Improving Charge Injection via a Blade-Coating Molybdenum Oxide Layer: Toward High-Performance Large-Area Quantum-Dot Light-Emitting Diodes.

A solution-processed molybdenum oxide (MoO x) as the hole injection layer (HIL) by doctor-blade coating was developed to improve the efficiency and lifetime of red-emitting quantum-dot light-emitting diodes (QD-LEDs). It has been demonstrated that by adding isopropyl alcohol into the MoO x precursor during the doctor-blade coating process, the morphology, composition, and the surface electronic structure of the MoO x HIL could be tailored. A high-quality MoO x film with optimized charge injection was obtained, based on which all-solution-processed highly efficient red-emitting QD-LEDs were realized by using a low-cost doctor-blade coating technique under ambient conditions. The red QD-LEDs exhibited the maximum current efficiency and external quantum efficiency of 16 cd/A and 15.1%, respectively. Moreover, the lifetime of red devices initializing at 100 cd/m2 was 3236 h under ambient conditions, which is about twice as long as those with a conventional poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) HIL. Large-area QD-LEDs with 4 in. emitting areas were fabricated with blade coating as well, which exhibit a high efficiency of 12.1 cd/A for red emissions. Our work paves a new way to the realization of efficient large-area QD-LEDs, and the processing and findings from this work can be expanded into next-generation lighting and flat-panel displays.

High efficiency quantum dot light emitting diodes from positive aging.

Colloidal quantum dot-polymer hybrid light emitting diodes (QLEDs) that exhibit external quantum efficiencies >12% for all three primary colors (21% from green) have been demonstrated. These high efficiencies result in part from a positive aging effect reported here for the first time, where positive aging means the efficiency of the QLED increased with time. We have achieved 470 h operational life time (T90) at 2550 nits for red QLEDs. At longer times, negative aging phenomena lead to lower luminance and limit the lifetime of the QLEDs. It is concluded that we have reasonable control over the efficiency of QLEDs. The next challenge is to achieve lifetimes sufficiently long for all three primary colors for applications such as in television and illumination.

Effects of ambient temperature and water vapor on chamber pressure and oxygen level during low atmospheric pressure stunning of poultry.

The characteristics of the vacuum used in a low atmospheric pressure stunning system to stun (render unconscious) poultry prior to slaughter are described. A vacuum chamber is pumped by a wet screw compressor. The vacuum pressure is reduced from ambient atmospheric pressure to an absolute vacuum pressure of ∼250 Torr (∼33 kPa) in ∼67 sec with the vacuum gate valve fully open. At ∼250 Torr, the sliding gate valve is partially closed to reduce effective pumping speed, resulting in a slower rate of decreasing pressure. Ambient temperature affects air density and water vapor pressure and thereby oxygen levels and the time at the minimum total pressure of ∼160 Torr (∼21 kPa) is varied from ∼120 to ∼220 sec to ensure an effective stun within the 280 seconds of each cycle. The reduction in total pressure results in a gradual reduction of oxygen partial pressure that was measured by a solid-state electrochemical oxygen sensor. The reduced oxygen pressure leads to hypoxia, which is recognized as a humane method of stunning poultry. The system maintains an oxygen concentration of <5% for at least 2 minutes, which ensures that birds are irreversibly stunned. Calculated pump down (pressure versus time) data match experimental data very closely because the programmable logic controller and the human machine interface enable precise and accurate control. The vacuum system operates in the turbulent viscous flow regime, and is best characterized by absolute vacuum pressure rather than gauge pressure. Neither the presence of broiler chickens nor different fore-line pipe designs of four parallel commercial systems affected the pressure-time data. Water in wet air always reduces the oxygen concentrations to a value lower than in dry air. The partial pressure of water and oxygen were found to depend on the pump down parameters due to the formation of fog in the chamber and desorption of water from the birds and the walls of the vacuum chamber.

Enhancing the efficiency of solution-processed polymer:colloidal nanocrystal hybrid photovoltaic cells using ethanedithiol treatment.

