Highly Efficient Deep Blue Cd-Free Quantum Dot Light-Emitting Diodes by a p-Type Doped Emissive Layer.

Environmentally friendly ZnSe/ZnS core/shell quantum dots (QDs) as an alternative blue emission material to Cd-based QDs have shown great potential for use in next-generation displays. However, it remains still challenging to realize a high-efficiency quantum dot light-emitting diode (QLED) based on ZnSe/ZnS QDs due to their insufficient electrical characteristics, such as excessively high electron mobility (compared to the hole mobility) and the deep-lying valence band. In this work, the effects of QDs doped with hole transport materials (hybrid QDs) on the electrical characteristics of a QLED are investigated. These hybrid QDs show a p-type doping effect, which leads to a change in the density of the carriers. Specifically, the hybrid QDs can balance electrons and holes by suppressing the overflow of electrons and improving injection of holes, respectively. These electrical characteristics help to improve device performance. In detail, an external quantum efficiency (EQE) of 6.88% is achieved with the hybrid QDs. This is increased by 180% compared to a device with pure ZnSe/ZnS QDs (EQE of 2.46%). This record is the highest among deep-blue Cd-free QLED devices. These findings provide the importance of p-type doping effect in QD layers and guidance for the study of the electrical properties of QDs.

Order-of-Magnitude, Broadband-Enhanced Light Emission from Quantum Dots Assembled in Multiscale Phase-Separated Block Copolymers.

Achieving high emission efficiency in solid-state quantum dots (QDs) is an essential requirement for high-performance QD optoelectronics. However, most QD films suffer from insufficient excitation and light extraction efficiencies, along with nonradiative energy transfer between closely adjacent QDs. Herein, we suggest a highly effective strategy to enhance the photoluminescence (PL) of QD composite films through an assembly of QDs and poly(styrene-b-4-vinylpyridine)) (PS-b-P4VP) block copolymer (BCP). A BCP matrix casted under controlled humidity provides multiscale phase-separation features based on (1) submicrometer-scale spinodal decomposition between polymer-rich and water-rich phases and (2) sub-10 nm-scale microphase separation between polymer blocks. The BCP-QD composite containing bicontinuous random pores achieves significant enhancement of both light absorption and extraction efficiencies via effective random light scattering. Moreover, the microphase-separated morphology substantially reduces the Förster resonance energy transfer efficiency from 53% (pure QD film) to 22% (BCP-QD composite), collectively achieving an unprecedented 21-fold enhanced PL over a broad spectral range.

Enhancing the luminescence of carbon nanodots in films by tailoring the functional groups through alkylamine-functionalization and reduction.

Enhancing the luminescence efficiency and stability of solid-state phosphors with facile processability is important for various applications. Carbon-based materials might have proper optical features and durability under ambient conditions. However, carbon-based phosphors usually showed severe quenching of the photoluminescence in the absence of solvent. Alkylamine-functionalization of carbon-based phosphors can alleviate the quenching, but it also resulted in low luminous efficiency. In this study, tailoring the functional groups of carbon nanodots (CNDs) was carefully studied through alkylamine-functionalization and reduction. The reduction with NaBH4 changed the electron-withdrawing functional groups on the alkylamine-functionalized CNDs to electron-donating groups, enhancing the luminescence efficiency. The delicate modulation of alkylamine-functionalization and reduction enabled efficient and robust photoluminescence in the film without any host materials.

Electrostatic Stabilized InP Colloidal Quantum Dots with High Photoluminescence Efficiency.

Electrostatically stabilized InP quantum dots (QDs) showing a high luminescence yield of 16% without any long alkyl chain coordinating ligands on their surface are demonstrated. This is achieved by UV-etching the QDs in the presence of fluoric and sulfuric acids. Fluoric acid plays a critical role in selectively etching nonradiative sites during the ligand-exchange process and in relieving the acidity of the solution to prevent destruction of the QDs. Given that the InP QDs show high luminescence without any electrical barriers, such as long alkyl ligands or inorganic shells, this method can be applied for QD treatment for application to highly efficient QD-based optoelectronic devices.

Serum-stable quantum dot-protein hybrid nanocapsules for optical bio-imaging.

