Introduction of a Chiral Biphenanthrene-Diol Unit to Achieve Circularly Polarized Thermally Activated Delayed Fluorescence.

Circularly polarized luminescence (CPL) materials are promising candidates for future display technology. However, such highly efficient emitters suffer from the issues of difficult chiral separation and low photoluminescence quantum yield (PLQY). In this work, the chiral 4,4'-biphenanthrene-3,3'-diol (BIPOL) unit was introduced into a thermally activated delayed fluorescence (TADF) framework for the first time. We presented two series of enantiomers, R/S-o-DCzBPNCN and R/S-p-DCzBPNCN, and the synthesis of enantiopure BIPOL can be prepared via normal column chromatography. Notably, o-DCzBPNCN showed narrow singlet-triplet gap of 0.05 eV, efficient TADF, and high PLQYs of 82 % in doped films. In addition, R/S-o-DCzBPNCN exhibited high luminescence dissymmetry factor (gPL ) values of -1.94×10-2 /+1.91×10-2 in doped films. The strategy of BIPOL introduction offers a new approach to organic emitters with stereospecific synthesis, TADF, and chiroptical properties.

Chiral Binaphthalene Building Blocks for Self-Assembled Nanoscale CPL Emitters.

The introduction of biuret hydrogen-bonding sites onto chiral binaphthalene-based chromophores was investigated as a route to sub-micron-sized, vesicle-like aggregates endowed with chiroptical properties. The synthesis was conducted from the corresponding chiral 4,4'-dibromo-1,1'-bis(2-naphthol) via Suzuki-Miyaura coupling to afford luminescent chromophores whose emission spectrum could be tuned from blue to yellow-green through extension of the conjugation. For all compounds, the spontaneous formation of hollow spheres with a diameter of ca. 200-800 nm was evidenced by scanning electron microscopy, along with strong asymmetry in the circularly polarized absorption spectra. For some compounds, the emission also displayed circular polarization with values of glum = ca. 10-3 which could be increased upon aggregation.

Large-Area Nonfullerene Organic Photovoltaic Modules with a High Certified Power Conversion Efficiency.

Achieving large-area organic photovoltaic (OPV) modules with reasonable cost and performance is an important step toward commercialization. In this work, solution-processed conventional and inverted OPV modules with an area of 216 cm2 were fabricated by the blade coating method. Film uniformity was controlled by adjusting the fabrication parameters of the blade coating procedure. The influence of the concentration of the solutions of the interfacial materials on OPV module performance was investigated. For OPV modules based on the PM6:Y6 photoactive layer, a certificated power conversion efficiency (PCE) of 9.10% was achieved for the conventional OPV modules based on the TASiW-12 interfacial layer while a certificated PCE of 11.27% was achieved for the inverted OPV modules based on the polyethylenimine (PEI) interfacial layer. As for OPV modules based on a commercially available photoactive layer, PV-X Plus, a PCE of 8.52% was achieved in the inverted OPV modules. A halogen-free solvent, o-xylene, was used as the solvent for PV-X Plus, which makes the industrial production much more environmentally friendly.

Circularly Polarized Photoluminescence of Chiral 2D Halide Perovskites at Room Temperature.

Chiral halide perovskites have attracted considerable attention because of their chiroptical, second-harmonic generation, and ferroelectricity properties and their potential application in chiroptoelectronics and chiral spintronics. However, the fundamental research of these properties is insufficient. In this work, chiral perovskites were synthesized using precursor solutions with various stoichiometric ratios ⟨n⟩. The chiral perovskite film prepared from the solution with ⟨n⟩ = 1 is composed of (R-/S-/rac-MBA)2PbBr4, whereas the films prepared from the solutions with ⟨n⟩ larger than 1 are a mixture of (R-/S-/rac-MBA)2(CsMA)n-1PbnBr3n+1 with n = 1 and large n values. A photoluminescence quantum yield of approximately 90 was obtained. Symmetric circular dichroism (CD) spectra were observed without an external magnetic field. Under various magnetic fields, magnetic field-induced CD features are superimposed with the intrinsic chirality-induced CD features. For the ⟨n⟩ = 1 chiral perovskite film, the energy level splitting induced by chiral molecules are a few 10 µeV, whereas the energy level splitting induced by magnetic fields are at the range of ∼-250 to ∼250 µeV. Circularly polarized photoluminescence spectra were observed at room temperature and associated with the spin-preserved energy funneling from highly energetic phases to the lower energetic phases.

