons is unknown. Here, we reveal the carrier protection mechanism by comparing three single-crystal lead bromide perovskites: CH3NH3PbBr3, CH(NH2)2PbBr3, and CsPbBr3. We observed hot fluorescence emission from energetic carriers with ~102-picosecond lifetimes in CH3NH3PbBr3 or CH(NH2)2PbBr3, but not in CsPbBr3. The hot fluorescence is correlated with liquid-like molecular reorientational motions, suggesting that dynamic screening protects energetic carriers via solvation or large polaron formation on time scales competitive with that of ultrafast cooling. Similar protections likely exist for band-edge carriers. The long-lived energetic carriers may enable hot-carrier solar cells with efficiencies exceeding the Shockley-Queisser limit.

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Screening in crystalline liquids protects energetic carriers in hybrid perovskites

A series of Mn2+-doped CsPbCl3 nanocrystals (NCs) was synthesized using reaction temperature and precursor concentration to tune Mn2+ concentrations up to 14%, and then studied using variable-temperature photoluminescence (PL) spectroscopy. All doped NCs show Mn2+ 4T1g → 6A1g d–d luminescence within the optical gap coexisting with excitonic luminescence at the NC absorption edge. Room-temperature Mn2+ PL quantum yields increase with increased doping, reaching ∼60% at ∼3 ± 1% Mn2+ before decreasing at higher concentrations. The low-doping regime is characterized by single-exponential PL decay with a concentration-independent lifetime of 1.8 ms, reflecting efficient luminescence of isolated Mn2+. At elevated doping, the decay is shorter, multiexponential, and concentration-dependent, reflecting the introduction of Mn2+–Mn2+ dimers and energy migration to traps. A large, anomalous decrease in Mn2+ PL intensity is observed with decreasing temperature, stemming from the strongly temperature-dependent exciton l...

Photoluminescence Temperature Dependence, Dynamics, and Quantum Efficiencies in Mn2+-Doped CsPbCl3 Perovskite Nanocrystals with Varied Dopant Concentration

Deep-blue, high color purity electroluminescence (EL) is demonstrated in an inverted light-emitting device using nontoxic ZnSe/ZnS core/shell quantum dots (QDs) as the emitter. The device exhibits moderate turn-on voltage (4.0 V) and color-saturated deep blue emission with a narrow full width at half maximum of ∼15 nm and emission peak at 441 nm. Their maximum luminance and current efficiency reach 1170 cd/m2 and 0.51 cd/A, respectively. The high performances are achieved through a ZnO nanoparticle based electron-transporting layer due to efficient electron injection into the ZnSe/ZnS QDs. Energy transfer processes between the ZnSe/ZnS QDs and hole-transporting materials are studied by time-resolved photoluminescence spectroscopy to understand the EL mechanism of the devices. These results provide a new guide for the fabrication of efficient deep-blue quantum dot light-emitting diodes and the realization of QD-based lighting sources and full-color panel displays.

High color purity ZnSe/ZnS core/shell quantum dot based blue light emitting diodes with an inverted device structure

Although Mn2+ doping in semiconductor nanocrystals (NCs) has been studied for nearly three decades, the near 100% photoluminescence (PL) quantum yield (QY) of Mn2+ emission has never been realized so far. Herein, greatly improved PL QYs of Mn2+ emissions are reported in Mn2+-doped CsPbCl3 NCs with various Mn2+ doping concentrations after CdCl2 post-treatment at room temperature. Specifically, the near-unity QY and near single-exponential decay of red Mn2+ emission peaking at 627 nm in doped CsPbCl3 NCs are obtained for the first time. The temperature dependence of steady-state and time-resolved PL spectra reveals that the CdCl2 post-treatment significantly reduces the nonradiative defect states and enhances the energy transfer from host to Mn2+ ions. Moreover, the Mn2+:CsPbCl3 NCs after CdCl2 post-treatment exhibit robust stability and high PL QYs after multipurification. The results will provide an effective route to obtain doped perovskite NCs with high performance for white lighting emitting diodes.

Near-Unity Red Mn2+ Photoluminescence Quantum Yield of Doped CsPbCl3 Nanocrystals with Cd Incorporation.

It is challenging to improve the emission efficiency of Mn-doped CsPbCl3 (Mn:CsPbCl3) nanocrystals (NCs) because the excellent optical performances are dependent on high doping efficiency and few defects and traps Steady-state and time-resolved photoluminescence (PL) spectroscopies were used to investigate the luminescence properties of Mn:CsPbCl3 NCs with different Mn doping levels synthesized in the presence of nickel chloride The doping efficiency of Mn ions in Mn:CsPbCl3 NCs was greatly enhanced in the presence of NiCl2, and the PL wavelength of Mn2+ ions was tuned from 594 to 638 nm by varying the concentration of dopant Mn from 011% to 1525% The high emission quantum yields of Mn:CsPbCl3 NCs with orange and red emissions peaked at 600 and 620 nm in hexane were 70% and 39%, respectively The improvement in doping and emission efficiencies of Mn2+ was attributed to the enhanced formation energies of the Mn doping under the Mn and Ni codoped configuration and the resulting reduction of defects and traps in Mn:CsPbCl3 NCs with incorporation of Ni2+ ions

Improved Doping and Emission Efficiencies of Mn-Doped CsPbCl3 Perovskite Nanocrystals via Nickel Chloride.

Quantum dot light-emitting diodes (QLEDs) with an excellent external quantum efficiency (EQE) and an excellent lifetime almost meet the requirements for low-brightness displays. However, the short operation lifetime under high brightness limits the application of QLEDs in outdoor displays and lightings. Herein, we report a highly efficient, stable red QLED using co-doped lithium and magnesium as well as a magnesium oxide shell-coated zinc oxide nanoparticle layer as an electron transport layer (ETL). The optimized QLED has a high peak EQE of 20.6%, a low efficiency roll-off at high current, and a remarkably long lifetime T95 of >11000 h at 1000 cd m-2, which is an indication of the realization of the most stable red QLED to date. The improvement in the long term stability of the QLED is attributed to the use of a co-doped and shell-coated zinc oxide ETL with a reduced level of electron injection to improve the charge balance in the device.

Yunjun Wang

Papers

Photoluminescence Temperature Dependence, Dynamics, and Quantum Efficiencies in Mn2+-Doped CsPbCl3 Perovskite Nanocrystals with Varied Dopant Concentration

High color purity ZnSe/ZnS core/shell quantum dot based blue light emitting diodes with an inverted device structure

Near-Unity Red Mn2+ Photoluminescence Quantum Yield of Doped CsPbCl3 Nanocrystals with Cd Incorporation.

Improved Doping and Emission Efficiencies of Mn-Doped CsPbCl3 Perovskite Nanocrystals via Nickel Chloride.

Highly Stable Red Quantum Dot Light-Emitting Diodes with Long T95 Operation Lifetimes.