Poly(acridan-grafted biphenyl germanium) with High Triplet Energy as a Universal Host for High-Efficiency Thermally Activated Delayed Fluorescence Full-Color Devices and Their Hybrid with Phosphor for White Light Electroluminescence.

Developing an effective host for highly efficient full-color electroluminescence devices through a solution-process is still a challenge at present. Here, we use the σ-π conjugated polymer, poly(acridan grafted biphenyl germanium) P(DMAC-Ge), having the highest triplet energy (ET) 2.86 eV among conjugated polymers as the host in sky-blue phosphorescence, TADFs (blue (B), green (G), and red (R)), and hybrid white (W) PLEDs. Upon doping with a sky-blue phosphor-emitter (Firpic), the resulting device gives the high EQEmax 19.7% with Bmax 24,918 cd/m2. The Ge-containing polymer backbone can provide as a channel for electron transport and charge trap into the guest as manifested by the electroluminescence dynamics. Further introducing the bipolar material DCzPPy as cohost, the devices with a sky-blue phosphor (Firpic) and each of the TADF-guests─B (DMAC-TRZ), G (DACT-II), and R (TPA-DCPP) in the EML─achieve the high maximum EQEs as 19.7%, 19.4%, 21.5% and 3.82% with the emission peaks at 470, 485, 508, and 630 nm, respectively. As the three guests (DMAC-TRZ, Ir-O, Ir-R) are doped together into the emitting layer, we obtain a TADF-phosphor (T-P) hybrid white PLED giving a record-high EQE 22.5% among the solution processed hybrid OLED with CIE (0.34, 0.40) and Bmax 28,945 cd/m2. These results manifest that P(DMAC-Ge) is a potential polymer host for full-color TADF and hybrid white light PLEDs with high performance.

Highly Efficient Solution-Processed Thermally Activated Delayed Fluorescence Bluish-Green and Hybrid White Organic Light-Emitting Diodes Using Novel Bipolar Host Materials.

Two pyridine-containing bipolar host materials with high triplet energy, 9,10-dihydro-9,9-dimethyl-10-(3-(6-(3-(9,9-dimethylacridin-10(9H)-yl)phenyl)pyridin-2-yl)phenyl acridin (DDMACPy) and N-(3-(6-(3-(diphenyl amino)phenyl)pyridin-2-yl)phenyl)-N-phenylbenzenamine (DTPAPy), are synthesized from the modification of the commonly adapted host material 2,6-bis(3-(9H-carbazol-9-yl)phenyl)pyridine (DCzPPy). The highest occupied molecular orbital levels of DDMACPy (5.50 eV) and DTPAPy (5.60 eV) are found to be shallower than that of DCzPPy (5.90 eV) that leads to the improvement in hole injection from the hole transport layer PEDOT:PSS (WF = 5.10 eV). These host materials are used in the emitting layer of bluish-green organic light-emitting diode (OLED) with the thermally activated delayed fluorescence (TADF) emitter, 9,9-dimethyl-9,10-dihydroacridine-2,4,6-triphenyl-1,3,5-triazine, as the guest. The DDMACPy-based device shows the highest performance among them, with the maximum external quantum efficiency (EQEmax), current efficiency (CEmax), and power efficiency (PEmax) of 21.0%, 53.1 cd A-1, and 44.0 lm W-1 at CIE (0.17, 0.42), respectively. By further doping with the red-emitting phosphor iridium(III) bis(2-phenylquinoline)(2,2,6,6-tetramethylheptane-3,5-ionate) [Ir(dpm)PQ2] and yellow-emitting phosphor iridium(III) bis(4-(4-t-butylphenyl)thieno[3,2-c]pyridinato-N,C20)acetylacetonate (PO-01-TB) emitters into the bluish-green emitting layer, a TADF-phosphor hybrid white OLED (T-P WOLED) is obtained with excellent EQEmax, CEmax, and PEmax of 17.4%, 48.7 cd A-1, and 44.5 lm W-1 at CIE (0.35, 0.44), respectively. Moreover, both the bluish-green and WOLED show a low efficiency roll-off with external quantum efficiencies at the brightness of 1000 cd m-2 (EQE1000) of 18.7 and 16.2%, respectively, which are the highest performance records among the solution-processed TADF bluish-green and T-P WOLEDs.