Tuning the Circular Dichroism and Circular Polarized Luminescence Intensities of Chiral 2D Hybrid Organic-Inorganic Perovskites through Halogenation of the Organic Ions.

Through the incorporation of various halogen-substituted chiral organic cations, the effects of chiral molecules on the chiroptical properties of hybrid organic-inorganic perovskites (HOIPs) are investigated. Among them, the HOIP having a Cl-substituted chiral cation exhibits the highest circular dichroism (CD) and circular polarized luminescence (CPL) intensities, indicating the existence of the largest rotatory strength, whereas the F-substituted HIOP shows the weakest intensities. The observed modulation can be correlated to the varied magnetic transition dipole of HOIPs, which is sensitive to the d-spacing between inorganic layers and the halogen-halogen interaction between organic cations and the inorganic sheets. These counteracting effects meet the optimal CD and CPL intensity with chlorine substitution, rendering the rotatory strength of HOIPs arranged in the order of (ClMBA)2 PbI4 >(BrMBA)2 PbI4 >(IMBA)2 PbI4 >(MBA)2 PbI4 >(FMBA)2 PbI4 .

Improved efficiency and air stability of two-dimensional p-i-n inverted perovskite solar cells by Cs doping.

Two-dimensional perovskite solar cells (2-D PSCs) have attracted much research attention in recent years because they are more stable in a regular environment than three-dimensional (3-D) ones are. In this study, we doped Cs into 2D perovskite (BA2(MA)2Pb3I10) films as the absorbing layers of the 2-D p-i-n inverted PSCs to investigate the influence of the Cs doping concentration on the properties of the 2-D perovskite films and the fabricated solar cells. Cs doping clearly improves the power conversion efficiency (PCE) and air stability of the PSCs. Doping perovskite with 10% Cs (the best doping concentration in this study) can increase the PSC efficiency from 7.98% to 10.11%. Scanning electron microscopy indicates the improved surface quality and crystallinity by Cs doping. However, excess Cs doping degrades the PCE of the PSCs. Furthermore, 10% Cs doped PSCs show air stability superior to that of undoped ones in unpackaged humidity environments. After exposure to 55% relative humidity (RH) in 19 °C air for 300 h, the PCE of the PSC decreased by only 39%, in contrast to 84% for the undoped PSC.

The influence of the interfacial layer on the stability of all-solution-processed organic light-emitting diodes.

Improving the stability of large-area organic light-emitting diodes is very important for practical applications. The interfacial layer plays a crucial role to improve the electron injection characteristic. In this work, devices prepared by various solution-processed interfacial materials and thermal-evaporated CsF were compared. In the devices with active area of 2.25 mm × 2.25 mm, we found that the performance and lifetime of the device with solution-processed Liq interfacial layer was comparable with the device with thermal-evaporated CsF. However, for the devices with active area of 2.4 cm × 3.7 cm, the device based on thermal-evaporated CsF was the champion in both performance and lifetime. The influence of the thickness of CsF on the stability was investigated. The most stable blue fluorescent devices can be achieved when the thickness of CsF is about 0.1 nm, while the most stable green phosphorescent devices can be obtained by depositing 0.2 nm CsF. The best current efficiency for the blue fluorescent device is 4 cd A-1, while the best one for the green phosphorescent device is 22 cd A-1. Furthermore, burning points causing the failure of the devices were investigated by scanning electron microscopy, atomic force microscopy, thermography and secondary ion mass spectrometry. We demonstrated that burning points are defects, which can be observed after long-time operation, showing higher local temperature and fragmentary electrode.

Lead-free cesium tin halide nanocrystals for light-emitting diodes and color down conversion.

Organometal halide perovskites are attracting a great deal of attention because of their long carrier diffusion lengths, wide wavelength tunability, and narrow-band emission. However, the toxicity of lead has caused considerable environmental and health concerns. In this work, lead-free cesium tin halide nanocrystals are synthesized and investigated. CsSnBr3 and CsSnI3 nanocrystals, 25 and 7 nm in size, are synthesized by a facile hot injection method. Absorption spectroscopy, photoluminescence spectroscopy, and X-ray diffraction were used to understand their structural and optical properties. CsSnBr3 and CsSnI3 nanocrystals show emission peaks at 683 and 938 nm, respectively. These nanocrystals show shelf stability for a few months. Temperature-dependent photoluminescence is utilized to know more about fundamental physical parameters, such as exciton binding energy, charge carrier-phonon interactions and band gap. Light-emitting diodes and color down-conversion films are also demonstrated using these lead free perovskite nanocrystals.

