Chiral Diketopyrrolopyrrole-Based Conjugated Polymers with Intramolecular Rotation-Isomeric Conformation Asymmetry for Near-Infrared Circularly Polarized Light-Sensing Organic Phototransistors.

Recent advances in chiral nanomaterials interacting with circularly polarized (CP) light open new expectations for optoelectronics in various research fields such as quantum- and biology-related technology. To fully utilize the great potential of chiral optoelectronic devices, the development of chiral optoelectronic devices that function in the near-infrared (NIR) region is required. Herein, we demonstrate a NIR-absorbing, chiroptical, low-band-gap polymer semiconductor for high-performance NIR CP light phototransistors. A newly synthesized diketopyrrolopyrrole-based donor-acceptor-type chiral π-conjugated polymer with an asymmetric alkyl side chain exhibits strong chiroptical activity in a wavelength range of 700-1000 nm. We found that the attachment of an enantiomerically pure stereogenic alkyl substituent to the π-conjugated chromophore backbone led to strong chiroptical activity through symmetry breaking of the π-conjugation of the backbone in a molecular rotational motion while maintaining the coplanar backbone conformation for efficient charge transport. The NIR CP light-sensing phototransistors based on a chiral π-conjugated polymer photoactive single channel layer exhibit a high photoresponsivity of 26 A W-1 under NIR CP light irradiation at 920 nm, leading to excellent NIR CP light distinguishability. This study will provide a rationale and strategy for designing chiral π-conjugated polymers for high-performance NIR chiral optoelectronics.

Chiroptical Synaptic Heterojunction Phototransistors Based on Self-Assembled Nanohelix of π-Conjugated Molecules for Direct Noise-Reduced Detection of Circularly Polarized Light.

High-performance chiroptical synaptic phototransistors are successfully demonstrated using heterojunctions composed of a self-assembled nanohelix of a π-conjugated molecule and a metal oxide semiconductor. To impart strong chiroptical activity to the device, a diketopyrrolopyrrole-based π-conjugated molecule decorated with chiral glutamic acid is newly synthesized; this molecule is capable of supramolecular self-assembly through noncovalent intermolecular interactions. In particular, nanohelix formed by intertwinded fibers with strong and stable chiroptical activity in a solid-film state are obtained through hydrogen-bonding-driven, gelation-assisted self-assembly. Phototransistors based on interfacial charge transfer at the heterojunction from the chiroptical nanohelix to the metal oxide semiconductor show excellent chiroptical detection with a high photocurrent dissymmetry factor of 1.97 and a high photoresponsivity of 218 A W-1 . The chiroptical phototransistor demonstrates photonic synapse-like, time-dependent photocurrent generation, along with persistent photoconductivity, which is attributed to the interfacial charge trapping. Through the advantage of synaptic functionality, a trained convolutional neural network successfully recognizes noise-reduced circularly polarized images of handwritten alphabetic characters with better than 89.7% accuracy.

Solution-processed near-infrared Cu(In,Ga)(S,Se)2 photodetectors with enhanced chalcopyrite crystallization and bandgap grading structure via potassium incorporation.

Although solution-processed Cu(In,Ga)(S,Se)2 (CIGS) absorber layers can potentially enable the low-cost and large-area production of highly stable electronic devices, they have rarely been applied in photodetector applications. In this work, we present a near-infrared photodetector functioning at 980 nm based on solution-processed CIGS with a potassium-induced bandgap grading structure and chalcopyrite grain growth. The incorporation of potassium in the CIGS film promotes Se uptake in the bulk of the film during the chalcogenization process, resulting in a bandgap grading structure with a wide space charge region that allows improved light absorption in the near-infrared region and charge carrier separation. Also, increasing the Se penetration in the potassium-incorporated CIGS film leads to the enhancement of chalcopyrite crystalline grain growth, increasing charge carrier mobility. Under the reverse bias condition, associated with hole tunneling from the ZnO interlayer, the increasing carrier mobility of potassium-incorporated CIGS photodetector improved photosensitivity and particularly external quantum efficiency more than 100% at low light intensity. The responsivity and detectivity of the potassium-incorporated CIGS photodetector reach 1.87 A W-1 and 6.45 [Formula: see text] 1010 Jones, respectively, and the - 3 dB bandwidth of the device extends to 10.5 kHz under 980 nm near-infrared light.

Spirally Wrapped Carbon Nanotube Microelectrodes for Fiber Optoelectronic Devices beyond Geometrical Limitations toward Smart Wearable E-Textile Applications.