We introduce shell cross-linked protein/quantum dot (QD) hybrid nanocapsules as a serum-stable systemic delivery nanocarrier for tumor-targeted in vivo bio-imaging applications. Highly luminescent, heavy-metal-free Cu0.3InS2/ZnS (CIS/ZnS) core-shell QDs are synthesized and mixed with amine-reactive six-armed poly(ethylene glycol) (PEG) in dichloromethane. Emulsification in an aqueous solution containing human serum albumin (HSA) results in shell cross-linked nanocapsules incorporating CIS/ZnS QDs, exhibiting high luminescence and excellent dispersion stability in a serum-containing medium. Folic acid is introduced as a tumor-targeting ligand. The feasibility of tumor-targeted in vivo bio-imaging is demonstrated by measuring the fluorescence intensity of several major organs and tumor tissue after an intravenous tail vein injection of the nanocapsules into nude mice. The cytotoxicity of the QD-loaded HSA-PEG nanocapsules is also examined in several types of cells. Our results show that the cellular uptake of the QDs is critical for cytotoxicity. Moreover, a significantly lower level of cell death is observed in the CIS/ZnS QDs compared to nanocapsules loaded with cadmium-based QDs. This study suggests that the systemic tumor targeting of heavy-metal-free QDs using shell cross-linked HSA-PEG hybrid nanocapsules is a promising route for in vivo tumor diagnosis with reduced non-specific toxicity.

Tunable emission from blue to white light in single-phase Na(0.34)Ca(0.66-x-y)Al(1.66)Si(2.34)O8:xEu2+,yMn2+ (x = 0.07) phosphor for white-light UV LEDs.

A series of single-phased emission-tunable Na(0.34)Ca(0.66)Al(1.66)Si(2.34)O(8):Eu(2+),Mn(2+) phosphors were successfully synthesized by a wet-chemical synthesis method. Photoluminescence excitation (PLE) spectra indicate that the phosphor can be efficiently excited by UV radiation from 250 to 420 nm. Also, NCASO:Eu(2+),Mn(2+) phosphor exhibit a broad blue emission band at 440 nm and an orange emission band at 570 nm, which originate from Eu(2+) and Mn(2+) ions, respectively. Therefore, overall emission color can be tuned from blue to white by increasing the concentration of Mn(2+) ions in the host lattice utilizing energy transfer from Eu(2+) to Mn(2+) ions. This energy transfer phenomenon was demonstrated to be a resonant type through dipole-dipole interaction determined with the help of PL spectra, decay time measurement, and energy transfer efficiency of the phosphor. These results indicate that NCASO:Eu(2+),Mn(2+) can be a promising single-phased white-emitting phosphor for white-light UV LEDs.

Energy transfer in Sr2MgSi2O7:Eu2+ phosphors in nano scale and their application to solid state lighting with excellent color rendering.

On the basis of structural information of its host material which shows excellent stability and absorption efficiency in ultra-violet (UV) region, a blue-emitting Sr2MgSi2O7:Eu2+ (SMS:Eu2+) phosphor was synthesized, and its photoluminescence (PL) performance was systematically optimized. In order to enhance its PL properties, Ce3+ was added as a sensitizer based on the energy transfer from the absorption energy of Ce3+ to Eu2+. It was due to the spectral overlap between the photoluminescence excitation spectrum of Ce3+ and the PL spectrum of Eu2+. Moreover, the energy transfer rate from Ce3+ to Eu2+ is generally faster than the emission rate of Ce3+ in the dipole-dipole interaction. Depending upon the amount of Ca2+ substituted into Sr site, their maximum wavelength was varied from -460 to -540 nm in terms of the crystal field effect confirmed by the structural analysis via Rietveld refinement method. Finally, the optimized blue-emitting SMS:Eu2+ and Ca(2+)-substituted yellowish green-emitting SMS:Eu2+ phosphors were applied with Eu(2+)-sensitized red-emitting Ca3Mg3(PO4)4:Mn2+ phosphor introduced in our previous research to UV light emitting diode (LED)-pumped white LEDs. The fabricated white LEDs showed a natural white light with the color coordinate of (0.3298, 0.3280) and the excellent color rendering index of 94.

Bendable inorganic thin-film battery for fully flexible electronic systems.

