Reproducible and High-Performance WOLEDs Based on Independent High-Efficiency Triplet Harvesting of Yellow Hot-Exciton ESIPT and Blue TADF Emitters.

Hot exciton organic light-emitting diode (OLED) emitters can balance the high performance of a device and reduce efficiency roll-off by fast reverse intersystem crossing from high-lying triplets (hRISC). In this study, an excited-state intramolecular proton transfer (ESIPT) fluorophore of 2-(benzo[d]thiazol-2-yl)-4-(pyren-1-yl)phenol (PyHBT) with the typical characteristic properties of a hot exciton is developed. With high efficiency of utilization of the exciton (91%), its yellow OLED exhibited high external quantum efficiency (EQE) of 5.6%, current efficiency (CE) of 16.8 cd A-1 , and power efficiency (PE) of 17.3 lm W-1 . The performance of the yellow emissive "hot exciton" ESIPT fluorophores is among the highest recorded. Due to the large Stokes shift of the ESIPT emitter, non-energy-transferred high-performance white OLEDs (WOLEDs) are developed, which are reproducible and highly efficient. This is possible because of the independent harvesting of most of the triplets in both complementary-color emitters without the interference of energy transfer. The PyHBT-based WOLEDs exhibit a maximum EQE of 14.3% and CE of 41.1 cd A-1 , which facilitates the high-yield mass production of inexpensive WOLEDs.

Simple Solution Preparation of Cs2SnI6 Films and Their Applications in Solid-State DSSCs.

Cs2SnI6 powder is, for the first time, solution-prepared via the formula CsI + SnI2 + I2 → Cs2SnI6. The product is highly pure and air/thermal stable. It is found that N,N-dimethylformamide (DMF) and methanol induce severe Cs2SnI6 deterioration with the appearance of a CsI phase in film preparation from Cs2SnI6 powder, while solvents of γ-butyrolactone (GBL) and ethylene glycol methyl ether (EGME) (Film-EGME) give better results. Then, by introducing EGME solvent, in situ preparation of Cs2SnI6 films (Film-1 to Film-4) is realized under solution reaction, which is found to be dominated by thermal dynamic process, i.e., highly pure/oriented Film-4 is obtained under the maximum reagent-concentration. Besides, for good reaction, the solubility of solvent should be balanced among all the reagents and products. Solid-state dye sensitized solar cells (ss-DSSCs) comprising a Cs2SnI6 electrolyte are investigated. The power conversion efficiencies (PCEs) of the ss-DSSCs based on solution-casted Film-EGME and the in situ-prepared Film-4 are 1.81% and 3.30%, respectively. Particularly, with the in situ prepared Cs2SnI6 films, it is found that the open circuit voltages of the ss-DSSCs are closely related to their gap states. When additive is added in Cs2SnI6 electrolyte, a PCE of 6.14% is obtained in an ss-DSSC. Our work highlights the importance of solvent in film preparation and the role of Cs2SnI6 gap states in device performance.

Highly Stable Silver Nanowires/Biomaterial Transparent Electrodes for Flexible Electronics.

Flexible transparent electrodes (FTEs) possess excellent optoelectrical properties, mechanical robustness, and environmental adaptability are important for the industrial scale development of flexible electronics. Silver nanowires (AgNWs) are widely used in FTEs owing to their excellent optoelectrical properties and mechanical flexibility. However, the high surface roughness and poor stability of AgNWs FTEs still limit their practical applications. Here, highly stable FTEs are demonstrated via combining AgNWs and biomaterial propolis which is eco-friendly and antioxidative. The AgNWs/propolis composite transparent electrodes exhibit excellent optoelectrical performance as well as a smooth surface (root-mean-square roughness ∼ 6.2 nm). Meanwhile, the composite electrodes possess high mechanical stability (10,000 bending cycles), thermal stability, and environmental adaptability (60 °C and 85 ± 3% humidity for 700 h). The versatile composite FTEs show great potential applications in organic light-emitting diodes and pressure sensors, which exhibit high performance, mechanical stability, and environmental adaptability. Our strategy of introducing biocompatible materials into metallic nanowires opens up new possibilities to achieve high-quality FTEs in a simple and eco-friendly way.