Fiber optoelectronics technology has recently attracted attention as enabling various form factors of wearable electronics, and the issue of how to control and optimize the configuration and physical properties of the electrode micropatterns in the microfiber devices has become important. Here, spirally wrapped carbon nanotube (CNT) microelectrodes with a controlled dimension are demonstrated for high-performance fiber optoelectronic devices. Inkjet-printed CNT microelectrodes with the desired dimension on an agarose hydrogel template are rolling-transferred onto a microfiber surface with an efficient electrical interface. A fiber organic field-effect transistor with spirally wrapped CNT microelectrodes verifies the feasibility of this strategy, where the transferred microelectrodes intimately contact the organic semiconductor active layer and the output current characteristics are simply controlled, resulting in characteristics that exceed the previous structural limitations. Furthermore, a fiber organic photodiode with spirally wrapped CNT microelectrodes, when used as a transparent electrode, exhibits a high Ilight/Idark ratio and good durability of bending. This fiber photodiode can be successfully incorporated into a textile photoplethysmography bandage for the real-time monitoring of human vital signals. This work offers a promising and efficient strategy to overcome the geometric factors limiting the performance of fiber-optic optoelectronic devices.

Ecofriendly Catechol Lipid Bioresin for Low-Temperature Processed Electrode Patterns with Strong Durability.

We demonstrated catechol lipid-based bioresin, which is collected from lacquer trees, to produce conductive pastes that can be processed at low temperatures, which are highly adhesive and multidurable. Our conductive paste, which consists of catechol lipid-based urushiol resin and a multimodal mixture of silver fillers, exhibited stable dispersion with shear thinning properties. The urushiol lacquer induced spontaneous reduction of silver salt at the surface of the silver fillers, thereby contributing to lower the contact resistance between conductive fillers in the electrical conduction. Furthermore, the directional volume shrinkage of the urushiol lacquer matrix in a cross-linking reaction resulted in a highly ordered microstructure of the silver fillers with layer-by-layer stacking of the silver flakes. This structure contributed to the improvement of the electrical contact between fillers as well as excellent mechanical hardness, anti-scratch capability, and the long-term environmental stability of the conductive films. Conductive films based on the silver paste with urushiol lacquer exhibited low electrical resistivity below 4.4 × 10-5 Ω cm, 5B-class strong adhesion strength, and high hardness exceeding 200 MPa. Finally, we demonstrated the facile room-temperature processability and screen printability of the UL-Ag paste by fabricating a printed antenna and three-dimensional (3D) electrode assembly based on a plastic 3D block.

High-Efficiency Polymer:Nonfullerene Solar Cells with Quaterthiophene-Containing Polyimide Interlayers.

Interfacial layers (interlayers) are one of the emerging approaches in organic solar cells with bulk heterojunction (BHJ) layers because the solar cell efficiency can be additionally improved by their presence. However, less attention is paid to the use of interlayers for polymer:nonfullerene solar cells, which have strong advantages over polymer:fullerene solar cells. In addition, most polymers used for the interlayers possess a low glass transition temperature (Tg). Here, it is demonstrated that two types of quarterthiophene-containing polyimides (PIs) with high Tg (>198 °C), which are synthesized using pyromellitic dianhydride (PMDA) and cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CTCDA), can act as an interfacial layer in the polymer:nonfullerene solar cells with the BHJ layers of poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'-c:4',5'-c']dithiophene-4,8-dione))] (PBDB-T) and 3,9-bis(2-methylene(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene) (ITIC), or (3-(1,1-dicyanomethylene)-1-methyl-indanone)-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']-dithiophene) (IT-M). Interestingly, the efficiency and stability of devices are improved by the PMDA-based PI interlayers with a stretched chain structure but degraded by the CTCDA-based PI interlayers with a bended chain structure.

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.

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.

Polymer Nanodot-Hybridized Alkyl Silicon Oxide Nanostructures for Organic Memory Transistors with Outstanding High-Temperature Operation Stability.

Organic memory devices (OMDs) are becoming more important as a core component in flexible electronics era because of their huge potentials for ultrathin, lightweight and flexible plastic memory modules. In particular, transistor-type OMDs (TOMDs) have been gradually spotlighted due to their structural advantages possessing both memory and driving functions in single devices. Although a variety of TOMDs have been developed by introducing various materials, less attention has been paid to the stable operation at high temperatures. Here we demonstrate that the polymer nanodot-embedded alkyl silicon oxide (ASiO) hybrid materials, which are prepared by sol-gel and thermal cross-linking reactions between poly(4-vinylphenol) (PVP) and vinyltriethoxysilane, can deliver low-voltage (1~5 V) TOMDs with outstanding operation stability (>4700 cycles) at high temperatures (150 °C). The efficient low-voltage memory function is enabled by the embedded PVP nanodots with particular lattice nanostructures, while the high thermal stability is achieved by the cross-linked ASiO network structures.

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.

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.