Critical role of electrons in the short lifetime of blue OLEDs.

Designing robust blue organic light-emitting diodes is a long-standing challenge in the display industry. The highly energetic states of blue emitters cause various degradation paths, leading to collective luminance drops in a competitive manner. However, a key mechanism of the operational degradation of organic light-emitting diodes has yet to be elucidated. Here, we show that electron-induced degradation reactions play a critical role in the short lifetime of blue organic light-emitting diodes. Our control experiments demonstrate that the operational lifetime of a whole device can only be explained when excitons and electrons exist together. We examine the atomistic mechanisms of the electron-induced degradation reactions by analyzing their energetic profiles using computational methods. Mass spectrometric analysis of aged devices further confirm the key mechanisms. These results provide new insight into rational design of robust blue organic light-emitting diodes.

Dipole Moment- and Molecular Orbital-Engineered Phosphine Oxide-Free Host Materials for Efficient and Stable Blue Thermally Activated Delayed Fluorescence.

To utilize thermally activated delayed fluorescence (TADF) technology for future displays, it is necessary to develop host materials which harness the full potential of blue TADF emitters. However, no publication has reported such hosts yet. Although the most popular host for blue TADF, bis[2-(diphenylphosphino)phenyl]ether oxide (DPEPO) guarantees high-maximum external quantum efficiency (EQEmax ) TADF devices, they exhibit very short operational lifetimes. In contrast, long-lifespan blue TADF devices employing stable hosts such as 3',5-di(9H-carbazol-9-yl)-[1,1'-biphenyl]-3-carbonitrile (mCBP-CN) exhibit much lower EQEmax than the DPEPO-employed devices. Here, an elaborative approach for designing host molecules is suggested to achieve simultaneously stable and efficient blue TADF devices. The approach is based on engineering the molecular geometry, ground- and excited-state dipole moments of host molecules. The engineered hosts significantly enhance delayed fluorescence quantum yields of TADF emitters, as stabilizing the charge-transfer excited states of the TADF emitters and suppressing exciton quenching, and improve the charge balance. Moreover, they exhibit both photochemical and electrochemical stabilities. The best device employing one of the engineered hosts exhibits 79% increase in EQEmax compared to the mCBP-CN-employed device, together with 140% and 92-fold increases in operational lifetime compared to the respective mCBP-CN- and the DPEPO-based devices.

Improved Efficiency and Lifetime of Deep-Blue Hyperfluorescent Organic Light-Emitting Diode using Pt(II) Complex as Phosphorescent Sensitizer.

Although the organic light-emitting diode (OLED) has been successfully commercialized, the development of deep-blue OLEDs with high efficiency and long lifetime remains a challenge. Here, a novel hyperfluorescent OLED that incorporates the Pt(II) complex (PtON7-dtb) as a phosphorescent sensitizer and a hydrocarbon-based and multiple resonance-based fluorophore as an emitter (TBPDP and ν-DABNA) in the device emissive layer (EML), is proposed. Such an EML system can promote efficient energy transfer from the triplet excited states of the sensitizer to the singlet excited states of the fluorophore, thus significantly improving the efficiency and lifetime of the device. As a result, a deep-blue hyperfluorescent OLED using a multiple resonance-based fluorophore (ν-DABNA) with Commission Internationale de L'Eclairage chromaticity coordinate y below 0.1 is demonstrated, which attains a narrow full width at half maximum of ≈17 nm, fourfold increased maximum current efficiency of 48.9 cd A-1 , and 19-fold improved half-lifetime of 253.8 h at 1000 cd m-2 compared to a conventional phosphorescent OLED. The findings can lead to better understanding of the hyperfluorescent OLEDs with high performance.

Significant Performance Improvement in n-Channel Organic Field-Effect Transistors with C60 :C70 Co-Crystals Induced by Poly(2-ethyl-2-oxazoline) Nanodots.