Advances in colloidal inorganic nanocrystal synthesis and processing have led to the demonstration of organic-inorganic hybrid photovoltaic (PV) cells using low-cost solution processes from blends of conjugated polymer and colloidal nanocrystals. However, the performance of such hybrid PV cells has been limited due to the lack of control at the complex interfaces between the organic and inorganic hybrid active materials. Here we show that the efficiency of hybrid PV devices can be significantly enhanced by engineering the polymer-nanocrystal interface with proper chemical treatment. Using two different conjugated polymers, poly(3-hexylthiophene) (P3HT) and poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT), we show that treating the polymer:nanocrystal hybrid film in an ethanedithiol-containing acetonitrile solution can increase the efficiency of the hybrid PV devices by 30-90%, and a maximum power conversion efficiency of 5.2 ± 0.3% was obtained in the PCPDTBT:CdSe devices at 0.2 sun (AM 1.5G), which was slightly reduced to 4.7 ± 0.3% at 1 sun. The ethanedithiol treatment did not result in significant changes in the morphology and UV-vis optical absorption of the hybrid thin films; however, infrared absorption, NMR, and X-ray photoelectron spectroscopies revealed the effective removal of organic ligands, especially the charged phosphonic acid ligands, from the CdSe nanorod surface after the treatment, accompanied by the possible monolayer passivation of nanorod surfaces with Cd-thiolates. We attribute the hybrid PV cell efficiency increase upon the ethanedithiol treatment to the reduction in charge and exciton recombination sites on the nanocrystal surface and the simultaneous increase in electron transport through the hybrid film.

Solution-processed, nanostructured hybrid solar cells with broad spectral sensitivity and stability.

Hybrid organic-inorganic solar cells, as an alternative to all-organic solar cells, have received significant attention for their potential advantages in combining the solution-processability and versatility of organic materials with high charge mobility and environmental stability of inorganic semiconductors. Here we report efficient and air-stable hybrid organic-inorganic solar cells with broad spectral sensitivity based on a low-gap polymer poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) and spherical CdSe nanoparticles. The solvents used for depositing the hybrid PCPDTBT:CdSe active layer were shown to strongly influence the film morphology, and subsequently the photovoltaic performance of the resulted solar cells. Appropriate post-deposition annealing of the hybrid film was also shown to improve the solar cell efficiency. The inclusion of a thin ZnO nanoparticle layer between the active layer and the metal cathode leads to a significant increase in device efficiency especially at long wavelengths, due to a combination of optical and electronic effects including more optimal light absorption in the active layer and elimination of unwanted hole leakage into the cathode. Overall, maximum power conversion efficiencies up to 3.7 ± 0.2% and spectral sensitivity extending above 800 nm were achieved in such PCPDTBT:CdSe nanosphere hybrid solar cells. Furthermore, the devices with a ZnO nanoparticle layer retained ∼70% of the original efficiency after storage under ambient laboratory conditions for over 60 days without any encapsulation.

Three-dimensional self-assembled hierarchical architectures of gamma-phase flowerlike bismuth oxide.

Three-dimensional (3D) self-assembled hierarchical bismuth oxide architectures were prepared via a solution precipitation synthesis at 85 degrees C in 45 min with the aid of polyethylene glycol-8000 (PEG-8000) as a capping agent. The morphology and crystalline phase evolution was studied versus reaction time and capping agent concentration and interpreted in terms of growth mechanisms. At higher capping agent concentrations, the as-grown 3D hierarchical flowerlike bismuth oxide was crystalline cubic gamma-phase that was previously formed only at temperature > or =640 degrees C. The morphology and crystal structure of these 3D cubic gamma-phase bismuth oxide flowers were not changed with calcining up to 600 degrees C. Photoluminescence was attributed to emission from the Bi(3+) ion by a (3)P(0),(1) --> (1)S(0) transition and from defects. The gamma-phase flowerlike bismuth oxide shows better ion conductivity than that of rodlike bismuth oxide formed without the capping agent. The flowerlike morphology was attributed to modification of the nucleation and growth kinetics by the capping agent.

Controlled shape growth of Eu- or Tb-doped luminescent Gd2O3 colloidal nanocrystals.

Controlled-shape synthesis of rare earth doped gadolinium oxide (Gd(2)O(3):Eu(3+) or Tb(3+)) colloidal nanocrystals by non-hydrolytic high temperature (approximately 290 degrees C) solution growth methods is reported. Various shapes of Gd(2)O(3) nanocrystals were synthesized, including spheres, plates, and curved rods. The nanocrystal shape was shown to be dependent on the synthesis parameters, such as type of metal precursor and surfactant, and their concentration ratio. The photoluminescence intensity from rare earth doped Gd(2)O(3) was shown to increase from nanoplates to nanospheres, which is discussed in terms of doping efficiency, crystal structure, and ratio of surface to volume.

Temporal evolution of white light emission from CdSe quantum dots.

