Improved green thermal activated delayed fluorescence OLEDs based on thermally evaporated distributed Bragg reflector (DBR) of MgF2/ZnS.

Unlike the traditional fabrication of distributed Bragg reflector (DBR) structure via atomic layer deposition or spin-coating, here the 1-6 pairs of magnesium fluoride (MgF2)/zinc sulfide (ZnS) alternative dielectric layers were grown via thermal evaporation. The absorption, transmission, reflection, and photoluminescence (PL) spectra were evaluated. 5 pair MgF2/ZnS denotes the largest reflectance (88.5% at 535 nm) together with a stopband at 450-650 nm among the 1- 6 pair dielectric layers, exhibiting the potential for using as DBR. Relative to the bare 4,4'-bis(carbazol-9-yl)biphenyl(CBP):(4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl) isophthalonitrile (4CzIPN) film, the PL intensity of CBP:4CzIPN/5 pair MgF2/ZnS DBR is enhanced and splitted into two peaks. The 5 pair alternative dielectric film presents more uniform aggregation over 4 pair MgF2/ZnS. The cross-sectional scanning electron microscopic image denotes explicit layering for the MgF2and ZnS. The organic light-emitting diode (OLED) incorporating 5 pair MgF2/ZnS DBR layers illustrates significantly improved electroluminescent (EL) performance due to the photons concentrated in the direction perpendicular to the DBR. The slightly narrowed EL spectrum is originated from the microcavity effect between the two Al electrodes. Here we develop a universal method for the DBR fabrication suitable to most of OLEDs.

Magnetic Testis Targeting and Magnetic Hyperthermia for Noninvasive, Controllable Male Contraception via Intravenous Administration.

Mild testicular hyperthermia by the photothermal effect of gold nanorods could realize controllable male contraception. However, associated limitations, such as testicular administration and infrared laser inflicting severe pain, and the nondegradability of nanoparticles potentially causing toxicity, have restricted further clinical application. Inspired by the excellent physicochemical properties of iron oxide nanoparticles (IONPs), and the finding that testicular injection of PEG-coated IONPs with a diameter of 50 nm (PEG@Fe3O4-50) following an alternating magnetic field (AMF) could achieve controllable male contraception; here we propose a noninvasive, targeting approach for male contraception via intravenous administration. The magnetic properties and testes targeting of IONPs were proven to be greatly affected by their surface chemistry and particle size. After systemic administration, citric acid stabilized IONPs with size of 100 nm (CA@Fe3O4-100) were found to be the best ideal thermoagent for realizing the noninvasive contraception. This study offers new strategies for male contraception.

Improved stability of blue TADF organic electroluminescent diodes via OXD-7 based mixed host.

Thermally activated delayed fluorescence (TADF) organic light-emitting diodes (OLEDs) have been demonstrated in applications such as displays and solid-state lightings. However, weak stability and inefficient emission of blue TADF OLEDs are two key bottlenecks limiting the development of solution processable displays and white light sources. This work presents a solution-processed OLED using a blue-emitting TADF small molecule bis[4-(9,9-dimethyl-9,10-dihydroacridine) phenyl]sulfone (DMAC-DPS) as an emitter. We comparatively investigated the effects of single host poly(N-vinylcarbazole) (PVK) and a co-host of 60% PVK and 30% 2,2'-(1,3-phenylene)-bis[5-(4-tert-butylphenyl)-1,3,4-oxadiazole] (OXD-7) on the device performance (the last 10% is emitter DMAC-DPS). The co-host device shows lower turn-on voltage, similar maximum luminance, and much slower external quantum efficiency (EQE) rolloff. In other words, device stability improved by doping OXD-7 into PVK, and the device impedance simultaneously and significantly reduced from 8.6 × 103 to 4.2 × 103 Ω at 1000 Hz. Finally, the electroluminescent stability of the co-host device was significantly enhanced by adjusting the annealing temperature.

Control of the pore size of honeycomb polymer film from micrometers to nanometers via substrate-temperature regulation and its application to photovoltaic and heat-resistant polymer films.

Honeycomb porous polystyrene (PS) films with an aspect ratio of pore depth to pore diameter at approximately 1.0 were fabricated using the breath figure (BF) method. Two modes of water droplet coalescence in the pore growth were observed in real-time by optical microscopy. Pore size significantly increases with the increase in humidity and the decrease in substrate temperature. The porous pattern could emerge even at room temperature under high humidity of 80%. Boiling point and solvent density significantly influence the pore distribution and pore depth. Chloroform and tetrahydrofuran achieve more uniform hexagonal patterns than benzene and dichloromethane. Subsequently, to obtain nanometer porous PS film, the fast-evaporation BF process was designed by regulating the gradient substrate temperature and evaporation time, and porous mesoscopic PS film was obtained. The minimum pore diameter and corresponding pore depth are about 120 nm and 27 nm, respectively. Finally, the fast-evaporation BF process was applied to the honeycomb film formation of photovoltaic polymer poly(3-hexylthiophene) (P3HT), and the heat-resistant polymers polysulfone (PSF) and polyimide (PI).