Solution-processed organic field-effect transistors (OFETs) have attracted great interest due to their potential as logic devices for bendable and flexible electronics. In relation to n-channel structures, soluble fullerene semiconductors have been widely studied. However, they have not yet met the essential requirements for commercialization, primarily because of low charge carrier mobility, immature large-scale fabrication processes, and insufficient long-term operational stability. Interfacial engineering of the carrier-injecting source/drain (S/D) electrodes has been proposed as an effective approach to improve charge injection, leading also to overall improved device characteristics. Here, it is demonstrated that a non-conjugated neutral dipolar polymer, poly(2-ethyl-2-oxazoline) (PEOz), formed as a nanodot structure on the S/D electrodes, enhances electron mobility in n-channel OFETs using a range of soluble fullerenes. Overall performance is especially notable for (C60 -Ih )[5,6]fullerene (C60 ) and (C70 -D5h(6) )[5,6]fullerene (C70 ) blend films, with an increase from 0.1 to 2.1 cm2 V-1 s-1 . The high relative mobility and eighteen-fold improvement are attributed not only to the anticipated reduction in S/D electrode work function but also to the beneficial effects of PEOz on the formation of a face-centered-cubic C60 :C70 co-crystal structure within the blend films.

Nano-crater morphology in hybrid electron-collecting buffer layers for high efficiency polymer:nonfullerene solar cells with enhanced stability.

Organic solar cells based on solution processes have strong advantages over conventional silicon solar cells due to the possible low-cost manufacturing of flexible large-area solar modules at low temperatures. However, the benefit of the low temperature process is diminished by a thermal annealing step at high temperatures (≥200 °C), which cannot be practically applied for typical plastic film substrates with a glass transition temperature lower than 200 °C, for inorganic charge-collecting buffer layers such as zinc oxide (ZnO) in high efficiency inverted-type organic solar cells. Here we demonstrate that novel hybrid electron-collecting buffer layers with a particular nano-crater morphology, which are prepared by a low-temperature (150 °C) thermal annealing process of ZnO precursor films containing poly(2-ethyl-2-oxazoline) (PEOz), can deliver a high efficiency (12.35%) similar to the pristine ZnO layers prepared by the conventional high-temperature process (200 °C) for inverted-type polymer:nonfullerene solar cells. The nano-crater morphology was found to greatly enhance the stability of solar cells due to improved adhesion between the active layers and ZnO:PEOz hybrid buffer layers.

Low-Voltage Solution-Processed Hybrid Light-Emitting Transistors.

We report the development of low operating voltages in inorganic-organic hybrid light-emitting transistors (HLETs) based on a solution-processed ZrO x gate dielectric and a hybrid multilayer channel consisting of the heterojunction In2O3/ZnO and the organic polymer "Super Yellow" acting as n- and p-channel/emissive layers, respectively. Resulting HLETs operate at the lowest voltages reported to-date (<10 V) and combine high electron mobility (22 cm2/(V s)) with appreciable current on/off ratios (≈103) and an external quantum efficiency of 2 × 10-2% at 700 cd/m2. The charge injection, transport, and recombination mechanisms within this HLET architecture are discussed, and prospects for further performance enhancement are considered.

Pronounced Side Chain Effects in Triple Bond-Conjugated Polymers Containing Naphthalene Diimides for n-Channel Organic Field-Effect Transistors.

Three triple bond-conjugated naphthalene diimide (NDI) copolymers, poly{[ N, N'-bis(2-R1)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]- alt-[(2,5-bis(2-R2)-1,4-phenylene)bis(ethyn-2,1-diyl)]} (PNDIR1-R2), were synthesized via Sonogashira coupling polymerization with varying alkyl side chains at the nitrogen atoms of the imide ring and 2,5-positions of the 1,4-diethynylbenzene moiety. Considering their identical polymer backbone structures, the side chains were found to have a strong influence on the surface morphology/nanostructure, thus playing a critical role in charge-transporting properties of the three NDI-based copolymers. Among the polymers, the one with an octyldodecyl (OD) chain at the nitrogen atoms of imide ring and a hexadecyloxy (HO) chain at the 2,5-positions of 1,4-diethynylbenzene, P(NDIOD-HO), exhibited the highest electron mobility of 0.016 cm2 V-1 s-1, as compared to NDI-based copolymers with an ethylhexyl chain at the 2,5-positions of 1,4-diethynylbenzene. The enhanced charge mobility in the P(NDIOD-HO) layers is attributed to the well-aligned nano-fiber-like surface morphology and highly ordered packing structure with a dominant edge-on orientation, thus enabling efficient in-plane charge transport. Our results on the molecular structure-charge transport property relationship in these materials may provide an insight into novel design of n-type conjugated polymers for applications in the organic electronics of the future.

