Highly efficient and stable InP/ZnSe/ZnS quantum dot light-emitting diodes.

Quantum dot (QD) light-emitting diodes (LEDs) are ideal for large-panel displays because of their excellent efficiency, colour purity, reliability and cost-effective fabrication1-4. Intensive efforts have produced red-, green- and blue-emitting QD-LEDs with efficiencies of 20.5 per cent4, 21.0 per cent5 and 19.8 per cent6, respectively, but it is still desirable to improve the operating stability of the devices and to replace their toxic cadmium composition with a more environmentally benign alternative. The performance of indium phosphide (InP)-based materials and devices has remained far behind those of their Cd-containing counterparts. Here we present a synthetic method of preparing a uniform InP core and a highly symmetrical core/shell QD with a quantum yield of approximately 100 per cent. In particular, we add hydrofluoric acid to etch out the oxidative InP core surface during the growth of the initial ZnSe shell and then we enable high-temperature ZnSe growth at 340 degrees Celsius. The engineered shell thickness suppresses energy transfer and Auger recombination in order to maintain high luminescence efficiency, and the initial surface ligand is replaced with a shorter one for better charge injection. The optimized InP/ZnSe/ZnS QD-LEDs showed a theoretical maximum external quantum efficiency of 21.4 per cent, a maximum brightness of 100,000 candelas per square metre and an extremely long lifetime of a million hours at 100 candelas per square metre, representing a performance comparable to that of state-of-the-art Cd-containing QD-LEDs. These as-prepared InP-based QD-LEDs could soon be usable in commercial displays.

Nickel Oxide Hole Injection Layers for Balanced Charge Injection in Quantum Dot Light-Emitting Diodes.

Quantum dot (QD) light-emitting diodes (QLEDs) are promising for next-generation displays, but suffer from carrier imbalance arising from lower hole injection compared to electron injection. A defect engineering strategy is reported to tackle transport limitations in nickel oxide-based inorganic hole-injection layers (HILs) and find that hole injection is able to enhance in high-performance InP QLEDs using the newly designed material. Through optoelectronic simulations, how the electronic properties of NiOx affect hole injection efficiency into an InP QD layer, finding that efficient hole injection depends on lowering the hole injection barrier and enhancing the acceptor density of NiOx is explored. Li doping and oxygen enriching are identified as effective strategies to control intrinsic and extrinsic defects in NiOx, thereby increasing acceptor density, as evidenced by density functional theory calculations and experimental validation. With fine-tuned inorganic HIL, InP QLEDs exhibit a luminance of 45 200 cd m-2 and an external quantum efficiency of 19.9%, surpassing previous inorganic HIL-based QLEDs. This study provides a path to designing inorganic materials for more efficient and sustainable lighting and display technologies.

Revealing the Band-Edge Exciton Fine Structure of Single InP Nanocrystals.

We investigate the fundamental optical properties of single zinc-blende InP/ZnSe/ZnS nanocrystals (NCs) using frequency- and time-resolved magneto-photoluminescence spectroscopy. At liquid helium temperature, highly resolved spectral fingerprints are obtained and identified as the recombination lines of the three lowest states of the band-edge exciton fine structure. The evolutions of the photoluminescence spectra and decays under magnetic fields show evidence for a ground dark exciton level 0L with zero angular momentum projection along the NC main elongation axis. It lies 300 to 600 µeV below the ±1L bright exciton doublet, which is finely split by the NC shape anisotropy. These spectroscopic findings are well reproduced with a model of exciton fine structure accounting for shape anisotropy of the InP core. Our spectral fingerprints are extremely sensitive to the NC morphologies and unveil highly uniform shapes with prolate deviations of less than 3% from perfect sphericity.

Bifunctional Electron-Transporting Agent for Red Colloidal Quantum Dot Light-Emitting Diodes.

Indium phosphide (InP) quantum dots have enabled light-emitting diodes (LEDs) that are heavy-metal-free, narrow in emission linewidth, and physically flexible. However, ZnO/ZnMgO, the electron-transporting layer (ETL) in high-performance red InP/ZnSe/ZnS LEDs, suffers from high defect densities, quenches luminescence when deposited on InP, and induces performance degradation that arises due to trap migration from the ETL to the InP emitting layer. We posited that the formation of Zn2+ traps on the outer ZnS shell, combined with sulfur and oxygen vacancy migration between ZnO/ZnMgO and InP, may account for this issue. We synthesized therefore a bifunctional ETL (CNT2T, 3',3'″,3'″″-(1,3,5-triazine-2,4,6-triyl)tris(([1,1'-biphenyl]-3-carbonitrile)) designed to passivate Zn2+ traps locally and in situ and to prevent vacancy migration between layers: the backbone of the small molecule ETL contains a triazine electron-withdrawing unit to ensure sufficient electron mobility (6 × 10-4 cm2 V-1 s-1), and the star-shaped structure with multiple cyano groups provides effective passivation of the ZnS surface. We report as a result red InP LEDs having an EQE of 15% and a luminance of over 12,000 cd m-2; this represents a record among organic-ETL-based red InP LEDs.