Organic Photovoltaics Printed via Sheet Electrospray Enabled by Quadrupole Electrodes.

Developing manufacturing methods that are scalable and compatible with a roll-to-roll process with low waste of material has become a pressing need to transfer organic photovoltaics (OPVs) to a viable renewable energy source. For this purpose, various spray printing methods have been proposed. Among them, electrospray (ES) is an attractive option due to its negligible material waste, tunable droplet size, and tolerance to the substrate defects and roughness. Conventional ES with a circular spray footprint often makes the droplets well separated and unlikely to merge, giving rise to "coffee rings" which cause a rough and flawed film morphology. Here, a quadrupole electrode is introduced to generate a compressing electric field that squeezes the conical ES profile into the shape of a thin sheet. The numerical simulation and experimental data of the trajectories of sprayed droplets show that the quadrupole apparatus can effectively increase the long axis to short axis ratio of the oval spray footprint and hence bring droplets closer to each other and make the merging more likely for the deposited droplets. By promoting the merging of droplets, individual coffee rings are also suppressed. Thus, the quadrupole ES offers untapped opportunities for effectively reducing voids and improving the flatness of the ES-printed active layer. The devices with a PM6:N3 active layer printed by the sheet ES exhibited the highest power conversion efficiency (PCE) of up to 15.98%, which is a noticeable improvement over that (14.85%) of counterparts fabricated by a conventional conical ES. This is the highest PCE reported for ES-printed OPVs and is one of the most efficient spray-deposited OPVs so far. In addition, the all-spray-printed devices reached a PCE of 14.55%, which is also among the most efficient all-spray-printed OPVs.

Room-temperature preparation of TiO2/graphene composite photoanodes for efficient dye-sensitized solar cells.

Semi-transparent TiO2/graphene photoanodes are prepared at room temperature via an electrophoretic deposition method followed by compression and applied in dye-sensitized solar cells (DSSCs). Compression enhances the power conversion efficiency (PCE) of a DSSC, which constitutes up 18.4 times improvement compared to the uncompressed device. Incorporating graphene into the compressed film further improves the PCE by 28.8%. Simultaneously, compressing and graphene incorporating can greatly increase the film's transmittance at long wavelengths, benefiting to the use of DSSCs as front unit in tandem solar cells. Scanning electron microscopy, porosity measurements, electrochemical impedance spectroscopy and open circuit voltage decay are performed to investigate the mechanisms. It is demonstrated that compressing a film can reduce the porosity and improve the inter-particle connections, which accounts for the increased light transmittance and enhanced PCE. The incorporated graphene can provide extra charge carrier pathway due to its excellent charge transport properties, as well as protect TiO2 nanostructure by preventing film cracking upon pressing due to its good flexibility, thus increases PCE to 6.75%, which, to our best knowledge, is the highest value among DSSCs with room-temperature prepared photoanodes.

Efficient Non-Fullerene Organic Photovoltaics Printed by Electrospray via Solvent Engineering.

