Solution-Processed Isoindigo- and Thienoisoindigo-Based Donor-Acceptor-Donor π-Conjugated Small Molecules: Synthesis, Morphology, Molecular Packing, and Field-Effect Transistor Characterization.

Molecular design and precise control of thin-film morphology and crystallinity of solution-processed small molecules are important for enhancing charge transport mobility of organic field-effect transistors and gaining more insight into the structure-property relationship. Here, two donor-acceptor-donor (D-A-D) architecture small molecules TRA-IID-TRA and TRA-TIID-TRA comprising an electron-donating triarylamine (TRA) and two different electron-withdrawing cores, isoindigo (IID) and thienoisoindigo (TIID), respectively, were synthesized and characterized. Replacing the phenylene rings of central IID A with thiophene gives a TIID core, which reduces the optical band gap and upshifts the energy levels of frontier molecular orbitals. The single-crystal structures and grazing-incidence wide-angle X-ray scattering (GIWAXS) analysis revealed that TRA-TIID-TRA exhibits the relatively tighter π-π stacking packing with preferential edge-on orientation, larger coherence length, and higher crystallinity due to the noncovalent S···O/S···π intermolecular interactions. The distinctly oriented and connected ribbon-like TRA-TIID-TRA crystalline film by the solution-shearing process achieved a superior hole mobility of 0.89 cm2 V-1 s-1 in the organic field-effect transistor (OFET) device, which is at least five times higher than that (0.17 cm2 V-1 s-1) of TRA-IID-TRA with clear cracks. Eventually, rational modulation of fused core in the π-conjugated D-A-D small molecule provides a new understanding of structural design for enhancing the performance of solution-processed organic semiconductors.

Organic Lead Halide Nanocrystals Providing an Ultra-Wide Color Gamut with Almost-Unity Photoluminescence Quantum Yield.

The most attractive aspect of perovskite nanocrystals (NCs) for optoelectronic applications is their widely tunable emission wavelength, but it has been quite challenging to tune it without sacrificing the photoluminescence quantum yield (PLQY). In this work, we report a facile ligand-optimized ion-exchange (LOIE) method to convert room-temperature spray-synthesized, perovskite parent NCs that emit a saturated green color to NCs capable of emitting colors across the entire visible spectrum. These NCs exhibited exceptionally stable and high PLQYs, particularly for the pure blue (96%) and red (93%) primary colors that are indispensable for display applications. Surprisingly, the blue- and red-emissive NCs obtained using the LOIE method preserved the cubic shape and cubic phase structure that they inherited from their parent NCs, while exhibiting high crystallinity and high color-purity. Together with the parent green-emissive NCs, the obtained blue- and red-emissive NCs provided a very wide color gamut, corresponding to a Digital Cinema Initiatives-P3 of 140% or an International Telecommunication Union Recommendation BT.2020 of 102%. With the superior optical merits of these LOIE-manipulated NCs, a corresponding color conversion luminescence device provided a high external quantum efficiency (10.5%) and extremely high brightness (970 000 cd/m2). This study provides a valid route toward highly stable, extremely emissive, and panchromatic perovskite NCs with potential use in a variety of future optoelectronic applications.

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.

High-Efficiency Red and Near-Infrared Organic Light-Emitting Diodes Enabled by Pure Organic Fluorescent Emitters and an Exciplex-Forming Cohost.

Three D-A-D-configured molecules DTPBT, DTPNT, and DTPNBT with high quantum yield of orange red (628 nm), red (659 nm), and deep-red/NIR (710 nm) fluorescence, respectively, were developed as emitting dopants in an exciplex-forming cohost (TCTA:3P-T2T) for high-efficiency fluorescence-based organic light-emitting diodes (OLEDs). The obtained physical properties together with theoretical calculations analyzed from these new molecules establish a clear structure-property relationship, in which the feature of central acceptor 2,1,3-benzothiadiazole (BT), naphtho[1,2-c:5,6-c']bis[1,2,5]thiadiazole (NT), and 2,1,3-naphthothiadiazole (NBT) plays the crucial role for governing the physical characteristics. The optimized device configured as ITO/HAT-CN/TAPC/TCTA/TCTA:3P-T2T:5% emitter/3P-T2T/LiF/Al gave a record-high efficiency of orange red (591 nm, 15%), red (647 nm, 10%), and deep-red/NIR (689 nm, 9%) electroluminescent devices. The effective harvest of triplet excitons with an exciplex-forming system in conjunction with efficient energy transfer between the exciplex and the dopant is beneficial for such high device efficiencies. More importantly, the stable exciplex-forming cohost and fast radiative decay rate of DTPNT render this particular device exhibiting high device stability as indicated by the low efficiency roll-off under high current densities (EQE (external quantum efficiency) values of 8.1% at 1000 cd m-2 and 6.8% at 10,000 cd m-2). These results reveal the potential of employing an exciplex-forming system as cohost for fluorescent dopants to furnish high-efficiency OLEDs with an emission wavelength extending to the red or even the NIR range.

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.

Two Novel Small Molecule Donors and the Applications in Bulk-Heterojunction Solar Cells.

Two novel small molecules DTRDTQX and DTIDTQX, based on ditolylaminothienyl group as donor moiety and quinoxaline as middle acceptor moiety with different terminal acceptor groups were synthesized and characterized in this work. In order to study the photovoltaic properties of DTRDTQX and DTIDTQX, bulk-heterojunction solar cells with the configuration of FTO/c-TiO2/DTRDTQX(or DTIDTQX):C70/MoO3/Ag were fabricated, in which DTRDTQX and DTIDTQX acted as the donors and neat C70 as the acceptor. When the weight ratio of DTRDTQX:C70 reached 1:2 and the active layer was annealed at 100°C, the optimal device was realized with the power conversion efficiency (PCE) of 1.44%. As to DTIDTQX:C70-based devices, the highest PCE of 1.70% was achieved with the optimal blend ratio (DTIDTQX:C70 = 1:2) and 100°C thermal annealing treatment. All the experimental data indicated that DTRDTQX and DTIDTQX could be employed as potential donor candidates for organic solar cell applications.