Efficient Deep Red Light-Sensing All-Polymer Phototransistors with p-type/n-type Conjugated Polymer Bulk Heterojunction Layers.

Here we demonstrate deep red light-sensing all-polymer phototransistors with bulk heterojunction layers of poly[4,8-bis[(2-ethylhexyl)-oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]-thiophenediyl] (PTB7) and poly[[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)] (P(NDI2OD-T2)). The device performances were investigated by varying the incident light intensity of the deep red light (675 nm), while the signal amplification capability was examined by changing the gate and drain voltages. The result showed that the present all-polymer phototransistors exhibited higher photoresponsivity (∼14 A/W) and better on/off photoswitching characteristics than the devices with the pristine polymers under illumination with the deep red light. The enhanced phototransistor performances were attributed to the well-aligned nanofiber-like morphology and nanocrystalline P(NDI2OD-T2) domains in the blend films, which are beneficial for charge separation and charge transport in the in-plane direction.

Modulation-Doped In2 O3 /ZnO Heterojunction Transistors Processed from Solution.

This paper reports the controlled growth of atomically sharp In2 O3 /ZnO and In2 O3 /Li-doped ZnO (In2 O3 /Li-ZnO) heterojunctions via spin-coating at 200 °C and assesses their application in n-channel thin-film transistors (TFTs). It is shown that addition of Li in ZnO leads to n-type doping and allows for the accurate tuning of its Fermi energy. In the case of In2 O3 /ZnO heterojunctions, presence of the n-doped ZnO layer results in an increased amount of electrons being transferred from its conduction band minimum to that of In2 O3 over the interface, in a process similar to modulation doping. Electrical characterization reveals the profound impact of the presence of the n-doped ZnO layer on the charge transport properties of the isotype In2 O3 /Li-ZnO heterojunctions as well as on the operating characteristics of the resulting TFTs. By judicious optimization of the In2 O3 /Li-ZnO interface microstructure, and Li concentration, significant enhancement in both the electron mobility and TFT bias stability is demonstrated.

Strong Composition Effects in All-Polymer Phototransistors with Bulk Heterojunction Layers of p-type and n-type Conjugated Polymers.

We report the composition effect of polymeric sensing channel layers on the performance of all-polymer phototransistors featuring bulk heterojunction (BHJ) structure of electron-donating (p-type) and electron-accepting (n-type) polymers. As an n-type component, poly(3-hexylthiopehe-co-benzothiadiazole) end-capped with 4-hexylthiophene (THBT-4ht) was synthesized via two-step reactions. A well-studied conjugated polymer, poly(3-hexylthiophene) (P3HT), was employed as a p-type polymer. The composition of BHJ (P3HT:THBT-4ht) films was studied in detail by varying the THBT-4ht contents (0, 1, 3, 5, 10, 20, 30, 40, and 100 wt %). The best charge separation in the P3HT:THBT-4ht films was measured at 30 wt % by the photoluminescence (PL) study, while the charge transport characteristics of devices were improved at the low THBT-4ht contents (<10 wt %). The photosensing experiments revealed that the photosensivity of all-polymer phototransistors was higher than that of the phototransistors with the pristine P3HT layers and strongly dependent on the BHJ composition. The highest (corrected) responsivity (RC) was achieved at 20 wt %, which can be attributable to the balance between the best charge separation and transport states, as investigated for crystal nanostructures and surface morphology by employing synchrotron-radiation grazing-incidence wide-angle X-ray scattering, high-resolution/scanning transmission electron microscopy, and atomic force microscopy.

Significant Stability Enhancement in High-Efficiency Polymer:Fullerene Bulk Heterojunction Solar Cells by Blocking Ultraviolet Photons from Solar Light.