Dipole Engineering through the Orientation of Interface Molecules for Efficient InP Quantum Dot Light-Emitting Diodes.

InP-based quantum dot (QD) light-emitting diodes (QLEDs) provide a heavy-metal-free route to size-tuned LEDs having high efficiency. The stability of QLEDs may be enhanced by replacing organic hole-injection layers (HILs) with inorganic layers. However, inorganic HILs reported to date suffer from inefficient hole injection, the result of their shallow work functions. Here, we investigate the tuning of the work function of nickel oxide (NiOx) HILs using self-assembled molecules (SAMs). Density functional theory simulations and near-edge X-ray absorption fine structure put a particular focus onto the molecular orientation of the SAMs in tuning the work function of the NiOx HIL. We find that orientation plays an even stronger role than does the underlying molecular dipole itself: SAMs having the strongest electron-withdrawing nitro group (NO2), despite having a high intrinsic dipole, show limited work function tuning, something we assign to their orientation parallel to the NiOx surface. We further find that the NO2 group─which delocalizes electrons over the molecule by resonance─induces a deep lowest unoccupied molecular orbital level that accepts electrons from QDs, producing luminescence quenching. In contrast, SAMs containing a trifluoromethyl group exhibit an angled orientation relative to the NiOx surface, better activating hole injection into the active layer without inducing luminescence quenching. We report an external quantum efficiency (EQE) of 18.8%─the highest EQE among inorganic HIL-based QLEDs (including Cd-based QDs)─in InP QLEDs employing inorganic HILs.

Tuning Hot Carrier Dynamics of InP/ZnSe/ZnS Quantum Dots by Shell Morphology Control.

Isotropic InP/ZnSe/ZnS quantum dots (QDs) are prepared at a high reaction temperature, which facilitates ZnSe shell growth on random facets of the InP core. Fast crystal growth enables stacking faults elimination, which induces anisotropic growth, and as a result, improves the photoluminescence (PL) quantum yield by nearly 20%. Herein, the effect of the QD morphology on photophysical properties is investigated by observing the PL blinking and ultrafast charge carrier dynamics. It is found that hot hole trapping is considerably suppressed in isotropic InP QDs, indicating that the stacking faults in the anisotropic InP/ZnSe structures act as defects for luminescence. These results highlight the importance of understanding the correlation between QD shapes and hot carrier dynamics, and present a way to design highly luminescent QDs for further promising display applications.

Negative Trion Auger Recombination in Highly Luminescent InP/ZnSe/ZnS Quantum Dots.

Upon demonstrating self-luminescing quantum dot based light-emitting devices (QD-LEDs), rapid Auger recombination acts as one of the performance limiting factors. Here, we report the Auger processes of highly luminescent InP/ZnSe/ZnS QDs with different midshell structures that affect the performances of QD-LEDs. Transient PL measurements reveal that exciton-exciton binding energy is dependent on the midshell thickness, which implies that the intercarrier Coulomb interaction caused by the introduction of excess charges may come under the influence of midshell thickness which is in contrast with the nearly stationary single exciton behavior. Photochemical electron-doping and optical measurements of a single QD show that negative trion Auger recombination exhibits strong correlation with midshell thickness, which is supported by the dynamics of a hot electron generated in the midshell. These results highlight the role of excess electrons and the effects of engineered shell structures in InP/ZnSe/ZnS QDs, which eventually determine the Auger recombination and QD-LED performances.

Electrochemical Charging Effect on the Optical Properties of InP/ZnSe/ZnS Quantum Dots.