Developing scalable processing methods with low material waste is still one of the remaining challenges for organic photovoltaics (OPVs) to become a practical renewable energy source. Here, we report the first study on printing active layers of OPVs containing non-fullerene acceptors (NFAs) by electrospray (ES). The properties of the solvent significantly influence the interfacial morphology of ES-printed organic thin-films, and solvent engineering is essential to facilitate the formation of efficient active-layer films. We introduce low-vapor-pressure non-halogen solvent o-xylene (OXY) into the high vapor pressure solvent of chloroform to form a binary solvent system with appropriate evaporation time, electric conductivity, and solubility. The characteristic times of the ES process using binary solvents are quantified to provide insights into the dynamic formation of thin films. A longer droplet evaporation time with decent solubility collectively decrease the roughness and domain size of the polymer/NFA blend films, thus increase the photocurrent and fill factor of the ES-printed OPV devices. The ES-printed active layers show enhanced crystallinity and phase separation of NFA molecules than the spin-coated films. The champion cell with an ES-printed PTB7-Th:FOIC active layer exhibits a power conversion efficiency of 9.45%, which is on par with the spin-coated cells and is among the highest of spray-deposited organic solar cells to date. This work demonstrates that ES is an effective method to prepare OPVs on NFAs.

Controlling Electrode Spacing by Polystyrene Microsphere Spacers for Highly Stable and Flexible Transparent Supercapacitors.

Transparent polymer electrolytes such as poly(vinyl alcohol)-based H+, Li+, K+, and Na+ gels have been widely used as both an electrolyte and a separator for flexible transparent supercapacitors (FTSCs). However, these gels sandwiched between the electrodes in FTSCs are easily compressed under bending and compression due to their viscous flow behavior, resulting in the deformation of electrode spacing and the unstable capacitance performance. To resolve this issue, herein, we introduce monodispersed polystyrene (PS) microspheres into PVA-LiCl polymer gel electrolytes as spacers to precisely control the electrode spacing during the assembly of FTSCs using single-walled carbon nanotubes/indium tin oxide-polyethylene terephthalate (ITO-PET) or MnO2/multiwalled carbon nanotubes/ITO-PET as transparent electrodes. The electrode spacing could be tuned by varying the diameter of PS microspheres, for example, 20, 40, and 80 µm. More importantly, the PS microsphere spacers protect the gel electrolyte from the squeeze when bending takes place, allowing the stable performance output by FTSCs under a bending state. After repeating bending tests, the capacitance remains 95.6%, indicating the high stability and flexibility of the devices with the assistance of PS microsphere spacers.

Interfacial engineering of graphene for highly efficient blue and white organic light-emitting devices.

Graphene as anodes of flexible organic light-emitting devices (OLEDs) has intrinsic drawbacks of a low work function and a high sheet resistance although it can eliminate the brittle feature of ITO. Chemical doping as a conventional approach is universally used to decrease the sheet resistance and adjust the work function of graphene electrodes, but it suffers from instability problems due to the volatility of chemical species. Here, an insulated poly(4-styrenesulphonate) (PSS) modification layer is firstly coated on the graphene surface along with improved air-stability and hole-injection ability via interfacial dipoles. Besides, the utilization of PSS is beneficial to reduce the leakage current of OLEDs. Then a gradient injection layer of poly(3,4-ethylenedioxythiophene):PSS (PEDOT:PSS)/tetrafluoroethyleneperfluoro-3,6-dioxa-4-methyl-7-octenesulphonic acid copolymer-doped PEDOT:PSS is covered onto the PSS-modified graphene to further promote hole injection and improve carrier balance inside OLEDs. With above interfacial modification technique, very high efficiencies of 201.9 cd A-1 (76.1 lm W-1, 45.2%) and 326.5 cd A-1 (128.2 lm W-1, 99.5%) for blue and white emissions are obtained, which are comparable to the most efficient display and lighting technologies so far.

Structure-Property Study on Two New D-A Type Materials Comprising Pyridazine Moiety and the OLED Application as Host.