A study of white light emission from magic sized CdSe quantum dots is reported. Quantum dots were synthesized using a hot solution method and exhibited strong white light with a quantum yield in the range of 10-30%. The emission of white light was attributed to photoluminescence (PL) from both excitons and surface states. The wavelength and intensity of the PL from both excitons and surface states were found to depend upon the particle size, reaction time, reaction temperature and precursor ratio.

White light emission from single layer poly (n-vinylcarbazole) polymeric light-emitting devices by mixing singlet and triplet excimer emissions.

White light electroluminescence (EL) was obtained by mixing emission from singlet and triplet excimers from a single poly (n-vinylcarbazole) (PVK) spin cast layer after irradiation of the solution with UV light. With increased UV light irradiation, the intensity from the triplet excimer (red-630 nm) of PVK increased compared with that of the singlet excimer (blue-460 nm) due to an increased population of both adjacent benzene rings being aligned with one another (fully overlapping) versus only one of the adjacent benzene rings being aligned (partially overlapping). The emission color changed from blue to white with increased UV irradiation time while the EL brightness and current density decreased and the turn-on voltage increased.

Synthesis and characterization of colloidal ternary ZnCdSe semiconductor nanorods.

For the synthesis of colloidal ternary ZnCdSe nanorods, CdSe nanorods were first prepared under a mixture of tetradecylphosphonic acid/trioctylphosphine oxide surfactants at 250 degrees C, and then ZnSe shell layer was grown onto CdSe nanorods at 180 degrees C, forming CdSeZnSe core/shell nanorods. Green-yellow emitting ternary ZnCdSe nanorods were obtained by a subsequent alloying process at 270 degrees C for 1-3 h through the diffusion of Zn ions into CdSe nanorods. The photoluminescence quantum yield (QY) of ZnCdSe nanorods was 5%-10%, which is higher than that from pristine CdSe nanorods (0.6%). The QY of these alloy nanorods depends on the alloying time and is discussed in terms of compositional disorders and defects produced by the alloying process. The Raman and time resolved photoluminescence spectroscopies were used to understand the detailed alloying process from CdSeZnSe core/shell to ZnCdSe alloy nanorods.

Enhanced and stable green emission of ZnO nanoparticles by surface segregation of Mg.

The effects of Mg addition on the emission of green photons from ZnO nanoparticles were studied. Energy dispersive x-ray spectroscopy (EDS) and Auger electron spectroscopy (AES) data demonstrated that ZnO nanoparticles with surface segregation of MgO (ZnO:MgO) were precipitated from colloidal reactions between Zn(2+),Mg(2+) and OH(-) ions suspended in ethanol. The photoluminescence emission spectra showed stronger green emission from suspended ZnO:MgO versus ZnO nanoparticles. ZnO:MgO also exhibited a stable green emission colour, which was slightly red-shifted from 495 to 520 nm with 168 days of ageing. It was postulated that the presence of MgO on the surface of ZnO prevented both the aggregation of ZnO nanoparticles via electrostatic stabilization of the suspension, and the formation of non-radiative recombination states on the surface, resulting in more intense, stable photoemission from ZnO. The red shift of the green emission from suspended ZnO nanoparticles with extended ageing was attributed to filling of radiative surface trap states in the bandgap.

Syntheses and applications of Mn-doped II-VI semiconductor nanocrystals.

Luminescent Mn-doped II-VI semiconductor nanocrystals have been intensively investigated over the last ten years. Several semiconductor host materials such as ZnS, CdS, and ZnSe have been used for Mn-doped nanocrystals with different synthetic routes and surface passivation. Beyond studies of their fundamental properties including photoluminescence and size, these luminescent nanocrystals have now been tested for practical applications such as electroluminescent displays and biological labeling agents (biomarkers). Here, we first review ZnS:Mn, CdS:Mn/ZnS core/shell, and ZnSe:Mn nanocrystal systems in terms of their synthetic chemistries and photoluminescent properties. Second, based on ZnS:Mn and CdS:Mn/ZnS core/shell nanocrystals as electroluminescent components, direct current electroluminescent devices having a hybrid organic/inorganic multilayer structure are reviewed. Highly luminescent and photostable CdS:Mn/ZnS nanocrystals can further be used as the luminescent biomarkers and some preliminary results are also discussed here.

Enhanced luminescence of SiO2:Eu3+ by energy transfer from ZnO nanoparticles.