Characterizing temperature-dependent optical properties of (MA0.13FA0.87) PbI3 single crystals using spectroscopic ellipsometry.

In this paper, we present spectroscopic ellipsometry measurements of (MA0.13FA0.87)PbI3 single crystals assessed at photon energies of 0.73-6.42 eV and at temperatures between 4.4 and 400 K. At room temperature, the refractive index was dispersed as a function of frequency, which is typical of a semiconductor. The absorption spectrum exhibited several electronic transitions. We estimated a room temperature direct band gap of 1.66 ± 0.02 eV and exciton binding energy of 40 meV. With decreasing temperature, the refractive index increased. The room-temperature thermo-optic coefficients were -1.7 × 10-4 and -2.5 × 10-4 K-1 at wavelength of 600 and 1200 nm. The exciton peak position and bandgap energy exhibited a redshift, which was attributed to a reverse ordering of the band structures. Additionally, an anomaly in exciton peak position and bandgap occurred at approximately 100-200 K due to the structural phase transition. This phenomenon was associated with the coexistence of MA/FA-disordered and MA/FA-ordered domains. Our results provide a foundation for the technological development of lead halide perovskites-based photonic devices at various temperatures.

Ultrastable, Deformable, and Stretchable Luminescent Organic-Inorganic Perovskite Nanocrystal-Polymer Composites for 3D Printing and White Light-Emitting Diodes.

Organic-inorganic perovskite nanocrystals with excellent optoelectronic properties have been utilized in various applications, despite their stability issues. The perovskite materials are sensitive to environments such as polar solvents, moisture, and heat. Thus, they are not used for extrusion three-dimensional (3D) printing, as it is usually conducted in the ambient environment and requires heating to liquefy the printed materials. In this work, 11 thermoplastic polymers conventionally used for extrusion 3D printing were investigated to test their capability as protective encapsulation materials for perovskite nanocrystals. Three of them exhibited good protective properties, and one (polycaprolactone, PCL) of these three could be blended with perovskite nanocrystals to form perovskite nanocrystal-PCL composites, which were deformable and stretchable once heated. Because of the low melting point of PCL, the perovskite nanocrystals maintained their optical properties after 3D printing, and the printed objects were still having fluorescent behavior. Moreover, fluorescent micrometer-sized fibers based on the perovskite nanocrystal-PCL composites could also be simply prepared using cotton candy makers. Perovskite nanocrystal-PCL composite films with different emission wavelengths were incorporated with blue light-emitting diodes (LEDs) to realize white LEDs with Commission Internationale de l'Éclairage chromaticity coordinates of (0.33, 0.33).

Publisher Correction: Non-Toxic Gold Nanoclusters for Solution-Processed White Light-Emitting Diodes.

A correction to this article has been published and is linked from the HTML and PDF versions of this paper. The error has been fixed in the paper.

Leakage-free solution-processed organic light-emitting diode using a ternary host with single-diode emission area up to 6 × 11.5 cm2.

The electrical current leakage and stability are studied for solution-processed OLEDs with areas of 4.45 mm2, 3 × 3.2 cm2, and 6 × 11.5 cm2. The emission layer of the OLED has a ternary or binary mixed host with hole-transporting molecules tris(4-carbazoyl-9-ylphenyl)amine (TCTA) and 9-(4-tert-butylphenyl)-3,6-bis(triphenylsilyl)-9H-carbazole (CzSi), together with the electron-transporting molecule 2,7-bis(diphenylphosphoryl)-9,9'-spirobi[fluorene] (SPPO13). The phosphorescent emitters are Ir(mppy)3 for green and bis[4-(4-tert-butylphenyl)thieno[3,2-c]pyridine][N,N'-diisopropylbenamidinato]iridium(iii) (PR-02) for orange. Poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl))diphenylamine)] (TFB) is used as the hole transport layer and PEDOT:PSS is used as the hole injection layer. On top of the emission layer, CsF/Al is deposited by thermal evaporation as the cathode. All organic layers are deposited by blade coating and the initial current leaking defects can be avoided by careful control of the coating conditions. The detrimental burning point caused by a local current short developed after long-time operation can be avoided by reducing the operation voltage using a ternary mixed host. The operation voltage is only 4 V at 100 cd m-2 and 5 V at 250 cd m-2 for the green emitting device. Furthermore, the crystallization defect is reduced by the ternary host. For the orange emitting device, the binary host is good enough with an operating voltage of 5 V at 100 cd m-2. For an area as large as 6 × 11.5 cm2, the OLED shows good stability and there is no burning point after an operation of over 1600 hours.