Semiconductor quantum dots (QDs) are spotlighted as a key type of emissive material for the next generation of light-emitting diodes (LEDs). This work presents the investigation of the electrochemical charging effect on the absorption and emission of the InP/ZnSe/ZnS QDs with different mid-shell thicknesses. The excitonic peak is gradually bleached during electrochemical charging, which is caused by 1Se (or 1Sh ) state filling when the electron (or hole) is injected into the InP core. Additional charges also lead to photoluminescence (PL) intensity reduction, however, it is greatly mitigated as the mid-shell thickness increases. Various PL measurements reveal that the PL reduction under electrochemical charging is attributed to the acoustic phonon-assisted Auger recombination. Here, the Auger recombination in QDs with a thick mid-shell is reduced under the electrochemically charged condition, indicating that QDs with larger volume are more stable emitters in charge-injecting devices such as LEDs. Furthermore, the negative and positive trion Auger recombination rate constants are estimated, respectively, via electrochemical charging. The negative trion Auger rate constants decrease with an increase in the mid-shell thickness increases, whereas the positive trion Auger rate constants are not heavily reliant on the mid-shell thickness.

Crystallographic and Photophysical Analysis on Facet-Controlled Defect-Free Blue-Emitting Quantum Dots.

The burgeoning demand for commercializing self-luminescing quantum dot (QD) light-emitting diodes (LEDs) has stimulated extensive research into environmentally friendly and efficient QD materials. Hydrofluoric acid (HF) additive improves photoluminescence (PL) properties of blue-emitting ZnSeTe QDs, ultimately reaching a remarkable quantum yield (QY) of 97% with an ultranarrow peak width of 14 nm after sufficient HF addition. The improvement in optical properties of the QDs is accompanied by a morphology change of the particles, forming cubic-shaped defect-free ZnSeTe QDs characterized by a zinc blende (ZB) crystal structure. This treatment improves the QD-emitting properties by facilitating facet-specific growth, selectively exposing stabilized (100) facets, and reducing the lattice disorders. The facet-specific growth process gives rise to defect-free monodispersed cubic dots that exhibit remarkably narrow and homogeneous PL spectra. Meticulous time-resolved spectroscopic studies allow an understanding of the correlation between ZnSeTe QDs' particle shape and performance following HF addition. These investigations shed light on the intricacies of the growth mechanism and the factors influencing the PL efficiency of the resulting QDs. The findings significantly contribute to understanding the role of HF treatment in tailoring the optical properties of ZnSeTe QDs, thereby bringing it closer to the realization of highly efficient and bright QD-LEDs for various practical applications.

Narrow Intrinsic Line Widths and Electron-Phonon Coupling of InP Colloidal Quantum Dots.

InP quantum dots (QDs) are the material of choice for QD display applications and have been used as active layers in QD light-emitting diodes (QDLEDs) with high efficiency and color purity. Optimizing the color purity of QDs requires understanding mechanisms of spectral broadening. While ensemble-level broadening can be minimized by synthetic tuning to yield monodisperse QD sizes, single QD line widths are broadened by exciton-phonon scattering and fine-structure splitting. Here, using photon-correlation Fourier spectroscopy, we extract average single QD line widths of 50 meV at 293 K for red-emitting InP/ZnSe/ZnS QDs, among the narrowest for colloidal QDs. We measure InP/ZnSe/ZnS single QD emission line shapes at temperatures between 4 and 293 K and model the spectra using a modified independent boson model. We find that inelastic acoustic phonon scattering and fine-structure splitting are the most prominent broadening mechanisms at low temperatures, whereas pure dephasing from elastic acoustic phonon scattering is the primary broadening mechanism at elevated temperatures, and optical phonon scattering contributes minimally across all temperatures. Conversely for CdSe/CdS/ZnS QDs, we find that optical phonon scattering is a larger contributor to the line shape at elevated temperatures, leading to intrinsically broader single-dot line widths than for InP/ZnSe/ZnS. We are able to reconcile narrow low-temperature line widths and broad room-temperature line widths within a self-consistent model that enables parametrization of line width broadening, for different material classes. This can be used for the rational design of more spectrally narrow materials. Our findings reveal that red-emitting InP/ZnSe/ZnS QDs have intrinsically narrower line widths than typically synthesized CdSe QDs, suggesting that these materials could be used to realize QDLEDs with high color purity.

Cu2O and Au/Cu2O particles: surface properties and applications in glucose sensing.