Polymorphous Luminescent Materials Based on 'T'-Shaped Molecules Bearing 4,7-Diphenylbenzo[c][1,2,5]thiadiazole Skeletons: Effect of Substituents on the Photophysical Properties.

Polymorphism, the intrinsic character of one chemical compound with at least two distinct phase arrangements, plays a very key role in the photophysical properties. In this contribution, four 'T'-shaped molecules bearing the 2,1,3-benzothiadiazole (BTD) skeleton, named 5 a-5 d, were prepared and characterized. All compounds exhibited excellent thermal stability and polymorphism in the solid state, evident from thermogravimetric analysis, differential scanning calorimetry, and polarized optical microscopy results. Intense emissions with high photoluminescent quantum yields were achieved both in solution (56-97 %) and neat films (33-98 %). All compounds possessed clearly pH-dependent luminescence properties in solution. Additionally, compound 5 d showed useful mechanochromic luminescence owing to the transformation between the crystal and amorphous state. Employing compounds 5 a-5 d as the dopant, solution-processable organic light-emitting diodes (OLEDs) were fabricated and presented a highest external quantum efficiency of 6.15 %, which is higher than the theoretical value of fluorescence-based OLEDs (∼5 %). This research provided a novel strategy for designing high-efficiency BTD-based polymorphic luminescent materials.

Low energy consumption phosphorescent organic light-emitting diodes using phenyl anthracenone derivatives as the host featuring bipolar and thermally activated delayed fluorescence.

A novel host material featuring the characteristics of bipolarity and thermally activated delayed fluorescence, 10-(4-(5,5-dimethylbenzofuro[3,2-c]acridin-13(5H)-yl)phenyl)-10-phenylanthracen-9(10H)-one (DphAn-5BzAc), has been designed and synthesized. By employing this material as the host of green emitter Ir(ppy)2acac, we have fabricated phosphorescent organic light-emitting diodes (PhOLEDs) with two hosting schemes, which are the single host system consisting of DhAn-5BzAc and the co-host system with 1,3-bis(carbazolyl)benzene (mCP). We found that the co-host based PhOLED achieved very low energy consumption values at high brightnesses, which were only 0.5, 5.9 and 94.0 mW m-2 at 100, 1000 and 10 000 cd m-2, respectively. The extremely low energy consumption for DhAn-based PhOLEDs were attributed to the excellent bipolar transport properties and thermally activated delayed fluorescence characteristics.

Highly efficient green TADF organic light-emitting diodes by simultaneously manipulating hole and electron transport.

This work demonstrates effective performance improvement by simultaneous manipulating of the hole injection and electron transport layers for (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile (4CzIPN) based green thermally activated delayed fluorescent (TADF) organic light-emitting diodes (OLEDs). A 3 wt% sorbitol doped PEDOT:PSS layer results in the highest maximum current efficiency (CEmax) of 28.28 cd A-1 and external quantum efficiency (EQE) of 17.04%. Single carrier devices denote that hole mobility gradually rises with the sorbitol ratio. The electroluminescence mainly originates from the emission of 4CzIPN. Atomic force microscopy images imply that 3 wt% sorbitol doped PEDOT:PSS film includes the largest PEDOT aggregate, which contributes to a higher electric conductivity thus the better performance of 3 wt% sorbitol doped device. Also the 4CzIPN ratio in the emissive layer was optimized, and 4 wt%-4CzIPN in CBP achieves the highest EQE of 20.99% and CEmax of 34.99 cd A-1. The EL spectrum is independent of the luminous angle at a low 4CzIPN ratio but becomes more sensitive to the luminous angle at a high 4CzIPN ratio. Finally, we find out that the TADF OLED performance is very sensitive to TPBi thickness ranging from 20 nm to 65 nm, and 40 nm of TPBi achieves a CEmax up to 64.10 cd A-1 and an excellent EQE of 25.14%, ascribing from its more balanced carrier transport.

Properties-Adjustable Alumina-Zirconia Nanolaminate Dielectric Fabricated by Spin-Coating.

