Discovery of Novel Pyrazole Acyl Thiourea Skeleton Analogue as Potential Herbicide Candidates.

To discover novel transketolase (TKL, EC 2.2.1.1) inhibitors with potential herbicidal applications, a series of pyrazole acyl thiourea derivatives were designed based on a previously obtained pyrazolamide acyl lead compound, employing a scaffold hopping strategy. The compounds were synthesized, their structures were characterized, and they were evaluated for herbicidal activities. The results indicate that 7a exhibited exceptional herbicidal activity against Digitaria sanguinalis and Amaranthus retroflexus at a dosage of 90 g ai/ha, using the foliar spray method in a greenhouse. This performance is comparable to that of commercial products, such as nicosulfuron and mesotrione. Moreover, 7a showed moderate growth inhibitory activity against the young root and stem of A. retroflexus at 200 mg/L in the small cup method, similar to that of nicosulfuron and mesotrione. Subsequent mode-of-action verification experiments revealed that 7a and 7e inhibited Setaria viridis TKL (SvTKL) enzyme activity, with IC50 values of 0.740 and 0.474 mg/L, respectively. Furthermore, they exhibited inhibitory effects on the Brassica napus acetohydroxyacid synthase enzyme activity. Molecular docking predicted potential interactions between these (7a and 7e) and SvTKL. A greenhouse experiment demonstrated that 7a exhibited favorable crop safety at 150 g ai/ha. Therefore, 7a is a promising herbicidal candidate that is worthy of further development.

A New Dioxasilepine-Aryldiamine Hybrid Electron-Blocking Material for Wide Linear Dynamic Range and Fast Response Organic Photodetector.

A new dioxasilepine and aryldiamine hybrid material DPSi-DBDTA is designed to act as the electron-blocking layer (EBL) for vacuum-processed organic photodetector (OPD). The O-Si-O-linked cyclic structure leads DPSi-DBDTA to have dipolar character, high LUMO, and good thermal and morphology stability suitable for vacuum deposition. An initial trial with C60-based single active layer OPD device manifests the superior capability of DPSi-DBDTA for dark current suppression compared to the typical aryldiamines. Here, the bare and MoO3-doped DPSi-DBDTA is further examined as EBLs for the visible light responsive OPD comprising DTDCPB/C70 bulk heterojunction (BHJ) as the active layer. In sync with the result of C60-based OPD, the low dark current density and high specific detectivity D* (7.085 × 1012 cm Hz1/2 W-1) are achieved. The device with 5% MoO3-doped EBL can exhibit a wide linear dynamic range (LDR) up to 154.166 dB, which is attributed to suppression of both dark current density and carrier recombination. Additionally, the devices also manifest fast time-resolved performance in both frequency and transient response measurements. Especially for the device with 20% MoO3-doped EBL, a wide cutoff frequency response 692.047 kHz and record-high transient response demonstrating ≤0.683 µs for transient photovoltage (TPV) and ≤0.478 µs for transient photocurrent (TPC) have been realized, which is possibly owing to the balance of mobility that mitigates the damage from traps. Such submicrosecond response is comparable with the state-of-the-art perovskite-PDs and Si-PDs.

New D-A-A'-Configured Small Molecule Donors Employing Conjugation to Red-shift the Absorption for Photovoltaics.

Four new donor-acceptor-acceptor' (D-A-A')-configured donors, CPNT, DCPNT, CPNBT, and DCPNBT equipped with naphtho[1,2-c:5,6-c']bis([1,2,5]-thiadiazole) (NT) or naphtho[2,3-c][1,2,5]thiadiazole (NBT) as the central acceptor (A) unit bridging triarylamine donor (D) and cyano or dicyanovinylene acceptor (A'), were synthesized and characterized. All molecules exhibit bathochromic absorption shifts as compared to those of the benzothiadiazole (BT)-based analogues owing to improved electron-withdrawing and quinoidal character of NT and NBT cores that lead to stronger intramolecular charge transfer. Favorable energy level alignments with C70 , together with the good thermal stability and the antiparallel dimeric packing render CPNT and DCPNT suitable donors for vacuum-processed organic photovoltaics (OPV)s. OPVs based on DCPNT : C70 active layers displayed the best power conversion efficiency (PCE)=8.3%, along with an open circuit voltage of 0.92 V, a short circuit current of 14.5 mA cm-2 and a fill factor of 62% under 1 sun intensity, simulated AM1.5G illumination. Importantly, continuous light-soaking with AM 1.5G illumination has verified the durability of the devices based on CPNT:C70 and DCPNT : C70 as the active blends. The devices were examined for their feasibility of indoor light harvesting under 500 lux illumination by a TLD-840 fluorescent lamp, giving PCE=12.8% and 12.6%, respectively. These results indicate that the NT-based D-A-A'-type donors CPNT and DCPNT are potential candidates for high-stability vacuum-processed OPVs suitable for indoor energy harvesting.

New D-A-A-Configured Small-Molecule Donors for High-Efficiency Vacuum-Processed Organic Photovoltaics under Ambient Light.