In this work we investigated the surface and facet-dependent catalytic properties of metal oxide particles as well as noble metal/metal oxide heterogeneous structures, with cuprous oxide (Cu(2)O) and Au/Cu(2)O being selected as model systems. As an example of application, we explored the potential of these materials in developing electrocatalytic devices. Cu(2)O particles were synthesized in various shapes, then used for testing their morphology-dependent electrochemical properties applied to the detection of glucose. While we did not attempt to obtain the best detection limit reported to date, the octahedral and hexapod Cu(2)O particles showed reasonable detection limits of 0.51 and 0.60 mM, respectively, which are physiologically relevant concentrations. However, detection limit seems to be less affected by particle shapes than sensitivity. Heterogeneous systems where Au NPs were deposited on the surface of Cu(2)O particles were also tested with similar results in terms of the effect of surface orientation.

Natural biopolymers: novel templates for the synthesis of nanostructures.

Biological systems such as proteins, viruses, and DNA have been most often reported to be used as templates for the synthesis of functional nanomaterials, but the properties of widely available biopolymers, such as cellulose, have been much less exploited for this purpose. Here, we report for the first time that cellulose nanocrystals (CNC) have the capacity to assist in the synthesis of metallic nanoparticle chains. A cationic surfactant, cetyltrimethylammonium bromide (CTAB), was critical to nanoparticle stabilization and CNC surface modification. Silver, gold, copper, and platinum nanoparticles were synthesized on CNCs, and the nanoparticle density and particle size were controlled by varying the concentration of CTAB, the pH of the salt solution, and the reduction time.

Biomagnetic glasses: preparation, characterization, and biosensor applications.

In this work, a novel avenue to create a generic approach for the fabrication of biofunctional materials with magnetic capabilities to be used in the design of highly stable, magnetically separable enzyme-based systems was explored. As a model system, immobilization of acetylcholinesterase (AChE) was investigated using biomagnetic glasses composed of a magnetic core with a size tunable porous silica shell. The efficiency of the immobilization was determined by analyzing the biosensing capability of these biomagnetic glasses for the detection of the organophosphorous pesticide paraoxon. Screen printed electrodes with the AChE-biomagnetic glasses showed higher current response and stability than for the free enzyme. The detection limit of the paraoxon biosensor was in the nanomolar range.

Magnetic particle-based hybrid platforms for bioanalytical sensors.

Biomagnetic nano and microparticles platforms have attracted considerable interest in the field of biological sensors due to their interesting physico-chemical properties, high specific surface area, good mechanical stability and opportunities for generating magneto-switchable devices. This review discusses recent advances in the development and characterization of active biomagnetic nanoassemblies, their interaction with biological molecules and their use in bioanalytical sensors.

A Strategy to enhance Eu3+ emission from LiYF4:Eu nanophosphors and green-to-orange multicolor tunable, transparent nanophosphor-polymer composites.

LiYF4:Eu nanophosphors with a single tetragonal phase are synthesized, and various strategies to enhance the Eu(3+) emission from the nanophosphors are investigated. The optimized Eu(3+) concentration is 35 mol%, and the red emission peaks due to the (5)D0 →(7)FJ (J = 1 and 2) transitions of Eu(3+) ions are further enhanced by energy transfer from a sensitizer pair of Ce(3+) and Tb(3+). The triple doping of Ce, Tb, and Eu into the LiYF4 host more effectively enhances the Eu(3+) emission than the core/shell strategies of LiYF4:Eu(35%)/LiYF4:Ce(15%), Tb(15%) and LiYF4:Ce(15%), Tb(15%)/LiYF4:Eu(35%) architectures. Efficient energy transfer from Ce(3+) to Eu(3+) through Tb(3+) results in three times higher Eu(3+) emission intensity from LiYF4:Ce(15%), Tb(15%), Eu(1%) nanophosphors compared with LiYF4:Eu(35%), which contains the optimized Eu(3+) concentration. Owing to the energy transfer of Ce(3+) → Tb(3+) and Ce(3+) → Tb(3+) → Eu(3+), intense green and red emission peaks are observed from LiYF4:Ce(13%), Tb(14%), Eu(1-5%) (LiYF4:Ce, Tb, Eu) nanophosphors, and the intensity ratio of green to red emission is controlled by adjusting the Eu(3+) concentration. With increasing Eu(3+) concentration, the LiYF4:Ce, Tb, Eu nanophosphors exhibit multicolor emission from green to orange. In addition, the successful incorporation of LiYF4:Ce, Tb, Eu nanophosphors into polydimethylsiloxane (PDMS) facilitates the preparation of highly transparent nanophosphor-PDMS composites that present excellent multicolor tunability.

Au nanospheres and nanorods for enzyme-free electrochemical biosensor applications.