ZnO nanoparticles embedded into SiO(2) by an ex situ method were shown to result in stable green emission with a peak at 510 nm compared to the normal peak at 495 nm from micron-sized ZnO powders. Green emission from ZnO nanoparticles was completely suppressed when they were embedded in SiO2 doped with Eu3+. Instead, the f-f emissions from Eu3+ were enhanced 5-10 times by energy transfer from the embedded ZnO nanoparticles to Eu3+. The Eu3+ luminescence increased as the Eu3+ concentration increased from 1 vs 5 mole % (for 10 mole % ZnO). In addition, the intensity increased as the embedded ZnO nanoparticles concentration increased up to 10 mole % (for 5 mole % Eu3+). The effects of phonon mediated energy transfer, quenching by activator interactions between Eu3+ ions, and energy back-transfer from Eu3+ ions to ZnO nanoparticles were discussed.

Rapid and effective labeling of brain tissue using TAT-conjugated CdS:Mn/ZnS quantum dots.

TAT (a cell penetrating peptide)-conjugated CdSratioMn/ZnS quantum dots (Qdots), intra-arterially delivered to a rat brain, rapidly (within a few minutes) labeled the brain tissue without manipulating the blood-brain-barrier (BBB). Qdot loading was sufficiently high that it allowed a gross fluorescent visualization of the whole rat brain using a low power hand-held UV lamp. Histological data clearly showed that TAT-conjugated Qdots migrated beyond the endothelial cell line and reached the brain parenchyma. Qdots without TAT did not label the brain tissue confirming the fact that TAT peptide was necessary to overcome the BBB. The present study clearly demonstrated the possibility of delivering a large amount of Qdot-based imaging agents to the brain tissue.

Synthesis of water-dispersible fluorescent, radio-opaque, and paramagnetic CdS:Mn/ZnS quantum dots: a multifunctional probe for bioimaging.

Ultra-small (3.1 nm) multifunctional CdS:Mn/ZnS core-shell semiconductor quantum dots (Qdots), which possess fluorescent, radio-opacity, and paramagnetic properties, have been shown here. To demonstrate in vivo bioimaging capability, a rat was administered endovascularly with Qdots conjugated with a TAT peptide. The labeling efficacy of these Qdots was demonstrated on the basis of the histological analysis of the microtome sliced brain tissue, clearly showing that TAT-conjugated Qdots stained brain blood vessels.

TAT conjugated, FITC doped silica nanoparticles for bioimaging applications.

Water-in-oil (w/o) microemulsion synthesis of 70 nm size monodisperse TAT (a cell penetrating peptide, CPP) conjugated, FITC (fluorescein isothiocyanate) doped silica nanoparticles (TAT-FSNPs) is reported; human lung adenocarcinoma (A549) cells (in vitro) and rat brain tissue (in vivo) were successfully labeled using TAT-FSNPs.

CdS:Mn nanocrystals passivated by ZnS: synthesis and luminescent properties.

Synthesis and characterization of highly luminescent ZnS-passivated CdS:Mn (CdS:Mn/ZnS) core/shell structured nanocrystals are reported. Mn-doped CdS core nanocrystals are produced ranging from 1.5 to 2.3 nm in diameter with epitaxial ZnS shell of wider band gap via a reverse micelle process. UV irradiation-stimulated photo-oxidation of the ZnS shell results in formation of sulfate (ZnSO(4)) as determined by x-ray photoelectron spectroscopy, which increases the photoluminescence emission intensity and subsequent photostability. Luminescent relaxation lifetime data present two different decay components, consisting of slow decay emission from the Mn center and a fast decay emission from a defect-related center. The impact of the density of surface defect states upon the emission spectra is discussed.

Water-soluble silica-overcoated CdS:Mn/ZnS semiconductor quantum dots.

Highly luminescent and photostable CdS:Mn/ZnS core/shell quantum dots are not water soluble because of their hydrophobicity. To create water-soluble quantum dots by an appropriate surface functionalization, CdS:Mn/ZnS quantum dots synthesized in a water-in-oil (W/O) microemulsion system (reverse micelles) were consecutively overcoated with a very thin silica layer ( approximately 2.5 nm thick) within the same reverse micellar system. The water droplet serves as a nanosized reactor for the controlled hydrolysis and condensation of a silica precursor, tetraethyl orthosilicate (TEOS), using an ammonium hydroxide (NH4OH) catalyst. Structural characterizations with transmission electron microscopy (TEM) and x-ray photoelectron spectroscopy (XPS) indicate that the silica-quantum dot nanocomposites consist of a layered structure. Owing to the amorphous, porous nature of a silica layer, the optical and photophysical properties of silica-overcoated CdS:Mn/ZnS quantum dots are found to remain close to those of uncoated counterparts.