In this paper, two new pyridazine based donor-acceptor type materials, i.e., 3CzPyaPy: 9,9'-(3-(6-(9H-carbazol-9-yl)pyridazin-3-yl)pyridine-2,6-diyl)bis(9H-carbazole) and 4CzPyPyaPy: 3,6-bis(2,6-di(9H-carbazol-9-yl)pyridin-3-yl)pyridazine, were synthesized with high yields. These two materials exhibited strong absorption/emission with high molar extinction coefficients and moderate photoluminescence quantum yield. The glass transition temperature of 3CzPyaPy was detected to be as high as 131 °C, showing its high thermal stability. Although the absorption energies and oxidation/reduction behaviors of the two materials were similar, the emission from 4CzPyPyaPy with longer effective-conjugation length presented hypsochromic shift both in films and in dilute solutions, contradicting to the common sense. The single crystal structure study disclosed their different space stretching and packing: 3CzPyaPy was twisted in larger angles and adopted dimerlike packing, while 4CzPyPyaPy showed smaller torsion angles and exhibited slipped herringbone packing. The dimerlike packing in 3CzPyaPy is responsible for its bathochromic shift of emission in solid state, while its unsymmetrical molecular structure accounts for that in solution. We believe that the unsymmetrical molecular structure of 3CzPyaPy is partially responsible for its high thermal-stability and also responsible for its HOMO dispersion which renders it slightly more difficult to oxidize. 3CzPyaPy was proved to be a bipolar-transport material and when served as a phosphor host, a green phosphorescent device achieved maximum efficiencies of 54.0 cd A-1, 42.4 lm W-1, and 17.7%, which are among the best with nonoptimized device structure, demonstrating its great potential for optoelectronic application. Furthermore, the new synthesized pyridazine derivatives and the corresponding structural and molecular-packing influences on material properties give a new insight into molecule tailoring.

Copper Mesh Templated by Breath-Figure Polymer Films as Flexible Transparent Electrodes for Organic Photovoltaic Devices.

UNLABELLED: Metal mesh is a significant candidate of flexible transparent electrodes to substitute the current state-of-the-art material indium tin oxide (ITO) for future flexible electronics. However, there remains a challenge to fabricate metal mesh with order patterns by a bottom-up approach. In this work, high-quality Cu mesh transparent electrodes with ordered pore arrays are prepared by using breath-figure polymer films as template. The optimal Cu mesh films present a sheet resistance of 28.7 Ω·sq(-1) at a transparency of 83.5%. The work function of Cu mesh electrode is tuned from 4.6 to 5.1 eV by Ag deposition and the following short-time UV-ozone treatment, matching well with the PEDOT: PSS (5.2 eV) hole extraction layer. The modified Cu mesh electrodes show remarkable potential as a substitute of ITO/PET in the flexible OPV and OLED devices. The OPV cells constructed on our Cu mesh electrodes present a similar power conversion efficiency of 2.04% as those on ITO/PET electrodes. The flexible OLED prototype devices can achieve a brightness of 10 000 cd at an operation voltage of 8 V.

A small change in molecular structure, a big difference in the AIEE mechanism.

An anthracene carboxamide derivative of the excited-state intramolecular proton-transfer compound of 2-(2'-hydroxyphenyl)benzothiazole has been newly developed to produce the prominent characteristics of aggregation-induced enhanced emission (AIEE) with a high solid-state fluorescence quantum efficiency of 78.1%. Compared with our previously reported phenyl carboxamide derivatives, a small tailoring of the molecular structure was found to result in a big difference in the dominant factor of the AIEE mechanism. In the phenyl carboxamide derivatives, the dominant factor of the AIEE mechanism is the restriction of the twisted intramolecular charge transfer (TICT) of the enol excited state, regardless of their different aggregation modes. In the anthracene carboxamide derivative, N-(3-(benzo[d]thiazol-2-yl)-4-hydroxyphenyl) anthracene-9-carboxamide, the AIEE characteristics are not dependent on the restriction of TICT, but mainly attributed to the cooperative effects of J-aggregation and the restriction of the cis-trans tautomerization in the keto excited state. A specific N···π interaction was found to be the main driving force for this J-aggregation, as revealed by the single crystal analysis. The AIEE mechanism of this anthracene carboxamide derivative was studied in detail through photophysical investigations and theoretical calculations. On the basis of its AIEE characteristics, a stable non-doped organic light-emitting diode was achieved, with high color purity and a remarkably low efficiency roll-off.