Au nanocrystals with different morphologies were prepared and used for enzyme-free electrochemical biosensor applications. To investigate the electrocatalytic properties of Au nanocrystals as a function on their morphologies, Au nanocrystals, Au nanospheres (NSs) on silica, Au NSs, and Au nanorods (NRs) with aspect ratios of 1:3 and 1:5, were coated on the screen printed electrodes and further measure the amperometric responses to hydrogen peroxide via three-electrode system. The electrodes modified with Au nanocrystals showed biosensing properties without any enzyme being attached or immobilized at their surface. The hydrogen peroxide detection limits of the biosensors with Au NSs, Au NRs (1:3), and Au NRs (1:5) were 6.48, 8.65, and 9.38 µM (S/N = 3), respectively. The biosensors with Au NSs, Au NRs (1:3), and Au NRs (1:5) showed the sensitivities of 11.13, 54.53, and 58.51 µA/mM, respectively. These results indicate that morphologies of Au nanocrystals significantly influence the sensitivity of the biosensors. In addition, the enzyme-free biosensors with Au nanocrystals were stable for 2 months. Au nanocrystal-based enzyme-free system, which is proposed in this study, can be used as a platform for various electrochemical biosensors.

Enzyme functionalized nanoparticles for electrochemical biosensors: a comparative study with applications for the detection of bisphenol A.

We developed electrochemical biosensors based on enzyme functionalized nanoparticles of different compositions for the detection of bisphenol A. We utilized for the first time magnetic nickel nanoparticles as an enzyme immobilization platform and electrode material to construct screen-printing enzyme biosensors for bisphenol A. We compared the analytical performance of these sensors with those based on iron oxide (Fe(3)O(4)) and gold nanoparticles. The proposed biosensor format exhibited fast and sensitive amperometric responses to bisphenol A with a response time of less then 30s. Among the three configurations, nickel provided comparable or better characteristics in terms of detection limit and sensitivity than Fe(3)O(4) and gold nanoparticles. The biosensors were characterized by good reproducibility, stability of more than 100 assays (residual activity for nickel was 98%) and a wide linear range which spanned from 9.1 × 10(-7) to 4.8 × 10(-5)M for nickel, 2.2 × 10(-8) to 4.0 × 10(-5)M for Fe(3)O(4) and 4.2 × 10(-8) to 3.6 × 10(-5)M for gold. The highest sensitivity was obtained with nickel. The detection limits for the three types of biosensors were: 7.1 × 10(-9), 8.3 × 10(-9) and 1 × 10(-8)M for nickel, Fe(3)O(4) and gold nanoparticles in that order, respectively. These results demonstrate that nickel nanoparticles can be successfully used in the construction of electrochemical enzyme sensors for the detection of phenolic compounds.

Effect of phosphor geometry on the luminous efficiency of high-power white light-emitting diodes with excellent color rendering property.

High-power white light-emitting diodes (LEDs) are fabricated by combining blue LEDs and green (Ba,Sr)(2)SiO(4):Eu(2+) and red CaAlSiN(3):Eu(2+) phosphors with varying phosphor geometry. The white LED having separated the phosphor layer by the silicone gel layer between green and red phosphor layers shows superior optical properties. The luminous efficiency (eta(L)) is improved by a decrease of reabsorption of green light by red phosphor owing to a difference among refractive indices. The white LED shows very high eta(L) of 51 lm/W and a high color rendering index of 95 under 350 mA. In addition, improved luminous properties of the white LED including a separated phosphor layer are confirmed via ray-trace simulation.

Origin of the discrepancy between photoluminescence brightness of TAG:Ce and electroluminescence brightness of TAG:Ce-based white LED expected from phosphor brightness.

A yellow-emitting Tb(3)Al(5)O(12):Ce(3+) (TAG:Ce) phosphor was coated on blue light-emitting diodes (LEDs) to obtain white LEDs (WLEDs). Since TAG:Ce showed 90% of the brightness of Y(3)Al(5)O(12):Ce(3+) (YAG:Ce), it was expected that TAG:Ce-based WLEDs showed 90% of brightness of YAG:Ce-based ones. However, the TAG:Ce-based WLED showed 74% of the brightness of YAG:Ce-based one. Considering the density and size of the phosphors, the higher density and larger size of TAG:Ce induced a great deal of sedimentation of TAG:Ce particles in an epoxy resin. It is believed that this is one of main reasons for the reduced optical power of the TAG:Ce-based WLED compared to that of the WLED expected from the brightness of TAG:Ce.