Dimerized Small-Molecular Acceptor Enables the Organic Bulk-Heterojunction Layer with High Thermal Stability.

Incorporation of a non-fullerene acceptor (NFA) into an organic bulk-heterojunction currently has realized the extendable spectral response and high photocurrent generation in organic photodiodes. However, to allow these organic materials to be industrially commercialized, the thermal stability which enables the materials to survive under the process integration and operation needs to be considered. Generally, NFA small molecules showed high crystallinity, which aggregated through heating and led to the poor thermal stability. To tackle the thermal stability issue of highly efficient NFAs, two IDIC-based NFA dimers─IDIC-T Dimer and IDIC-TT Dimer─were designed, synthesized, and characterized; the thermal stability of the BHJ layer incorporating these dimer molecules was evaluated and compared with that of the BHJ layer using the monomer, IDIC-4Cl, as acceptors. Eventually, a power conversion efficiency of 9.44% was achieved for organic photovoltaic devices based on the NFA dimer. The dimers also showed remarkable thermal stability than the IDIC-4Cl monomer, which provided a promising direction for the polymer/small-molecule system in organic photodiodes for industrial practicability.

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.

Bulk-Heterojunction Adjustment Enables a Self-filtering Organic Photodetector with a Narrowband Response.

Image-sensor technology is the foundation of many emerging applications, where the photodetector is designed to interact with incoming photons that have specific colors or wavelengths. A color filter is therefore crucial to enable the selective spectral response of the photodetector and to eliminate the crosstalk interference resulting from ambient lights. Unfortunately, a reduced detection sensitivity of the photodetector is inevitable due to an imperfect light filtering, which greatly limits the practical applications of selective-response photodetectors. Herein, we demonstrate a bulk-heterojunction (BHJ) organic composite featuring a self-filtering light responsive characteristic. Through a careful optimization of the BHJ film, the organic photodetector (OPD) demonstrates a high-selective spectral response to the infrared (IR) radiation without the need of applying a color filter. As a result, the self-filtering top-illuminated OPD exhibits a narrowband external quantum efficiency (EQE) of 53% with a narrow full width at half-maximum (fwhm) of 56 nm centering at 1080 nm. A high responsivity of 0.46 A W-1 is also achieved at 1080 nm wavelength due to the self-filtering characteristic.

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 .

Electric-Field-Induced Excimer Formation at the Interface of Deep-Blue Emission Poly(9,9-dioctyl-2,7-fluorene) with Polyelectrolyte or Its Precursor as Electron-Injection Layer in Polymer Light-Emitting Diode and Its Prevention for Stable Emission and Higher Performance.

Conjugated polyelectrolytes and their precursors as electron-injection layer (EIL) in polymer light-emitting diode have attracted extensive attention because they allow the use of environmentally stable high work function metals as cathode with efficient electron injection. Here, for the first time, we find that an undesirable green emission component (470-650 nm) in the electroluminescence spectra is observed during continuous operation of deep-blue emission ß-phase poly(9,9-dioctyl-2,7-fluorene) (ß-PFO) device upon introducing polyelectrolyte poly[9,9-bis(6'-(18-crown-6)methoxy)hexyl fluorene] chelating to potassium ion (PFCn6:K+) as EIL. This phenomenon also happens to nonchelating PFCn6, poly[(9,9-bis(3'-( N, N-dimethylamino)propyl)-2,7-fluorene)- alt-2,7-(9,9-dioctylfluorene)], or even nonemissive poly[4-((18-crown-6)methoxy)methyl styrene] chelating to K+ (PSCn6:K+). It can be ascribed to electric-field induction accompanied by thermal motion of a highly polar side chain in the polyelectrolyte leading to local segmental alignment of PFO main chains at the emitting layer (EML)/EIL interface and thus formation of green emission excimer, which is supported by the following observations: appearance of green emission component using nonemissive PSCn6:K+ as EIL, absence of green emission component as the device is operated at low-temperature (78 K) at which molecular thermal motion are frozen, and absence of green emission upon introducing 2,2',2″-(1,3,5-phenylbenzenetriyl)tris[1-phenyl-1 H-benzimidazole] as buffer layer in between EML and EIL for the prevention of direct contact of EML with polyelectrolyte or its precursor EIL.