High-performance flexible power sources have gained attention, as they enable the realization of next-generation bendable, implantable, and wearable electronic systems. Although the rechargeable lithium-ion battery (LIB) has been regarded as a strong candidate for a high-performance flexible energy source, compliant electrodes for bendable LIBs are restricted to only a few materials, and their performance has not been sufficient for them to be applied to flexible consumer electronics including rollable displays. In this paper, we present a flexible thin-film LIB developed using the universal transfer approach, which enables the realization of diverse flexible LIBs regardless of electrode chemistry. Moreover, it can form high-temperature (HT) annealed electrodes on polymer substrates for high-performance LIBs. The bendable LIB is then integrated with a flexible light-emitting diode (LED), which makes an all-in-one flexible electronic system. The outstanding battery performance is explored and well supported by finite element analysis (FEA) simulation.

Nanoplasmon-enhanced transparent plasma display devices.

Plasmon-enhanced transparent plasma display devices are demonstrated via the resonant interface between Ag nanoparticles and a Eu(3+)-doped phosphor. Enhanced emission from the phosphor by metallic nanoparticles leads to an increase of the luminous efficacy in the transparent plasma display device. This is a prototype of the plasmon-enhanced transparent plasma display device.

Yellow-emitting γ-Ca2SiO4:Ce3+, Li+ phosphor for solid-state lighting: luminescent properties, electronic structure, and white light-emitting diode application.

A new yellow-emitting γ-Ca2SiO4:Ce3+,Li+ phosphor was synthesized via a solid-state reaction. The phosphor showed a strong yellow emission with a wide bandwidth of 135.4 nm under blue light excitation. Absorption and photoluminescence measurements and density functional theory calculations suggest that the luminescence of the phosphor can be attributed primarily to the transitions of 5d→4f (2F(7/2) and 2F(5/2)) of Ce3+ ions occupying Ca(1) sites in the host crystal. White light-emitting diodes (LEDs) were fabricated by combining this phosphor with a blue LED, and excellent white light with a high color rendering index of 86 was created owing to the wide emission bandwidth of the phosphor.

Improved light extraction efficiency in organic light emitting diodes with a perforated WO3 hole injection layer fabricated by use of colloidal lithography.

We present an organic light emitting diode with a perforated WO3 hole injection layer to improve the light extraction efficiency. The two-dimensionally perforated WO3 layer was fabricated by use of colloidal lithography. The light extraction efficiency was improved due to Bragg scattering of waveguide modes and surface plasmon polaritons, and the operating voltage was also decreased. As a result, the external quantum efficiency and the power efficiency were increased as compared with those of conventional organic light emitting diodes without WO3 layer. The angular dependence of emission characteristics was investigated by measuring radiant intensity profiles for emission angles and azimuthal angles.

Novel blue-emitting Na(x)Ca(1-x)Al(2-x)Si(2+x)O8:Eu2+ (x = 0.34) phosphor with high luminescent efficiency for UV-pumped light-emitting diodes.

A novel blue-emitting phosphor, Na(0.34)Ca(0.66)Al(1.66)Si(2.34)O(8):Eu(2+) (NCASO:Eu(2+)), was prepared by a wet chemical synthesis method based on the hydrolysis of tetraorthosiliate (TEOS) and confirmed the formation of NCASO:Eu(2+) from Rietveld analysis. Photoluminescence (PL) results showed that the phosphor can be efficiently excited by UV light from 250 to 420 nm, and emitted bright broad blue emission, which has maximum intensity at around 445 nm. Under 365 nm excitation, the PL emission intensity area of optimized NCASO:Eu(2+) was found to be 99.72% of that of a commercial BaMgAl(10)O(17):Eu(2+) (BAM:Eu(2+)) phosphor. Moreover, the optical absorbance, internal quantum efficiency, and external quantum efficiency of NCASO:Eu(2+) were calculated to be 112%, 94%, and 105% of that of the commercial BAM:Eu(2+) phosphor, respectively. The WLEDs were fabricated using the blue NCASO:Eu(2+) phosphor, a green-emitting ß-SiAlON:Eu(2+), and a red-emitting CaAlSiN(3):Eu(2+) phosphors with a near-UV chip. The WLED device exhibited an excellent color-rendering index R(a) of 94 at a correlated color temperature of 5956 K with CIE coordinates of x = 0.323, y = 0.335. These results suggest that NCASO:Eu(2+) is a promising blue-emitting phosphor for UV LED applications.