Achievement of extremely high stability for inverted-type polymer:fullerene solar cells is reported, which have bulk heterojunction (BHJ) layers consisting of poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-alt-3-fluorothieno[3,4-b]thiophene-2-carboxylate] (PTB7-Th) and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM), by employing UV-cut filter (UCF) that is mounted on the front of glass substrates. The UCF can block most of UV photons below 403 nm at the expense of ≈20% reduction in the total intensity of solar light. Results show that the PTB7-Th:PC71BM solar cell with UCF exhibits extremely slow decay in power conversion efficiency (PCE) but a rapidly decayed PCE is measured for the device without UCF. The poor device stability without UCF is ascribed to the oxidative degradation of constituent materials in the BHJ layers, which give rise to the formation of PC71BM aggregates, as measured with high resolution and scanning transmission electron microscopy and X-ray photoelectron spectroscopy. The device stability cannot be improved by simply inserting poly(ethylene imine) (PEI) interfacial layer without UCF, whereas the lifetime of the PEI-inserted PTB7-Th:PC71BM solar cells is significantly enhanced when UCF is attached.

Acidity-Controlled Conducting Polymer Films for Organic Thermoelectric Devices with Horizontal and Vertical Architectures.

Organic thermoelectric devices (OTEDs) are recognized one of the next generation energy conversion platforms because of their huge potentials for securing electricity continuously from even tiny heat sources in our daily life. The advantage of OTEDs can be attributable to the design freedom in device shapes and the low-cost fabrication by employing solution coating processes at low temperatures. As one of the major OTE materials to date, poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) has been used, but no study has been yet carried out on its acidity control even though the acidic components in OTEDs can seriously affect the device performance upon operation. Here we demonstrate that the addition of aniline (a weak base) can control the acidity of PEDOT:PSS and enhance the performance of OTEDs. In particular, the vertical OTEDs with aniline-doped PEDOT:PSS films (active area = 1.0 cm2) could continuously generate electricity (0.06 nW) even at low temperatures (<38 °C) when they were mounted on a desk lamp (power = 24 W).

Broadband pH-Sensing Organic Transistors with Polymeric Sensing Layers Featuring Liquid Crystal Microdomains Encapsulated by Di-Block Copolymer Chains.

We report broadband pH-sensing organic field-effect transistors (OFETs) with the polymer-dispersed liquid crystal (PDLC) sensing layers. The PDLC layers are prepared by spin-coating using ethanol solutions containing 4-cyano-4'-pentyl-biphenyl (5CB) and a diblock copolymer (PAA-b-PCBOA) that consists of LC-philic block [poly(4-cyano-biphenyl-4-oxyundecyl acrylate) (PCBOA)] and acrylic acid block [poly(acrylic acid) (PAA)]. The spin-coated sensing layers feature of 5CB microdomains (<5 µm) encapsulated by the PAA-b-PCBOA polymer chains. The resulting LC-integrated-OFETs (PDLC-i-OFETs) can detect precisely and reproducibly a wide range of pH with only small amounts (10-40 µL) of analyte solutions in both static and dynamic perfusion modes. The positive drain current change is measured for acidic solutions (pH < 7), whereas basic solutions (pH > 7) result in the negative change of drain current. The drain current trend in the present PDLC-i-OFET devices is explained by the shrinking-expanding mechanism of the PAA chains in the diblock copolymer layers.

Inverted polymer fullerene solar cells exceeding 10% efficiency with poly(2-ethyl-2-oxazoline) nanodots on electron-collecting buffer layers.

Polymer solar cells have been spotlighted due to their potential for low-cost manufacturing but their efficiency is still less than required for commercial application as lightweight/flexible modules. Forming a dipole layer at the electron-collecting interface has been suggested as one of the more attractive approaches for efficiency enhancement. However, only a few dipole layer material types have been reported so far, including only one non-ionic (charge neutral) polymer. Here we show that a further neutral polymer, namely poly(2-ethyl-2-oxazoline) (PEOz) can be successfully used as a dipole layer. Inclusion of a PEOz layer, in particular with a nanodot morphology, increases the effective work function at the electron-collecting interface within inverted solar cells and thermal annealing of PEOz layer leads to a state-of-the-art 10.74% efficiency for single-stack bulk heterojunction blend structures comprising poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-alt-3-fluorothieno[3,4-b]thiophene-2-carboxylate] as donor and [6,6]-phenyl-C71-butyric acid methyl ester as acceptor.