All-Solution-Processed Red and Orange-Red Organic Light-Emitting Diodes with High-Efficiencies: The Effect of Mixed-Host Emissive Layers and Thermal Annealing Treatment.

The instability of the organic light-emitting diodes (OLEDs) during operation can be attributed to the existence of point defects on the organic layers. In this work, the effect of mixed-host emissive layer and the thermal annealing treatment were investigated to eliminate defects and to boost the device performance. The mixed-host system includes 4,4',4''-tri (9-carbazoyl) triphenylamine (TCTA) and 2,7-bis(diphenylphosphoryl)-9, 9'-spirobi[fluorene] (SPPO13). The mixed-host emissive layer with thermal annealing treatment showed low roughness and few pinholes, and the devices fabricated from this emissive layer exhibited high efficiencies, high stabilities, and long lifetimes. The red and orange-red OLEDs exhibited efficiencies of 13.9 cd/A and 24.35 cd/A, respectively. The longest half-lifetime (L0 =500 cd/m2 ) of the red and orange-red OLEDs were 158 h and 180 h, respectively. Efforts were made to solve problems in large-area coating and to reduce the number of defects on in organic layer. Large-active-area (active area=3 cm×4 cm) red phosphorescent OLEDs (PhOLEDs) devices were realized with very high current efficiency up to 9 cd/A.

White-Light Photosensors Based on Ag Nanoparticle-Reduced Graphene Oxide Hybrid Materials.

The unique and outstanding electrical and optical properties of graphene make it a potential material to be used in the construction of high-performance photosensors. However, the fabrication process of a graphene photosensor is usually complicated and the size of the device also is restricted to micrometer scale. In this work, we report large-area photosensors based on reduced graphene oxide (rGO) implemented with Ag nanoparticles (AgNPs) via a simple and cost-effective method. To further optimize the performance of photosensors, the absorbance and distribution of the electrical field intensity of graphene with AgNPs was simulated using the finite-difference time-domain (FDTD) method through use of the surface plasmon resonance effect. Based on the simulated results, we constructed photosensors using rGO with 60⁻80 nm AgNPs and analyzed the characteristics at room temperature under white-light illumination for outdoor environment applications. The on/off ratio of the photosensor with AgNPs was improved from 1.166 to 9.699 at the bias voltage of -1.5 V, which was compared as a sample without AgNPs. The proposed photosensor affords a new strategy to construct cost-effective and large-area graphene films which raises opportunities in the field of next-generation optoelectronic devices operated in an outdoor environment.

Non-Toxic Gold Nanoclusters for Solution-Processed White Light-Emitting Diodes.

Solution-processed optoelectronic devices are attractive because of the potential low-cost fabrication and the compatibility with flexible substrate. However, the utilization of toxic elements such as lead and cadmium in current optoelectronic devices on the basis of colloidal quantum dots raises environmental concerns. Here we demonstrate that white-light-emitting diodes can be achieved by utilizing non-toxic and environment-friendly gold nanoclusters. Yellow-light-emitting gold nanoclusters were synthesized and capped with trioctylphosphine. These gold nanoclusters were then blended with the blue-light-emitting organic host materials to form the emissive layer. A current efficiency of 0.13 cd/A was achieved. The Commission Internationale de l'Eclairage chromaticity coordinates of (0.27, 0.33) were obtained from our experimental analysis, which is quite close to the ideal pure white emission coordinates (0.33, 0.33). Potential applications include innovative lighting devices and monitor backlight.

Thermally Stable High-Performance Polymer Solar Cells Enabled by Interfacial Engineering.