Synthesis of green emitting and transparent zn2siO4:mn2+ thin film phosphors on 2D photonic crystal patterned quartz substrates.

Zn2SiO4:Mn2+ thin film phosphors (TFPs) have been synthesized by RF magnetron sputtering, using a single multicomponent stoichiometric target. And 2D photonic crystal patterns were introduced on a quartz substrate to enhance the light extraction efficiency. In order to introduce 2D photonic crystal patterns on a quartz substrate, nanosphere lithography was used. Polystyrene spheres, with diameter of 330 nm, were transferred on the quartz substrate and subsequently were served as an etch mask. Quartz substrates were patterned by CF4 gas-based reactive ion etching. Zn2SiO4:Mn2+ were deposited on that 2D photonic crystal patterned quartz substrate and the effect of height of photonic crystal layers were investigated. The light extraction efficiency of Zn2SiO4:Mn2+ thin film phosphors deposited on the photonic crystal patterned quartz substrate was enhanced three times to compared with that of flat Zn2SiO4:Mn2+ thin film phosphors due to the Bragg diffraction and leaky mode caused by PCLs. Transmittance of Zn2SiO4:Mn2+ TFPs deposited on the photonic crystal patterned substrate was high enough, above 70% in the visible light region with respect to that of quartz substrate.

Photoluminescence enhancement of synthesized ZnS-based-nanocrystals and aging effect on its emitting color.

Various colors-emitting ZnS:Cu,Cl, ZnS:Cu,Cl,Mn and ZnS:Mn nanocrystals (NCs) which were shown to be about 3 nm sized-particle were synthesized by using a solution chemistry. And the luminescences of the synthesized ZnS-based NCs were investigated through photoluminescence excitation (PLE) and photoluminescence (PL) spectroscopy. The PLE and PL intensities of the ZnS-based NCs depends on their reflux time, and red shifted maximum PLE wavelengths of the synthesized NCs showed with increasing reflux time. The increased maximum PL intensity of NCs with increasing reflux time is due to the enhanced crystallinity of the NCs. And the shifted emitting colors of the NCs showed after aging treatment compared to those of refluxed NCs. The amount of shifted wavelength of Cu,CI doped ZnS, Cu,CI and Mn co-doped ZnS, only Mn doped ZnS NCs were -22 nm, +18 nm, and +14 nm, respectively.

Metal oxide charge transfer complex for effective energy band tailoring in multilayer optoelectronics.

Metal oxides are intensively used for multilayered optoelectronic devices such as organic light-emitting diodes (OLEDs). Many approaches have been explored to improve device performance by engineering electrical properties. However, conventional methods cannot enable both energy level manipulation and conductivity enhancement for achieving optimum energy band configurations. Here, we introduce a metal oxide charge transfer complex (NiO:MoO3-complex), which is composed of few-nm-size MoO3 domains embedded in NiO matrices, as a highly tunable carrier injection material. Charge transfer at the finely dispersed interfaces of NiO and MoO3 throughout the entire film enables effective energy level modulation over a wide work function range of 4.47 - 6.34 eV along with enhanced electrical conductivity. The high performance of NiO:MoO3-complex is confirmed by achieving 189% improved current efficiency compared to that of MoO3-based green OLEDs and also an external quantum efficiency of 17% when applied to blue OLEDs, which is superior to 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile-based conventional devices.

Localized surface plasmon enhanced cathodoluminescence from Eu3+-doped phosphor near the nanoscaled silver particles.

We elucidate that the luminescence from Eu3+-doped phosphor excited by the electron collision can be modified on location near the metallic nanoparticles. The Eu3+-doped phosphor was fabricated on the nanoscaled Ag particles ranging of 5 nm to 30 nm diameter. As a result of the cathodoluminescence measurements, the phosphor films on the Ag particles showed up to twofold more than that of an isolated phosphor film. Enhanced cathodoluminescence originated from the resonant coupling between the localized surface plasmon of Ag nanoparticles and radiating energy of the phosphor. Cathodoluminescent phosphor for high luminous display devices can be addressed by locating phosphor near the surface of metallic nanoparticles.