Optoelectronic Properties of High Triplet σ-π-Conjugated Poly[(biphenyl group IV-A atom (C, Si, Ge, Sn)] Backbones.

A series of σ-π-conjugated polymers composed of biphenyl and X atom as backbone repeat unit (where X is the group IV-A atom: carbon, silicon, germanium, or tin) grafted with two alkoxy-substituted biphenyls at the X atom as side chains are synthesized and their optoelectronic properties are studied systematically. We choose biphenyl rather than alkyl as the side chain because its frontier molecular orbital distributions are close to those of our previously reported σ-π-conjugated polymer grafted with transport moieties. The present σ-π polymers with various X atoms show significant differences in triplet energy (ET) ranging from 2.58 to 2.83 eV with the sequence Ge > Si > C > Sn and in charge mobilities from 10-9 to 10-7 cm2/(V s) with the sequence Si > Ge > Sn > C, indicating that the properties of the σ-π polymers are largely affected by their X atoms. The Ge- and Sn-based σ-π-conjugated polymers show the highest and lowest ET values, respectively, due to their different levels of π-electron delocalization caused by size effects and (d-p)π orbital interaction. For their charge transport properties, the Si-based conjugated σ-π polymer gives the highest hole and electron mobilities due to the stronger σ-π conjugation and shorter Si-C bond length between the attached carbon atom in biphenyl and Si. On the contrary, the C-based σ-π-conjugated polymer gives the lowest charge mobilities due to a lack of d orbital in the C atom leading to a poor σ-π conjugation characteristic. These σ-π polymers with different ET levels and charge transport properties show a significant effect on their electroluminescence characteristics. Among them, the Ge-based σ-π-conjugated polymer when used as host shows the best device performance due to its higher ET and reasonable charge mobility. Such findings of different optoelectronic properties of these σ-π-conjugated polymers provide useful guidelines for the selection of backbone for designing σ-π-conjugated polymer host grafted with charge transport moieties.

Acridan-Grafted Poly(biphenyl germanium) with High Triplet Energy, Low Polarizability, and an External Heavy-Atom Effect for Highly Efficient Sky-Blue TADF Electroluminescence.

We propose the novel σ-π conjugated polymer poly(biphenyl germanium) grafted with two electron-donating acridan moieties on the Ge atom for use as the host material in a polymer light-emitting diode (PLED) with the sky-blue-emitting thermally activated delayed fluorescence (TADF) material DMAC-TRZ as the guest. Its high triplet energy (ET ) of 2.86 eV is significantly higher than those of conventional π-π conjugated polymers (ET =2.65 eV as the limit) and this guest emitter (ET =2.77 eV). The TADF emitter emits bluer emission than in other host materials owing to the low orientation polarizability of the germanium-based polymer host. The Ge atom also provides an external heavy-atom effect, which increases the rate of reverse intersystem crossing in this TADF guest, so that more triplet excitons are harvested for light emission. The sky-blue TADF electroluminescence with this host/guest pair gave a record-high external quantum efficiency of 24.1 % at maximum and 22.8 % at 500 cd m-2 .

High Brightness Fluorescent White Polymer Light-Emitting Diodes by Promoted Hole Injection via Reduced Barrier by Interfacial Dipole Imparted from Chlorinated Indium Tin Oxide to the Hole Injection Layer PEDOT:PSS.