In this paper, an alumina-zirconia (Al2O3-ZrO2) nanolaminate dielectric was fabricated by spin-coating and the performance was investigated. It was found that the properties of the dielectric can be adjusted by changing the content of Al2O3/ZrO2 in nanolaminates: when the content of Al2O3 was higher than 50%, the properties of nanolaminates, such as the optical energy gap, dielectric strength (Vds), capacitance density, and relative permittivity were relatively stable, while the change of these properties became larger when the content of Al2O3 was less than 50%. With the content of ZrO2 varying from 50% to 100%, the variation of these properties was up to 0.482 eV, 2.12 MV/cm, 135.35 nF/cm², and 11.64, respectively. Furthermore, it was demonstrated that the dielectric strength of nanolaminates were influenced significantly by the number (n) of bilayers. Every increment of one Al2O3-ZrO2 bilayer will enhance the dielectric strength by around 0.39 MV/cm (Vds ≈ 0.86 + 0.39n). This could be contributed to the amorphous alumina which interrupted the grain boundaries of zirconia.

High-performance flexible inverted organic light-emitting diodes by exploiting MoS2 nanopillar arrays as electron-injecting and light-coupling layers.

Inverted organic light-emitting diodes (IOLEDs) on plastic substrates have great potential application in flexible active-matrix displays. High energy consumption, instability and poor electron injection are key issues limiting the commercialization of flexible IOLEDs. Here, we have systematically investigated the electrooptical properties of molybdenum disulfide (MoS2) and applied it in developing highly efficient and stable blue fluorescent IOLEDs. We have demonstrated that MoS2-based IOLEDs can significantly improve electron-injecting capacity. For the MoS2-based device on plastic substrates, we have achieved a very high external quantum efficiency of 7.3% at the luminance of 9141 cd m-2, which is the highest among the flexible blue fluorescent IOLEDs reported. Also, an approximately 1.8-fold improvement in power efficiency was obtained compared to glass-based IOLEDs. We attributed the enhanced performance of flexible IOLEDs to MoS2 nanopillar arrays due to their light extraction effect. The van der Waals force played an important role in the formation of MoS2 nanopillar arrays by thermal evaporation. Notably, MoS2-based flexible IOLEDs exhibit an intriguing efficiency roll-up, that is, the current efficiency increases slightly from 14.0 to 14.6 cd A-1 with the luminance increasing from 100 to 5000 cd m-2. In addition, we observed that the initial brightness of 500 cd m-2 can be maintained at 97% after bending for 500 cycles, demonstrating the excellent mechanical stability of flexible IOLEDs. Furthermore, we have successfully fabricated a transparent, flexible IOLED with low efficiency roll-off at high current density.

Super color purity green organic light-emitting diodes with ZrO2/zircone nanolaminates as a distributed Bragg reflector deposited by atomic layer deposition.

ZrO2/zircone nanolaminate thin films fabricated by atomic layer deposition were used for a distributed Bragg reflector (DBR) in green organic light-emitting diodes (OLEDs). It is found that the novel ZrO2/zircone DBR structure significantly improves the light purity of green OLEDs without interfering with intrinsic electroluminescence properties. The full width at half maximum (FWHM) of the EL spectral band for the green OLEDs decreases with respect to increasing the ZrO2/zircone pairs. The FWHMs of OLEDs with 0, 2, 4, and 6 pairs of ZrO2/zircone layers are 72 nm, 48 nm, 24 nm, and 12 nm, respectively. A super-narrow FWHM of 12 nm is achieved by using six pairs of the DBR structure. The EQE is increased from 10.7% to 16.1% with four pairs of ZrO2/zircone layers.

Influence of deposition substrate temperature on the morphology and molecular orientation of chloroaluminum phthalocyanine films as well the performance of organic photovoltaic cells.

The dependence of the morphology of neat chloroaluminum phthalocyanine (ClAlPc) films on substrate temperature (Tsub) during deposition is investigated by variable angle spectroscopic ellipsometry (VASE), x-ray diffraction (XRD), and atomic force microscopy (AFM) to obtain detailed information about the molecular orientation, phase separation, and crystallinity. AFM images indicate that both grain size and root mean square (RMS) roughness noticeably increase with Tsub both in neat and blend films. Increasing Tsub from room temperature to 420 K increases the horizontal orientation of the ClAlPc molecules with an increase of the mean molecular tilt angle from 60.13° (300 K) to 65.86° (420 K). The UV-vis absorption band of the corresponding films increases and the peak wavelength slightly red shifts with the Tsub increase. XRD patterns show a clear diffraction peak at Tsub over 390 K, implying the π-stacking of interconnected ClAlPc molecules at high Tsub. Planar and bulk heterojunction (BHJ) photovoltaic cells containing pristine ClAlPc films and ClAlPc:C60 blend films fabricated at Tsub of 390 K show increases in the power conversion efficiency (ηPCE) of 28% (ηPCE = 3.12%) and 36% (ηPCE = 3.58%), respectively, relative to devices as-deposited at room temperature. The maximum short circuit current in BHJs is obtained at 390 K in the Tsub range from 300 K to 450 K.