Four new donor-acceptor-acceptor (D-A-A) type molecules (DTCPB, DTCTB, DTCPBO, and DTCTBO), wherein benzothiadiazole or benzoxadiazole serves as the central A bridging triarylamine (D) and cyano group (terminal A), have been synthesized and characterized. The intramolecular charge-transfer character renders these molecules with strong visible light absorption and forms antiparallel dimeric crystal packing with evident π-π intermolecular interactions. The characteristics of the vacuum-processed photovoltaic device with a bulk heterojunction active layer employing these molecules as electronic donors combining C70 as electronic acceptor were examined and a clear structure-property-performance relationship was concluded. Among them, the DTCPB-based device delivers the best power conversion efficiency (PCE) up to 6.55% under AM 1.5 G irradiation. The study of PCE dependence on the light intensity indicates the DTCPB-based device exhibits superior exciton dissociation and less propensity of geminated recombination, which was further verified by a steady photoluminescence study. The DTCPB-based device was further optimized to give an improved PCE up to 6.96% with relatively high stability under AM 1.5 G continuous light-soaking for 150 h. This device can also perform a PCE close to 16% under a TLD-840 fluorescent lamp (800 lux), indicating its promising prospect for indoor photovoltaic application.

Influence of Singlet and Charge-Transfer Excitons on the Open-Circuit Voltage of Rubrene/Fullerene Organic Photovoltaic Device.

We demonstrated that the open-circuit voltage (VOC) of rubrene/C60 organic photovoltaic (OPV) devices can be substantially improved by changing the rubrene thickness. A shoulder exhibited in a range of 500-550 nm was observed. This result indicated that the singlet excitons of rubrene were increased when the thickness of the rubrene layer was increased. Capacitance-voltage measurements were conducted for estimating the built-in potential of the devices. The calculated VOC was higher than that of the experiment, thus indicating that energetic losses occurred in the devices. We reused the reciprocity and revised Marcus theory for determining the charge-transfer (CT) properties of the devices. The CT properties of the CT states at the rubrene/C60 interface remained similar. The nonradiative energetic losses become smaller when the rubrene layer was increased, thus indicating the bimolecular recombination was increased. The increased recombination thermally activated the electrons in C60 into rubrene for forming the singlet excitons in rubrene. The reduction in reorganization energy indicated that the electroluminescence of rubrene was enhanced, thereby improving VOC. These results proved that the two-step thermal activation of C60 electrons and the improved VOC of rubrene were caused by the increased singlet excitons of rubrene.

Cathodic-controlled and near-infrared organic upconverter for local blood vessels mapping.

Organic materials are used in novel optoelectronic devices because of the ease and high compatibility of their fabrication processes. Here, we demonstrate a low-driving-voltage cathodic-controlled organic upconverter with a mapping application that converts near-infrared images to produce images of visible blood vessels. The proposed upconverter has a multilayer structure consisting of a photosensitive charge-generation layer (CGL) and a phosphorescent organic light-emitting diode (OLED) for producing clear images with a high resolution of 600 dots per inch. In this study, temperature-dependent electrical characterization was performed to analyze the interfacial modification of the cathodic-controlled upconverter. The result shows that the upconverter demonstrated a high conversion efficiency of 3.46% because of reduction in the injection barrier height at the interface between the CGL and the OLED.

Downscaling the Sample Thickness to Sub-Micrometers by Employing Organic Photovoltaic Materials as a Charge-Generation Layer in the Time-of-Flight Measurement.

Time-of-flight (TOF) measurements typically require a sample thickness of several micrometers for determining the carrier mobility, thus rendering the applicability inefficient and unreliable because the sample thicknesses are orders of magnitude higher than those in real optoelectronic devices. Here, we use subphthalocyanine (SubPc):C70 as a charge-generation layer (CGL) in the TOF measurement and a commonly hole-transporting layer, N,N'-diphenyl-N,N'-bis(1,1'-biphenyl)-4,4'-diamine (NPB), as a standard material under test. When the NPB thickness is reduced from 2 to 0.3 µm and with a thin 10-nm CGL, the hole transient signal still shows non-dispersive properties under various applied fields, and thus the hole mobility is determined accordingly. Only 1-µm NPB is required for determining the electron mobility by using the proposed CGL. Both the thicknesses are the thinnest value reported to data. In addition, the flexibility of fabrication process of small molecules can deposit the proposed CGL underneath and atop the material under test. Therefore, this technique is applicable to small-molecule and polymeric materials. We also propose a new approach to design the TOF sample using an optical simulation. These results strongly demonstrate that the proposed technique is valuable tool in determining the carrier mobility and may spur additional research in this field.

Improving performance and lifetime of small-molecule organic photovoltaic devices by using bathocuproine-fullerene cathodic layer.

In this study, we compared the use of neat bathocuproine (BCP) and BCP:C60 mixed buffer layers in chloroboron subphthalocyanine (SubPc)/C60 bilayer organic photovoltaic (OPV) devices and analyzed their influence on device performance. Replacing the conventional BCP with BCP:C60 enabled manipulating the optical field distribution for optimizing the optical properties of the devices. Estimation of the interfacial barrier indicated that the insertion of the BCP:C60 between the C60 and electrode can effectively reduce the barrier for electrons and enhance electron collection at the electrode. Temperature-dependent measurements of the OPV devices performed to calculate the barrier height at the SubPc/C60 interface suggested that band bending was larger when the BCP:C60 buffer layer was used, reflecting increased exciton dissociation efficiency. In addition, the device lifetime was considerably improved when the BCP:C60 buffer layer was used. The device performance was stabilized after the photodegradation of the active layers, thereby increasing the device lifetime compared with the use of the neat BCP buffer layer. Atomic force microscopy images showed that the neat BCP was easily crystallized and could degrade the cathodic interface, whereas the blend of C60 and BCP suppressed the crystallization of BCP. Therefore, the optimal buffer layer improved both the device performance and the device lifetime.