Interfacial engineering plays an important role in determining the performance and stability of polymer solar cells (PSCs). In this study, thermally stable highly efficient PSCs are fabricated by incorporating a solution-processed cathode interfacial layer (CIL), including 4,4'-({[methyl(4-sulfonatobutyl)ammonio]bis(propane-3,1-diyl)}bis(dimethylammoniumdiyl))bis(butane-1-sulfonate) (MSAPBS) and polyethylenimine (PEI). For PSCs based on blends of poly{4,8-bis[5-(2-ethylhexyl)thiophen-2-yl]benzo[1,2-b;4,5-b']dithiophene-2,6-diyl-alt-[4-(2-ethylhexyl)-3fluorothieno[3,4-b]thiophene-2-carboxylate-2,6-diyl]} (PBDTTT-EFT) and [6,6]-phenyl C71 -butyric acid methyl ester (PC71 BM), the maximum power conversion efficiency (PCE) of inverted PSCs reaches 8.1 % and 7.2 % for MSAPBS and PEI CILs, respectively. The inverted PEI devices exhibit remarkable stability (lifetime >6000 h) under accelerated thermal aging (at 80 °C in ambient environment), which is much superior to that of the device with commonly used LiF CIL (lifetime≈33 h). This stability represents the best result reported for PSCs. The promising results based on this strategy can stimulate further work on the development of novel CILs for PSCs and pave the way towards the realization of commercially viable PSCs with high performance and long-term stability.

Toward Long-Term Stable and Efficient Large-Area Organic Solar Cells.

Here, we report that long-term stable and efficient organic solar cells (OSCs) can be obtained through the following strategies: i) combination of rapid-drying blade-coating deposition with an appropriate thermal annealing treatment to obtain an optimized morphology of the active layer; ii) insertion of interfacial layers to optimize the interfacial properties. The resulting devices based on poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b']dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene-2-carboxylate-2,6-diyl)] (PBDTTT-EFT):[6,6]-phenyl C71 butyric acid methyl ester (PC71 BM) blend as the active layer exhibits a power conversion efficiency (PCE) up to 9.57 %, which represents the highest efficiency ever reported for blade-coated OSCs. Importantly, the conventional structure devices based on poly(3-hexylthiophene) (P3HT):phenyl-C61 -butyric acid methyl ester (PCBM) blend can retain approximately 65 % of their initial PCE for almost 2 years under operating conditions, which is the best result ever reported for long-term stable OSCs under operational conditions. More encouragingly, long-term stable large-area OSCs (active area=216 cm2 ) based on P3HT:PCBM blend are also demonstrated. Our findings represent an important step toward the development of large-area OSCs with high performance and long-term stability.

Enhanced Conversion Efficiency of III-V Triple-junction Solar Cells with Graphene Quantum Dots.

Graphene has been used to synthesize graphene quantum dots (GQDs) via pulsed laser ablation. By depositing the synthesized GQDs on the surface of InGaP/InGaAs/Ge triple-junction solar cells, the short-circuit current, fill factor, and conversion efficiency were enhanced remarkably. As the GQD concentration is increased, the conversion efficiency in the solar cell increases accordingly. A conversion efficiency of 33.2% for InGaP/InGaAs/Ge triple-junction solar cells has been achieved at the GQD concentration of 1.2 mg/ml, corresponding to a 35% enhancement compared to the cell without GQDs. On the basis of time-resolved photoluminescence, external quantum efficiency, and work-function measurements, we suggest that the efficiency enhancement in the InGaP/InGaAs/Ge triple-junction solar cells is primarily caused by the carrier injection from GQDs to the InGaP top subcell.

Efficient Low-Temperature Solution-Processed Lead-Free Perovskite Infrared Light-Emitting Diodes.

Lead-free perovskite infrared light-emitting diodes are achieved by using a halide perovskite CsSnI3 as an emissive layer. The film shows compact micrometer-sized grains with only a few pinholes and cracks at the grain boundaries. The device exhibits maximum radiance of 40 W sr-1 m-2 at a current density of 364.3 mA cm-2 and maximum external quantum efficiency of 3.8% at 4.5 V.

Large-Area Nano-patterning and Fabrication of Vertical Transistor Array by Non-close-packed Polystyrene Spheres.

We demonstrated a large-area nanopatterning technique with the help of a non-close-packed PS sphere layer over a large-area substrate. The non-close-packed PS sphere layer is fabricated by blade coating method. It was demonstrated that non-close-packed PS spheres can be achieved within an area of 18 cm × 25 cm on a rigid glass substrate and within an area of 10 cm × 10 cm on a flexible substrate. We also demonstrated that the blade-coated non-close-packed PS sphere layer was suitable for the mass production of vertical organic transistors over a large area.