The energy transfer mechanism of a photoexcited and electroluminescent organic hybrid thin film of blue, green, and red laser dyes.

Though optically pumped lasing has been realized for years, electrically pumped lasing has not yet been achieved in organic semiconductor devices. In order to make a better understanding of the laser mechanisms of the organic materials, we prepared organic thin films consisting of three efficient laser dyes of a blue emitter, 4″,4″'-N,N-diphenylamine-4,4'-diphenyl-1,1'-binaphthyl (BN), a green emitter, 1,4-bis[2-[4-[N,N-di(p-tolyl)amino] phenyl]vinyl]benzene (DSB), and a red emitter, 4-(dicyanomethylene)-2-t-butyl-6(1,1,7,7-tetramethyljulolidy-l-9-enyl)-4H-pyran (DCJTB) with different doping concentrations for the first time to investigate the cascade energy transfer process. The energy transfer schemes in the co-doped thin films in photoluminescence and electroluminescence have been investigated. The results indicated that the DSB molecules acted as a bridge to deliver energy more effectively from the host (BN) to the guest (DCJTB). Meanwhile, the maximum current efficiency (C E) and power efficiency (P E) of the organic light-emitting devices (OLEDs) with the emitting layer of lower doping concentration were 13.5 cd/A and 14.1 lm/W, respectively.

Polyhedral oligomeric silsesquioxane (POSS)-based multifunctional organic-silica hybrid monoliths.

A facile polyhedral oligomeric silsesquioxane (POSS)-based hybrid monolith with multiple mechanisms was developed by an in situ polymerization. High mechanical stability and good separation capabilities to polar and hydrophobic analytes were successfully achieved. An ideal versatile organic-silica hybrid monolith was presented for easy access to the efficient separation of various analytes.

Electroneutral silica-based hybrid monolith for hydrophilic interaction capillary electrochromatography.

A novel electroneutral and polar silica-based hybrid monolith was developed by an in situ copolymerization of 2-hydroxyethylmethacrylate (HEMA) and polyhedral oligomeric silsesquioxane methacryl substituted (POSS-MA), and successfully employed for hydrophilic interaction capillary electrochromatography (HI-CEC). A good mechanical stability of the prepared monolith was gained with the permeability decreasing from 6.52×10(-14) m2 to 4.61×10(-14) m2 when mobile phase changed from ACN to water. A significant cathodal EOF was obtained through attracting ions from the mobile phase despite the fact that it was devoid of ionizable functional groups on the surface of stationary phases, and a typical HI-CEC mechanism was achieved. The morphologies of the hybrid silica-based monolithic matrixes were observed, and the performance of this silica-based hybrid monolith was also investigated. Satisfactory column performances were carried out for both the neutral and charged analytes with HI-CEC. The analytes including uncharged amides and phenols, charged nucleic acid bases and nucleosides and enkephalins, were well separated with good peak symmetry. High separation efficiencies of charged alkaloids and enkephalins could get up to 145,000 plates/m and 75,000 plates/m, respectively.

Preparation and characterization of hybrid-silica monolithic column with mixed-mode of hydrophilic and strong anion-exchange interactions for pressurized capillary electrochromatography.

A novel organic-silica hybrid monolithic stationary phase with a mixed-mode of hydrophilic and strong anion-exchange interactions (HI-SAX) was prepared with a modified "one-pot" process of functional monomers and alkoxysilanes. Using a hydrosoluble initiator 2,2'-azobis(2-methylpropionamidine) dihydrochloride (AIBA), the homogeneous prepolymerization system of this hybrid monolith was successfully obtained by a simple operation. The polycondensation of alkoxysilanes (tetramethoxysilane (TMOS) and vinyl-trimethoxysilane (VTMS)) and the in situ copolymerization of a quaternary ammonium group-containing acrylic monomer ([2-(acryloyloxy)ethyl] trimethyl ammonium methyl sulfate (AETA)) on the precondensed siloxanes were achieved. The morphologies of the hybrid-silica monolithic matrixes were observed by SEM, and the performances of the organic-silica hybrid monolithic columns were investigated by pressurized capillary electrochromatography. The mechanical stability and reproducibility of the obtained hybrid monolithic column preformed acceptable. Both hydrophilic interaction chromatography mechanism and strong anion-exchanged interaction were investigated. A mixed mode of HI-SAX was obtained for the analysis of nucleotides with a good resolution, and the separation of polar and basic nucleic acid bases and nucleosides was also achieved without peak tailing.