Making silole photovoltaically active by attaching carbazolyl donor groups to the silolyl acceptor core.

Appending carbazolyl groups to a hexaphenylsilole core yielded thermally and morphologically stable carbazolylsiloles; the silole carrying two carbazolyl peripheral groups showed photovoltaic activity.

Structural control of the photoluminescence of silole regioisomers and their utility as sensitive regiodiscriminating chemosensors and efficient electroluminescent materials.

We synthesized a group of silole regioisomers 1(x,y), whose photoluminescence varied dramatically with its regiostructure. By internally hindering the intramolecular rotation, we succeeded in creating a novel silole (1(3,4)) that is strongly luminescent in solutions and whose fluorescence quantum yield in acetone is as high as 83%. We revealed that 1(3,4) was a sensitive chemosensor capable of optically discriminating nitroaromatic regioisomers of p-, o-, and m-nitroanilines. Against general belief, crystal formation of 1(2,4) blue-shifted its emission color and boosted its emission efficiency. The light-emitting diode based on the crystal of 1(2,4) emitted a strong blue light (464 nm) in a high current efficiency (5.86 cd/A).

Light-emitting tridentate cyclometalated platinum(II) complexes containing sigma-alkynyl auxiliaries: tuning of photo- and electrophosphorescence.

The synthesis and structural, photophysical, electrochemical, and electroluminescent properties of a class of platinum(II) complexes bearing sigma-alkynyl ancillary ligands, namely [(C/N/N)Pt(C[triple bond]C]nR] [H(C/N/N) = 6-aryl-2,2'-bipyridine; n = 1-4; R = aryl, alkyl, or trimethylsilyl], have been studied. Substituents with different steric and electronic properties were introduced into the tridentate cyclometalating and arylacetylide ligands, and the pi-conjugation length of the oligoynyl moiety was homologously extended from ethynyl to octatetraynyl. The X-ray crystal structures of several derivatives confirm the Pt-(CC) ligation and reveal various intermolecular interactions, such as pi-pi, Pt...Pt, and C-H...F-C. The complexes display good thermal stability and intense phosphorescence in fluid and glassy solutions with high quantum yields and microsecond lifetimes. Their emission energies are sensitive to solvent polarity, the electronic affinities of the substituents on both the cyclometalating and arylacetylide groups, and the length of the oligoynyl ligand. By choosing appropriate cyclometalating and sigma-alkynyl ligands, the emission color of this class of platinum(II) complexes can be tuned from green-yellow to saturated red. In addition to (3)MLCT [Pt(5d) --> pi*(C/N/N)] and (3)IL(C/N/N), intriguing (3)IL(alkynyl) excited states localized on -(C[triple bond]C)(4)- and -(C[triple bond]Cpyrenyl-1) moieties that afford narrow-bandwidth emissions have been observed. Selected Pt(II) complexes were doped into the emissive region of multilayer, vapor-deposited organic light-emitting diodes. The tunable electrophosphorescence energy resembles that recorded in fluid solutions for these emitters, and the devices exhibit high luminance and efficiencies (up to 4.2 cd A(-1)).

[(C(wedge)N(wedge)N)Pt(C identical to C)nR] (HC(wedge)N(wedge)N = 6-aryl-2,2'-bipyridine, n = 1-4, R = aryl, SiMe3) as a new class of light-emitting materials and their applications in electrophosphorescent devices.

Tridentate cyclometalated platinum(II) complexes bearing sigma-alkynyl ligands exhibit tunable photoluminescence and enhanced stability during vacuum deposition; OLEDs based on these materials display orange to red electrophosphorescence with low turn-on voltages (approximately 4 V), maximum luminance approaching 10,000 cd m-2 and efficiency up to 4.2 cd A-1.