Widely tunable emissions of colloidal Zn(x)Cd(1-x)Se alloy quantum dots using a constant Zn/Cd precursor ratio.

The widely tunable emissions of Zn(x)Cd(1-x)Se alloy quantum dots (QDs), which emit green to red wavelengths from 534 to 620 nm, are reported. Green-, yellow-, orange-, and red-emitting QDs were synthesized by varying a point of time for oleylamine (as a co-surfactant) addition and a Se precursor amount, and keeping a constant Zn/Cd precursor ratio. With reaction time the alloying and particle growth of the alloy QDs progressed simultaneously in the opposite direction in the variation of their band gap. However, the band gap energies of all QDs were observed to be gradually blue-shifted due to the slight dominance of alloying over the particle growth effect. The compositions of alloy QDs were estimated based on their sizes and band gap energies. Zn(x)Cd(1-x)Se core QDs were also overcoated with a ZnSe shell with a higher band gap to enhance their quantum yields.

Extremely Stable Luminescent Crosslinked Perovskite Nanoparticles under Harsh Environments over 1.5 Years.

Organic-inorganic hybrid perovskite nanoparticles (NPs) are a very strong candidate emitter that can meet the high luminescence efficiency and high color standard of Rec.2020. However, the instability of perovskite NPs is the most critical unsolved problem that limits their practical application. Here, an extremely stable crosslinked perovskite NP (CPN) is reported that maintains high photoluminescence quantum yield for 1.5 years (>600 d) in air and in harsher liquid environments (e.g., in water, acid, or base solutions, and in various polar solvents), and for more than 100 d under 85 °C and 85% relative humidity without additional encapsulation. Unsaturated hydrocarbons in both the acid and base ligands of NPs are chemically crosslinked with a methacrylate-functionalized matrix, which prevents decomposition of the perovskite crystals. Counterintuitively, water vapor permeating through the crosslinked matrix chemically passivates surface defects in the NPs and reduces nonradiative recombination. Green-emitting and white-emitting flexible large-area displays are demonstrated, which are stable for >400 d in air and in water. The high stability of the CPN in water enables biocompatible cell proliferation which is usually impossible when toxic Pb elements are present. The stable materials design strategies provide a breakthrough toward commercialization of perovskite NPs in displays and bio-related applications.

Thermodynamic-driven polychromatic quantum dot patterning for light-emitting diodes beyond eye-limiting resolution.

The next-generation wearable near-eye displays inevitably require extremely high pixel density due to significant decrease in the viewing distance. For such denser and smaller pixel arrays, the emissive material must exhibit wider colour gamut so that each of the vast pixels maintains the colour accuracy. Electroluminescent quantum dot light-emitting diodes are promising candidates for such application owing to their highly saturated colour gamuts and other excellent optoelectronic properties. However, previously reported quantum dot patterning technologies have limitations in demonstrating full-colour pixel arrays with sub-micron feature size, high fidelity, and high post-patterning device performance. Here, we show thermodynamic-driven immersion transfer-printing, which enables patterning and printing of quantum dot arrays in omni-resolution scale; quantum dot arrays from single-particle resolution to the entire film can be fabricated on diverse surfaces. Red-green-blue quantum dot arrays with unprecedented resolutions up to 368 pixels per degree is demonstrated.

Self-assembled SiO2 photonic crystal infiltrated by Ormosil:Eu(DBM)(3)phen phosphor and its enhanced photoluminescence.

Luminescence films were prepared by infiltration of the tris(dibenzoylmethane) mono(1, 10-phenanthroline) europium incorporated ormosil into colloidal SiO(2) photonic crystal templates. Because a stopband of the template was not overlapped with the PL excitation and emission bands, the stopband did not suppress the PL intensity. The PL intensity of the infiltrated film into the template was about 13.1 times higher than that of the plane film prepared without the template. Three major terms, which are the mass term, the scattering term, and the crystallinity term, were considered as factors that improve the PL intensity. The relative ratio of the effects of the mass term : the scattering term : the crystallinity term was 2.1 : 2.8 : 2.2.