Broadband All-Polymer Phototransistors with Nanostructured Bulk Heterojunction Layers of NIR-Sensing n-Type and Visible Light-Sensing p-Type Polymers.

We report 'broadband light-sensing' all-polymer phototransistors with the nanostructured bulk heterojunction (BHJ) layers of visible (VIS) light-sensing electron-donating (p-type) polymer and near infrared (NIR) light-sensing electron-accepting (n-type) polymer. Poly[{2,5-bis-(2-ethylhexyl)-3,6-bis-(thien-2-yl)-pyrrolo[3,4-c]pyrrole-1,4-diyl}-co-{2,2'-(2,1,3-benzothiadiazole)]-5,5'-diyl}] (PEHTPPD-BT), which is synthesized via Suzuki coupling and employed as the n-type polymer, shows strong optical absorption in the NIR region (up to 1100 nm) in the presence of weak absorption in the VIS range (400~600 nm). To strengthen the VIS absorption, poly(3-hexylthiophene) (P3HT) is introduced as the p-type polymer. All-polymer phototransistors with the BHJ (P3HT:PEHTPPD-BT) layers, featuring a peculiar nano-domain morphology, exhibit typical p-type transistor characteristics and efficiently detect broadband (VIS~NIR) lights. The maximum corrected responsivity (without contribution of dark current) reaches up to 85~88% (VIS) and 26~40% (NIR) of theoretical responsivity. The charge separation process between P3HT and PEHTPPD-BT components in the highest occupied molecular orbital is proposed as a major working mechanism for the effective NIR sensing.

Pronounced Cosolvent Effects in Polymer:Polymer Bulk Heterojunction Solar Cells with Sulfur-Rich Electron-Donating and Imide-Containing Electron-Accepting Polymers.

The performance of solar cells with a polymer:polymer bulk heterojunction (BHJ) structure, consisting of poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-alt-3-fluorothieno[3,4-b]thiophene-2-carboxylate] (PTB7-Th) donor and poly[[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)] (P(NDI2OD-T2)) acceptor polymers, was investigated as a function of cosolvent (p-xylene:chlorobenzene (pXL:CB)) composition ratio. A remarkable efficiency improvement (∼38%) was achieved by spin-coating the photoactive blend layer from pXL:CB = 80:20 (volume) rather than pXL alone, but the efficiency then decreased when the CB content increased further to pXL:CB = 60:40. The improved efficiency was correlated with a particular PTB7-Th:P(NDI2OD-T2) donor-acceptor blend nanostructure, evidenced by a fiber-like surface morphology, a red-shifted optical absorption, and enhanced PL quenching. Further device optimization for pXL:CB = 80:20 films yielded a power conversion efficiency of ∼5.4%. However, these devices showed very poor stability (∼15 min for a 50% reduction in initial efficiency), owing specifically to degradation of the PTB7-Th donor-component. Replacing PTB7-Th with a more stable donor polymer will be essential for any application potential to be realized.

Liquid crystal-gated-organic field-effect transistors with in-plane drain-source-gate electrode structure.

We report planar liquid crystal-gated-organic field-effect transistors (LC-g-OFETs) with a simple in-plane drain-source-gate electrode structure, which can be cost-effectively prepared by typical photolithography/etching processes. The LC-g-OFET devices were fabricated by forming the LC layer (4-cyano-4'-pentylbiphenyl, 5CB) on top of the channel layer (poly(3-hexylthiophene), P3HT) that was spin-coated on the patterned indium-tin oxide (ITO)-coated glass substrates. The LC-g-OFET devices showed p-type transistor characteristics, while a current saturation behavior in the output curves was achieved for the 50-150 nm-thick P3HT (channel) layers. A prospective on/off ratio (>1 × 10(3)) was obtained regardless of the P3HT thickness, whereas the resulting hole mobility (0.5-1.1 cm(2)/(V s)) at a linear regime was dependent on the P3HT thickness. The tilted ordering of 5CB at the LC-P3HT interfaces, which is induced by the gate electric field, has been proposed as a core point of working mechanism for the present LC-g-OFETs.