We demonstrated that introducing poly(3,4-ethylenedioxythiophene) polystyrene sulfonate as a hole transport layer (HTL) on top of chlorinated indium tin oxide (Cl-ITO) anode can lead to a deeper highest occupied molecular orbital level of the HTL (promoting from 5.22 to 5.42 eV) due to the interfacial dipole imparted by the Cl-ITO, which allows barrier-free hole injection to the emitting layer with polyspirobifluorene doped with the yellow emitter rubrene and significantly prevents excitons quenching by residual chlorine radicals on the surface of Cl-ITO. By use of poly[9,9-bis(6'-(18-crown-6)methoxy)hexyl)fluorene] chelating to potassium ion (PFCn6:K+) as electron injection layer and air-stable high work function (EΦ) metal aluminum as the cathode, the performance of fluorescent white polymer light-emitting diode (WPLED) achieves the high maximum brightness (Bmax) of 61 523 cd/m2 and maximum luminance efficiency (ηL, max) of 10.3 cd/A. Replacing PFCn6:K+/Al cathode by CsF/Al, the Bmax and ηL, max are promoted to 87 615 cd/m2 (the record value in WPLED) and 11.1 cd/A, respectively.

Bipolar and Unipolar Silylene-Diphenylene σ-π Conjugated Polymer Route for Highly Efficient Electrophosphorescence.

σ-π conjugated polymer strategy is proposed for designing electroluminescent host polymers with silylene-diphenylene as the backbone repeat unit giving a high triplet energy (ET = 2.67 eV). By incorporation of high ET (3.0 eV) electron (oxadiazole, OXD) and hole (triphenyl amine, TPA) transport moieties, or TPA alone (in this case, the main chain acts as electron transport channel) as side arms on the silylene, the high ET bipolar and unipolar polymers are formed, allowing a use of iridium green phosphor (Ir(ppy)2(acac), Ir-G) (ET = 2.40 eV) as the dopant. The matching of energy levels of the dopant with the hosts, leading to charge trapping into it; and singlets and triplets of the exciplex and excimer can be harvested via energy transfer to the dopant. Using these host-guest systems as the emitting layer, chlorinated indium-tin-oxide (Cl-ITO) as the anode, and benzimidazole derivative (TPBI) as the electron transport layer, this two-layer device gives the high luminance efficiency 80.1 cd/A and external quantum efficiency 21.2%, which is the best among the report values for polymer light emitting diode (PLED) in the literatures. This example manifests that σ-π conjugated polymer strategy is a promising route for designing polymer host for efficient electrophosphorescence.

Patterned nitroxide polymer brushes for thin-film cathodes in organic radical batteries.

Nitroxide polymer brushes were covalently patterned on flexible conducting substrates via surface-initiated atom transfer radical polymerization and microcontact printing. As a cathode of organic radical batteries, the nitroxide polymer brushes prevent the nitroxide polymer from dissolving into electrolyte solvents, which improves the cycle-life performance of batteries.

Three-dimensional electrodes for dye-sensitized solar cells: synthesis of indium-tin-oxide nanowire arrays and ITO/TiO2 core-shell nanowire arrays by electrophoretic deposition.

Dye-sensitized solar cells (DSSCs) show promise as a cheaper alternative to silicon-based photovoltaics for specialized applications, provided conversion efficiency can be maximized and production costs minimized. This study demonstrates that arrays of nanowires can be formed by wet-chemical methods for use as three-dimensional (3D) electrodes in DSSCs, thereby improving photoelectric conversion efficiency. Two approaches were employed to create the arrays of ITO (indium-tin-oxide) nanowires or arrays of ITO/TiO(2) core-shell nanowires; both methods were based on electrophoretic deposition (EPD) within a polycarbonate template. The 3D electrodes for solar cells were constructed by using a doctor-blade for coating TiO(2) layers onto the ITO or ITO/TiO(2) nanowire arrays. A photoelectric conversion efficiency as high as 4.3% was achieved in the DSSCs made from ITO nanowires; this performance was better than that of ITO/TiO(2) core-shell nanowires or pristine TiO(2) films. Cyclic voltammetry confirmed that the reaction current was significantly enhanced when a 3D ITO-nanowire electrode was used. Better separation of charge carriers and improved charge transport, due to the enlarged interfacial area, are thought to be the major advantages of using 3D nanowire electrodes for the optimization of DSSCs.