Influence of nickel(II) oxide nanoparticle addition on the performance of organic field effect transistors.

Here, the improved performance of organic field effect transistors (OFET) by doping inorganic nanoparticles into a semiconducting polymer as a channel layer is briefly reported. Nickel(II) oxide nanoparticle (NiOnp) was used as an inorganic dopant while regioregular poly(3-hexylthiophene) (P3HT) was used as a matrix polymer for the channel layer in the OFETs. The doping ratio of NiOnp was made 1 wt.% so that it would minimally influence the nanostructure of the P3HT channel layer. The results showed that the optical absorption spectrum of the P3HT film was slightly red-shifted by the NiOnp doping, which reflects the improved crystallinity of the P3HT domains in the P3HT:NiOnp films. The drain current of the OFETs with the P3HT:NiOnp films was significantly enhanced ca. three-to-seven fold by the NiOnp doping under appying gate voltages while the hole mobility of the OFETs P3HT:NiOnp films was improved as much as three fold by the NiOnp doping. The enhanced performance has been assigned to the role of NiOnp that has relatively higher hole mobility than the P3HT polymer.

Liquid crystal-on-organic field-effect transistor sensory devices for perceptive sensing of ultralow intensity gas flow touch.

We demonstrate liquid crystal-on-organic field-effect transistor (LC-on-OFET) sensory devices that can perceptively sense ultralow level gas flows. The LC-on-OFET devices were fabricated by mounting LC molecules (4-cyano-4'-pentylbiphenyl - 5CB) on the polymer channel layer of OFET. Results showed that the presence of LC molecules on the channel layer resulted in enhanced drain currents due to a strong dipole effect of LC molecules. Upon applying low intensity nitrogen gas flows, the drain current was sensitively increased depending on the intensity and time of nitrogen flows. The present LC-on-OFET devices could detect extremely low level nitrogen flows (0.7 sccm-11 µl/s), which could not be felt by human skins, thanks to a synergy effect between collective behavior of LC molecules and charge-sensitive channel layer of OFET. The similar sensation was also achieved using the LC-on-OFET devices with a polymer film skin, suggesting viable practical applications of the present LC-on-OFET sensory devices.

Hybrid phototransistors based on bulk heterojunction films of poly(3-hexylthiophene) and zinc oxide nanoparticle.

Hybrid phototransistors (HPTRs) were fabricated on glass substrates using organic/inorganic hybrid bulk heterojunction films of p-type poly(3-hexylthiophene) (P3HT) and n-type zinc oxide nanoparticles (ZnO(NP)). The content of ZnO(NP) was varied up to 50 wt % in order to understand the composition effect of ZnO(NP) on the performance of HPTRs. The morphology and nanostructure of the P3HT:ZnO(NP) films was examined by employing high resolution electron microscopes and synchrotron radiation grazing angle X-ray diffraction system. The incident light intensity (P(IN)) was varied up to 43.6 µW/cm², whereas three major wavelengths (525 nm, 555 nm, 605 nm) corresponded to the optical absorption of P3HT were applied. Results showed that the present HPTRs showed typical p-type transistor performance even though the n-type ZnO(NP) content increased up to 50 wt %. The highest transistor performance was obtained at 50 wt %, whereas the lowest performance was measured at 23 wt % because of the immature bulk heterojunction morphology. The drain current (I(D)) was proportionally increased with P(IN) due to the photocurrent generation in addition to the field-effect current. The highest apparent and corrected responsivities (R(A) = 4.7 A/W and R(C) = 2.07 A/W) were achieved for the HPTR with the P3HT:ZnO(NP) film (50 wt % ZnO(NP)) at P(IN) = 0.27 µW/cm² (555 nm).